WorldWideScience

Sample records for broadband time-resolved spectroscopy

  1. 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.)

  2. Time-resolved ESR spectroscopy

    International Nuclear Information System (INIS)

    Beckert, D.

    1986-06-01

    The time-resolved ESR spectroscopy is one of the modern methods in radiospectroscopy and plays an important role in solving various problems in chemistry and biology. Proceeding from the basic ideas of time-resolved ESR spectroscopy the experimental equipment is described generally including the equipment developed at the Central Institute of Isotope and Radiation Research. The experimental methods applied to the investigation of effects of chemically induced magnetic polarization of electrons and to kinetic studies of free radicals in polymer systems are presented. The theory of radical pair mechanism is discussed and theoretical expressions are summarized in a computer code to compute the theoretical polarization for each pair of the radicals

  3. Time-resolved vibrational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Tokmakoff, Andrei [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Champion, Paul [Northeastern Univ., Boston, MA (United States); Heilweil, Edwin J. [National Inst. of Standards and Technology (NIST), Boulder, CO (United States); Nelson, Keith A. [Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Ziegler, Larry [Boston Univ., MA (United States)

    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 fiveof 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.

  4. Time-resolved fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Gustavsson, Thomas; Mialocq, Jean-Claude

    2007-01-01

    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)

  5. Time-resolved spectroscopy in synchrotron radiation

    International Nuclear Information System (INIS)

    Rehn, V.; Stanford Univ., CA

    1980-01-01

    Synchrotron radiation (SR) from large-diameter storage rings has intrinsic time structure which facilitates time-resolved measurements form milliseconds to picoseconds and possibly below. The scientific importance of time-resolved measurements is steadily increasing as more and better techniques are discovered and applied to a wider variety of scientific problems. This paper presents a discussion of the importance of various parameters of the SR facility in providing for time-resolved spectroscopy experiments, including the role of beam-line optical design parameters. Special emphasis is placed on the requirements of extremely fast time-resolved experiments with which the effects of atomic vibrational or relaxation motion may be studied. Before discussing the state-of-the-art timing experiments, we review several types of time-resolved measurements which have now become routine: nanosecond-range fluorescence decay times, time-resolved emission and excitation spectroscopies, and various time-of-flight applications. These techniques all depend on a short SR pulse length and a long interpulse period, such as is provided by a large-diameter ring operating in a single-bunch mode. In most cases, the pulse shape and even the stability of the pulse shape is relatively unimportant as long as the pulse length is smaller than the risetime of the detection apparatus, typically 1 to 2 ns. For time resolution smaller than 1 ns, the requirements on the pulse shape become more stringent. (orig./FKS)

  6. 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...

  7. 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....

  8. 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.

  9. Time resolved spectroscopy of GRB 030501 using INTEGRAL

    DEFF Research Database (Denmark)

    Beckmann, V.; Borkowski, J.; Courvoisier, T.J.L.

    2003-01-01

    The gamma-ray instruments on-board INTEGRAL offer an unique opportunity to perform time resolved analysis on GRBs. The imager IBIS allows accurate positioning of GRBs and broad band spectral analysis, while SPI provides high resolution spectroscopy. GRB 030501 was discovered by the INTEGRAL Burst...... the Ulysses and RHESSI experiments....

  10. Emerging biomedical applications of time-resolved fluorescence spectroscopy

    Science.gov (United States)

    Lakowicz, Joseph R.; Szmacinski, Henryk; Koen, Peter A.

    1994-07-01

    Time-resolved fluorescence spectroscopy is presently regarded as a research tool in biochemistry, biophysics, and chemical physics. Advances in laser technology, the development of long-wavelength probes, and the use of lifetime-based methods are resulting in the rapid migration of time-resolved fluorescence to the clinical chemistry lab, to the patient's bedside, to flow cytometers, to the doctor's office, and even to home health care. Additionally, time-resolved imaging is now a reality in fluorescence microscopy, and will provide chemical imaging of a variety of intracellular analytes and/or cellular phenomena. In this overview paper we attempt to describe some of the opportunities available using chemical sensing based on fluorescence lifetimes, and to predict those applications of lifetime-based sensing which are most likely in the near future.

  11. 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 me......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...

  12. 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....

  13. Time-resolved photoelectron spectroscopy of nitrobenzene and its aldehydes

    Science.gov (United States)

    Schalk, Oliver; Townsend, Dave; Wolf, Thomas J. A.; Holland, David M. P.; Boguslavskiy, Andrey E.; Szöri, Milan; Stolow, Albert

    2018-01-01

    We report the first femtosecond time-resolved photoelectron spectroscopy study of 2-, 3- and 4-nitrobenzaldehyde (NBA) and nitrobenzene (NBE) in the gas phase upon excitation at 200 nm. In 3- and 4-NBA, the dynamics follow fast intersystem crossing within 1-2 picoseconds. In 2-NBA and NBE, the dynamics are faster (∼ 0.5 ps). 2-NBA undergoes hydrogen transfer similar to solution phase dynamics. NBE either releases NO2 in the excited state or converts internally back to the ground state. We discuss why these channels are suppressed in the other nitrobenzaldehydes.

  14. Time-resolved spectroscopy defines perturbation in molecules

    International Nuclear Information System (INIS)

    Ahmed, K.

    1998-01-01

    Time-resolved LIF spectroscopy is employed in order to investigate perturbations in different excited electronic state of alkali molecules. Dunham Coefficients are used to search the selected excited ro-vibrational level, which is overlap with the other nearby excited states. Lifetime measurement has been performed of more than 50 ro-vibrational levels. Out of these 25 levels were observed drastically different lifetimes from the other unperturbed levels. In this report, influence of different perturbations on this anomalous behavior is investigated and discussed. (author)

  15. Examining Electron-Boson Coupling Using Time-Resolved Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sentef, Michael; Kemper, Alexander F.; Moritz, Brian; Freericks, James K.; Shen, Zhi-Xun; Devereaux, Thomas P.

    2013-12-26

    Nonequilibrium pump-probe time-domain spectroscopies can become an important tool to disentangle degrees of freedom whose coupling leads to broad structures in the frequency domain. Here, using the time-resolved solution of a model photoexcited electron-phonon system, we show that the relaxational dynamics are directly governed by the equilibrium self-energy so that the phonon frequency sets a window for “slow” versus “fast” recovery. The overall temporal structure of this relaxation spectroscopy allows for a reliable and quantitative extraction of the electron-phonon coupling strength without requiring an effective temperature model or making strong assumptions about the underlying bare electronic band dispersion.

  16. Introduction to Time-Resolved Spectroscopy: Nanosecond Transient Absorption and Time-Resolved Fluorescence of Eosin B

    Science.gov (United States)

    Farr, Erik P.; Quintana, Jason C.; Reynoso, Vanessa; Ruberry, Josiah D.; Shin, Wook R.; Swartz, Kevin R.

    2018-01-01

    Here we present a new undergraduate laboratory that will introduce the concepts of time-resolved spectroscopy and provide insight into the natural time scales on which chemical dynamics occur through direct measurement. A quantitative treatment of the acquired data will provide a deeper understanding of the role of quantum mechanics and various…

  17. Ultrafast time-resolved spectroscopy of xanthophylls at low temperature.

    Science.gov (United States)

    Cong, Hong; Niedzwiedzki, Dariusz M; Gibson, George N; Frank, Harry A

    2008-03-20

    Many of the spectroscopic features and photophysical properties of xanthophylls and their role in energy transfer to chlorophyll can be accounted for on the basis of a three-state model. The characteristically strong visible absorption of xanthophylls is associated with a transition from the ground state S0 (1(1)Ag-) to the S2 (1(1)Bu+) excited state. The lowest lying singlet state denoted S1 (2(1)Ag-), is a state into which absorption from the ground state is symmetry forbidden. Ultrafast optical spectroscopic studies and quantum computations have suggested the presence of additional excited singlet states in the vicinity of S1 (2(1)Ag-) and S2 (1(1)Bu+). One of these is denoted S* and has been suggested in previous work to be associated with a twisted molecular conformation of the molecule in the S1 (2(1)Ag-) state. In this work, we present the results of a spectroscopic investigation of three major xanthophylls from higher plants: violaxanthin, lutein, and zeaxanthin. These molecules have systematically increasing extents of pi-electron conjugation from nine to eleven conjugated carbon-carbon double bonds. All-trans isomers of the molecules were purified by high-performance liquid chromatography (HPLC) and studied by steady-state and ultrafast time-resolved optical spectroscopy at 77 K. Analysis of the data using global fitting techniques has revealed the inherent spectral properties and ultrafast dynamics of the excited singlet states of each of the molecules. Five different global fitting models were tested, and it was found that the data are best explained using a kinetic model whereby photoexcitation results in the promotion of the molecule into the S2 (1(1)Bu+) state that subsequently undergoes decay to a vibrationally hot S1 (1(1)Ag-) state and with the exception of violaxanthin also to the S* state. The vibrationally hot S1 (1(1)Ag-) state then cools to a vibrationally relaxed S1 (2(1)Ag-) state in less than a picosecond. It was also found that a portion

  18. 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.

  19. Femtosecond time-resolved transient absorption spectroscopy of xanthophylls.

    Science.gov (United States)

    Niedzwiedzki, Dariusz M; Sullivan, James O; Polívka, Tomás; Birge, Robert R; Frank, Harry A

    2006-11-16

    Xanthophylls are a major class of photosynthetic pigments that participate in an adaptation mechanism by which higher plants protect themselves from high light stress. In the present work, an ultrafast time-resolved spectroscopic investigation of all the major xanthophyll pigments from spinach has been performed. The molecules are zeaxanthin, lutein, violaxanthin, and neoxanthin. beta-Carotene was also studied. The experimental data reveal the inherent spectral properties and ultrafast dynamics including the S(1) state lifetimes of each of the pigments. In conjunction with quantum mechanical computations the results address the molecular features of xanthophylls that control the formation and decay of the S* state in solution. The findings provide compelling evidence that S* is an excited state with a conformational geometry twisted relative to the ground state. The data indicate that S* is formed via a branched pathway from higher excited singlet states and that its yield depends critically on the presence of beta-ionylidene rings in the polyene system of pi-electron conjugated double bonds. The data are expected to be beneficial to researchers employing ultrafast time-resolved spectroscopic methods to investigate the mechanisms of both energy transfer and nonphotochemical quenching in higher plant preparations.

  20. Plasma polarization spectroscopy. Time resolved spectroscopy in soft x-ray region on recombining plasma

    International Nuclear Information System (INIS)

    Iwamae, Atsushi; Hasuo, Masahiro; Atake, Makoto; Hasegawa, Noboru; Kawachi, Tetsuya

    2007-01-01

    We present an experimental study of polarization of emission radiations from recombining plasmas generated by the interaction of 60 fs ultra-short laser pulses with a gas jet. Time-resolved spectroscopy with a temporal resolution of 5 ps with repetitive accumulation is used to follow the recombination time histories. (author)

  1. Determination of quenching coefficients by time resolved emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Gans, T.; Schulz-von der Gathen, V.; Doebele, H.F. [Essen Univ. (Gesamthochschule) (Germany). Inst. fuer Laser- und Plasmaphysik

    2001-07-01

    Capacitively coupled RF discharges (CCRF discharges) at 13.56 MHz in hydrogen exhibit a field reversal phase of about 10 ns during which an intense electron current provides collisional excitation, within the sheath region. After this strongly dominant short pulsed electron impact excitation, it is possible to determine quenching coefficients from the lifetime of the fluorescence at various pressures by time resolved OES even for high energy levels and without any restrictions of optical selection rules. This novel technique allows the measurement of quenching coefficients for atomic and molecular emission lines of hydrogen itself, as well as for emission lines of small admixtures (e.g. noble gases) to the hydrogen discharge, since with a fast gate-able ICCD camera operating at 13.56 MHz it is possible to measure even faint emission lines temporally resolved.

  2. Determination of quenching coefficients by time resolved emission spectroscopy

    International Nuclear Information System (INIS)

    Gans, T.; Schulz-von der Gathen, V.; Doebele, H.F.

    2001-01-01

    Capacitively coupled RF discharges (CCRF discharges) at 13.56 MHz in hydrogen exhibit a field reversal phase of about 10 ns during which an intense electron current provides collisional excitation, within the sheath region. After this strongly dominant short pulsed electron impact excitation, it is possible to determine quenching coefficients from the lifetime of the fluorescence at various pressures by time resolved OES even for high energy levels and without any restrictions of optical selection rules. This novel technique allows the measurement of quenching coefficients for atomic and molecular emission lines of hydrogen itself, as well as for emission lines of small admixtures (e.g. noble gases) to the hydrogen discharge, since with a fast gate-able ICCD camera operating at 13.56 MHz it is possible to measure even faint emission lines temporally resolved

  3. Femtosecond time-resolved transient absorption spectroscopy of xanthophylls

    Czech Academy of Sciences Publication Activity Database

    Niedzwiedzki, D.; Sullivan, J.O.; Polívka, Tomáš; Birge, R.R.; Frank, H.A.

    2006-01-01

    Roč. 110, č. 45 (2006), s. 22872-22885 ISSN 1520-6106 Institutional research plan: CEZ:AV0Z50510513 Keywords : xanthophyll * spectroscopy study Subject RIV: BO - Biophysics Impact factor: 4.115, year: 2006

  4. Application of microfluidic devices for time resolved FTIR spectroscopy

    International Nuclear Information System (INIS)

    Wagner, C.

    2012-01-01

    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 μm 2 ) 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

  5. 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.......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....

  6. Time-resolved photoelectron spectroscopy using synchrotron radiation time structure

    International Nuclear Information System (INIS)

    Bergeard, N.; Silly, M.G.; Chauvet, C.; Guzzo, M.; Ricaud, J.P.; Izquierdo, M.; Sirotti, F.; Krizmancic, D.; Guzzo, M.; Stebel, L.; Pittana, P.; Sergo, R.; Cautero, G.; Dufour, G.; Rochet, F.

    2011-01-01

    Synchrotron radiation time structure is becoming a common tool for studying dynamic properties of materials. The main limitation is often the wide time domain the user would like to access with pump-probe experiments. In order to perform photoelectron spectroscopy experiments over time scales from milliseconds to picoseconds it is mandatory to measure the time at which each measured photoelectron was created. For this reason the usual CCD camera based two-dimensional detection of electron energy analyzers has been replaced by a new delay-line detector adapted to the time structure of the SOLEIL synchrotron radiation source. The new two-dimensional delay-line detector has a time resolution of 5 ns and was installed on a Scienta SES 2002 electron energy analyzer. The first application has been to characterize the time of flight of the photo emitted electrons as a function of their kinetic energy and the selected pass energy. By repeating the experiment as a function of the available pass energy and of the kinetic energy, a complete characterization of the analyzer behaviour in the time domain has been obtained. Even for kinetic energies as low as 10 eV at 2 eV pass energy, the time spread of the detected electrons is lower than 140 ns. These results and the time structure of the SOLEIL filling modes assure the possibility of performing pump-probe photoelectron spectroscopy experiments with the time resolution given by the SOLEIL pulse width, the best performance of the beamline and of the experimental station. (authors)

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

    International Nuclear Information System (INIS)

    CARR, G.L.; LAVEIGNE, J.D.; LOBO, R.P.S.M.; REITZE, D.H.; TANNER, D.B.

    1999-01-01

    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

  8. Time-resolved VUV spectroscopy in the EXTRAP-T2 reversed field pinch

    International Nuclear Information System (INIS)

    Hedqvist, A.; Rachlew-Kaellne, E.

    1998-01-01

    Time-resolved VUV spectroscopy has been used to investigate the effects of impurities in a reversed field pinch operating with a resistive shell. Results of electron temperature, impurity ion densities, particle confinement time and Z eff together with a description of the interpretation and the equipment are presented. (author)

  9. Time-resolved VUV spectroscopy in the EXTRAP-T2 reversed field pinch

    Science.gov (United States)

    Hedqvist, Anders; Rachlew-Källne, Elisabeth

    1998-09-01

    Time-resolved VUV spectroscopy has been used to investigate the effects of impurities in a reversed field pinch operating with a resistive shell. Results of electron temperature, impurity ion densities, particle confinement time and 0741-3335/40/9/004/img1 together with a description of the interpretation and the equipment are presented.

  10. 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 T...

  11. 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...

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

    International Nuclear Information System (INIS)

    Kimura, Takaumi; Kato, Yoshiharu; Meinrath, G.; Yoshida, Zenko; Choppin, G.R.

    1995-01-01

    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)

  13. Time resolved optical emission spectroscopy of cross-beam pulsed laser ablation on graphite targets

    International Nuclear Information System (INIS)

    Sangines, R.; Sanchez Ake, C.; Sobral, H.; Villagran-Muniz, M.

    2007-01-01

    Cross-beam pulsed laser ablation with two delayed lasers is performed on two perpendicular graphite targets. The time delay between lasers is varied by up to 5 μs, and physical changes on the second plasma, due to the interaction with the first generated one, are determined by time resolved optical emission spectroscopy

  14. Laser induced breakdown spectroscopy of the uranium including calcium. Time resolved measurement spectroscopic analysis (Contract research)

    International Nuclear Information System (INIS)

    Akaoka, Katsuaki; Maruyama, Youichiro; Oba, Masaki; Miyabe, Masabumi; Otobe, Haruyoshi; Wakaida, Ikuo

    2010-05-01

    For the remote analysis of low DF TRU (Decontamination Factor Transuranic) fuel, Laser Breakdown Spectroscopy (LIBS) was applied to uranium oxide including a small amount of calcium oxide. The characteristics, such as spectrum intensity and plasma excitation temperature, were measured using time-resolved spectroscopy. As a result, in order to obtain the stable intensity of calcium spectrum for the uranium spectrum, it was found out that the optimum observation delay time of spectrum is 4 microseconds or more after laser irradiation. (author)

  15. 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

  16. 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)

    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 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)

  17. Time-resolved resonance fluorescence spectroscopy for study of chemical reactions in laser-induced plasmas.

    Science.gov (United States)

    Liu, Lei; Deng, Leimin; Fan, Lisha; Huang, Xi; Lu, Yao; Shen, Xiaokang; Jiang, Lan; Silvain, Jean-François; Lu, Yongfeng

    2017-10-30

    Identification of chemical intermediates and study of chemical reaction pathways and mechanisms in laser-induced plasmas are important for laser-ablated applications. Laser-induced breakdown spectroscopy (LIBS), as a promising spectroscopic technique, is efficient for elemental analyses but can only provide limited information about chemical products in laser-induced plasmas. In this work, time-resolved resonance fluorescence spectroscopy was studied as a promising tool for the study of chemical reactions in laser-induced plasmas. Resonance fluorescence excitation of diatomic aluminum monoxide (AlO) and triatomic dialuminum monoxide (Al 2 O) was used to identify these chemical intermediates. Time-resolved fluorescence spectra of AlO and Al 2 O were used to observe the temporal evolution in laser-induced Al plasmas and to study their formation in the Al-O 2 chemistry in air.

  18. Space- and time-resolved raman and breakdown spectroscopy: advanced lidar techniques

    Science.gov (United States)

    Silviu, Gurlui; Marius Mihai, Cazacu; Adrian, Timofte; Oana, Rusu; Georgiana, Bulai; Dimitriu, Dan

    2018-04-01

    DARLIOES - the advanced LIDAR is based on space- and time-resolved RAMAN and breakdown spectroscopy, to investigate chemical and toxic compounds, their kinetics and physical properties at high temporal (2 ns) and spatial (1 cm) resolution. The high spatial and temporal resolution are needed to resolve a large variety of chemical troposphere compounds, emissions from aircraft, the self-organization space charges induced light phenomena, temperature and humidity profiles, ice nucleation, etc.

  19. 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

  20. Ionic classification of Xe laser lines: A new approach through time resolved spectroscopy

    International Nuclear Information System (INIS)

    Schinca, D.; Duchowicz, R.; Gallardo, M.

    1992-01-01

    Visible and UV laser emission from a highly ionized pulsed Xe plasma was studied in relation to the ionic assignment of the laser lines. Time-resolved spectroscopy was used to determine the ionic origin of the studied lines. The results are in agreement with an intensity versus pressure analysis performed over the same wavelength range. From the temporal behaviour of the spontaneous emission, a probable classification can be obtained. (author). 7 refs, 7 figs, 1 tab

  1. 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 laser s * plasma diagnostics * absorption spectroscopy * time resolved Subject RIV: BL - Plasma and Gas Discharge Physics Impact factor: 3.179, year: 2013

  2. Time-resolved single-shot terahertz time-domain spectroscopy for ultrafast irreversible processes

    Science.gov (United States)

    Zhai, Zhao-Hui; Zhong, Sen-Cheng; Li, Jun; Zhu, Li-Guo; Meng, Kun; Li, Jiang; Liu, Qiao; Peng, Qi-Xian; Li, Ze-Ren; Zhao, Jian-Heng

    2016-09-01

    Pulsed terahertz spectroscopy is suitable for spectroscopic diagnostics of ultrafast events. However, the study of irreversible or single shot ultrafast events requires ability to record transient properties at multiple time delays, i.e., time resolved at single shot level, which is not available currently. Here by angular multiplexing use of femtosecond laser pulses, we developed and demonstrated a time resolved, transient terahertz time domain spectroscopy technique, where burst mode THz pulses were generated and then detected in a single shot measurement manner. The burst mode THz pulses contain 2 sub-THz pulses, and the time gap between them is adjustable up to 1 ns with picosecond accuracy, thus it can be used to probe the single shot event at two different time delays. The system can detect the sub-THz pulses at 0.1 THz-2.5 THz range with signal to noise ratio (SNR) of ˜400 and spectrum resolution of 0.05 THz. System design was described here, and optimizations of single shot measurement of THz pulses were discussed in detail. Methods to improve SNR were also discussed in detail. A system application was demonstrated where pulsed THz signals at different time delays of the ultrafast process were successfully acquired within single shot measurement. This time resolved transient terahertz time domain spectroscopy technique provides a new diagnostic tool for irreversible or single shot ultrafast events where dynamic information can be extracted at terahertz range within one-shot experiment.

  3. 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.

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

    International Nuclear Information System (INIS)

    Boschini, F.; Hedayat, H.; Piovera, C.; Dallera, C.; Gupta, A.; Carpene, E.

    2015-01-01

    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 2 single crystals as a benchmark

  5. Photophysical characterization and time-resolved spectroscopy of a anthradithiophene dimer: exploring the role of conformation in singlet fission

    KAUST Repository

    Dean, Jacob C.; Zhang, Ruomeng; Hallani, Rawad K.; Pensack, Ryan D.; Sanders, Samuel N.; Oblinsky, Daniel G.; Parkin, Sean R.; Campos, Luis M.; Anthony, John E.; Scholes, Gregory D.

    2017-01-01

    carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance

  6. Time-resolved x-ray laser induced photoelectron spectroscopy of isochoric heated copper

    International Nuclear Information System (INIS)

    Nelson, A.J.; Dunn, J.; Hunter, J.; Widmann, K.

    2005-01-01

    Time-resolved x-ray photoelectron spectroscopy is used to probe the nonsteady-state evolution of the valence band electronic structure of laser heated ultrathin (50 nm) copper. A metastable phase is studied using a 527 nm wavelength 400 fs laser pulse containing 0.1-2.5 mJ laser energy focused in a large 500x700 μm 2 spot to create heated conditions of 0.07-1.8x10 12 W cm -2 intensity. Valence band photoemission spectra are presented showing the changing occupancy of the Cu 3d level with heating are presented. These picosecond x-ray laser induced time-resolved photoemission spectra of laser-heated ultrathin Cu foil show dynamic changes in the electronic structure. The ultrafast nature of this technique lends itself to true single-state measurements of shocked and heated materials

  7. Time-resolved spectroscopy using a chopper wheel as a fast shutter

    International Nuclear Information System (INIS)

    Wang, Shicong; Wendt, Amy E.; Boffard, John B.; Lin, Chun C.

    2015-01-01

    Widely available, small form-factor, fiber-coupled spectrometers typically have a minimum exposure time measured in milliseconds, and thus cannot be used directly for time-resolved measurements at the microsecond level. Spectroscopy at these faster time scales is typically done with an intensified charge coupled device (CCD) system where the image intensifier acts as a “fast” electronic shutter for the slower CCD array. In this paper, we describe simple modifications to a commercially available chopper wheel system to allow it to be used as a “fast” mechanical shutter for gating a fiber-coupled spectrometer to achieve microsecond-scale time-resolved optical measurements of a periodically pulsed light source. With the chopper wheel synchronized to the pulsing of the light source, the time resolution can be set to a small fraction of the pulse period by using a chopper wheel with narrow slots separated by wide spokes. Different methods of synchronizing the chopper wheel and pulsing of the light sources are explored. The capability of the chopper wheel system is illustrated with time-resolved measurements of pulsed plasmas

  8. 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.)

  9. Photolytic interruptions of the bacteriorhodopsin photocycle examined by time-resolved resonance raman spectroscopy.

    Science.gov (United States)

    Grieger, I; Atkinson, G H

    1985-09-24

    An investigation of the photolytic conditions used to initiate and spectroscopically monitor the bacteriorhodopsin (BR) photocycle utilizing time-resolved resonance Raman (TR3) spectroscopy has revealed and characterized two photoinduced reactions that interrupt the thermal pathway. One reaction involves the photolytic interconversion of M-412 and M', and the other involves the direct photolytic conversion of the BR-570/K-590 photostationary mixture either to M-412 and M' or to M-like intermediates within 10 ns. The photolytic threshold conditions describing both reactions have been quantitatively measured and are discussed in terms of experimental parameters.

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

    International Nuclear Information System (INIS)

    Huang, C.Y.; Malvezzi, A.M.; Bloembergen, N.; Kurz, H.

    1985-01-01

    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

  11. 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...... photoconductivity compared to P3HT alone, consistent with efficient charge transfer. The photoconductivity dynamics show fast, picosecond trapping or recombination in the hybrid blend while the all-organic film shows no such loss of mobile charge over ns time scales. The ac conductivity for all samples is well...

  12. Time-resolved luminescent spectroscopy of YAG:Ce single crystal and single crystalline films

    International Nuclear Information System (INIS)

    Zorenko, Yu.; Gorbenko, V.; Savchyn, V.; Vozniak, T.; Puzikov, V.; Danko, A.; Nizhankovski, S.

    2010-01-01

    The peculiarities of the luminescence and energy transfer from YAG host to the emission centers formed by the Y Al antisite defects and Ce 3+ ions have been studied in YAG:Ce single crystals, grown from the melt by modified Bridgman method in Ar and CO 2 + H 2 atmospheres, and YAG:Ce single crystalline film, grown by liquid phase epitaxy method, using the comparative time-resolved luminescent spectroscopy under excitation by synchrotron radiation in the range of fundamental adsorption of this garnet.

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

    International Nuclear Information System (INIS)

    Bergstroem, H.

    1991-10-01

    Radiative lifetimes have been studied in neutral boron, carbon, silicon and strontium, in singly ionized gadolinium and tantalum and in molecular carbon monoxide and C 2 . 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)

  14. Time-resolved X-ray photoelectron spectroscopy techniques for the study of interfacial charge dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Neppl, Stefan, E-mail: sneppl@lbl.gov; Gessner, Oliver

    2015-04-15

    Highlights: • Ultrafast interfacial charge transfer is probed with atomic site specificity. • Femtosecond X-ray photoelectron spectroscopy using a free electron laser. • Efficient and flexible picosecond X-ray photoelectron pump–probe scheme using synchrotron radiation. - Abstract: X-ray photoelectron spectroscopy (XPS) is one of the most powerful techniques to quantitatively analyze the chemical composition and electronic structure of surfaces and interfaces in a non-destructive fashion. Extending this technique into the time domain has the exciting potential to shed new light on electronic and chemical dynamics at surfaces by revealing transient charge configurations with element- and site-specificity. Here, we describe prospects and challenges that are associated with the implementation of picosecond and femtosecond time-resolved X-ray photoelectron spectroscopy at third-generation synchrotrons and X-ray free-electron lasers, respectively. In particular, we discuss a series of laser-pump/X-ray-probe photoemission experiments performed on semiconductor surfaces, molecule-semiconductor interfaces, and films of semiconductor nanoparticles that demonstrate the high sensitivity of time-resolved XPS to light-induced charge carrier generation, diffusion and recombination within the space charge layers of these materials. Employing the showcase example of photo-induced electronic dynamics in a dye-sensitized semiconductor system, we highlight the unique possibility to probe heterogeneous charge transfer dynamics from both sides of an interface, i.e., from the perspective of the molecular electron donor and the semiconductor acceptor, simultaneously. Such capabilities will be crucial to improve our microscopic understanding of interfacial charge redistribution and associated chemical dynamics, which are at the heart of emerging energy conversion, solar fuel generation, and energy storage technologies.

  15. 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. © 2012 American Institute of Physics

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

    Energy Technology Data Exchange (ETDEWEB)

    Baudelet, Matthieu; Boueri, Myriam [Laboratoire de Spectrometrie Ionique et Moleculaire, Universite Claude Bernard Lyon 1, UMR CNRS 5579, 43, Bd. du 11 Novembre 1918, F-69622 Villeurbanne Cedex (France); Yu Jin [Laboratoire de Spectrometrie Ionique et Moleculaire, Universite Claude Bernard Lyon 1, UMR CNRS 5579, 43, Bd. du 11 Novembre 1918, F-69622 Villeurbanne Cedex (France)], E-mail: jin.yu@lasim.univ-lyon1.fr; Mao, Samuel S; Piscitelli, Vincent; Xianglei, Mao; Russo, Richard E [Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2007-12-15

    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.

  17. Femtosecond Broadband Stimulated Raman Spectroscopy

    International Nuclear Information System (INIS)

    Lee, Soo-Y; Yoon, Sagwoon; Mathies, Richard A

    2006-01-01

    Femtosecond broadband stimulated Raman spectroscopy (FSRS) is a new technique where a narrow bandwidth picosecond Raman pump pulse and a red-shifted broadband femtosecond Stokes probe pulse (with or without time delay between the pulses) act on a sample to produce a high resolution Raman gain spectrum with high efficiency and speed, free from fluorescence background interference. It can reveal vibrational structural information and dynamics of stationary or transient states. Here, the quantum picture for femtosecond broadband stimulated Raman spectroscopy (FSRS) is used to develop the semiclassical coupled wave theory of the phenomenon and to derive an expression for the measurable Raman gain in FSRS. The semiclassical theory is applied to study the dependence of lineshapes in FSRS on the pump-probe time delay and to deduce vibrational dephasing times in cyclohexane in the ground state

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

    International Nuclear Information System (INIS)

    Dicke, Benjamin

    2013-01-01

    Gallium(tris-8-hydroxyquinoline) (Gaq 3 ) 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) (Alq 3 ). Knowledge of the first excited state S 1 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 S 1 of Gaq 3 dissolved in benzyl alcohol was analyzed. A structural model for the excited state structure of the Gaq 3 molecule based on the several times reproduced results of the XAFS experiments is proposed. According to this model it was found that the Ga-N A bond length is elongated, while the Ga-O A bond length is shortened upon photoexcitation. The dynamics of the structural changes were not the focus of this thesis. Nevertheless the excited state lifetime

  19. The application of time-resolved luminescence spectroscopy to a remote uranyl sensor

    International Nuclear Information System (INIS)

    Varineau, P.T.; Duesing, R.; Wangen, L.E.

    1991-01-01

    Time resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote sensing device using fiber optic cables coupled with a micro flow cell in order to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO 2 2+ can diffuse in to a reaction/analysis chamber which holds phosphoric acid, a reagent which enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10 4 to 10 -9 M. 17 refs., 5 figs

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

    International Nuclear Information System (INIS)

    Ressler, T.; Jentoft, R.E.; Wienold, J.; Girgsdies, F.; Neisius, T.; Timpe, O.

    2003-01-01

    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 MoO 3 in propene and in propene and oxygen

  1. Femtosecond time-resolved impulsive stimulated Raman spectroscopy using sub-7-fs pulses: Apparatus and applications

    Energy Technology Data Exchange (ETDEWEB)

    Kuramochi, Hikaru [Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198 (Japan); Takeuchi, Satoshi; Tahara, Tahei, E-mail: tahei@riken.jp [Molecular Spectroscopy Laboratory, RIKEN, 2-1 Hirosawa, Wako 351-0198 (Japan); Ultrafast Spectroscopy Research Team, RIKEN Center for Advanced Photonics (RAP), 2-1 Hirosawa, Wako 351-0198 (Japan)

    2016-04-15

    We describe details of the setup for time-resolved impulsive stimulated Raman spectroscopy (TR-ISRS). In this method, snapshot molecular vibrational spectra of the photoreaction transients are captured via time-domain Raman probing using ultrashort pulses. Our instrument features transform-limited sub-7-fs pulses to impulsively excite and probe coherent nuclear wavepacket motions, allowing us to observe vibrational fingerprints of transient species from the terahertz to 3000-cm{sup −1} region with high sensitivity. Key optical components for the best spectroscopic performance are discussed. The TR-ISRS measurements for the excited states of diphenylacetylene in cyclohexane are demonstrated, highlighting the capability of our setup to track femtosecond dynamics of all the Raman-active fundamental molecular vibrations.

  2. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    Science.gov (United States)

    Elkins, Madeline H.; Williams, Holly L.; Neumark, Daniel M.

    2016-05-01

    The excited state relaxation dynamics of the solvated electron in H2O and D2O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H2O and 102 ± 8 fs in D2O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

  3. Exploring the Dynamics of Superconductors by Time-Resolved Far-Infrared Spectroscopy

    International Nuclear Information System (INIS)

    Carr, G. L.; Lobo, R. P. S. M.; LaVeigne, J.; Reitze, D. H.; Tanner, D. B.

    2000-01-01

    We have examined the recombination of excess quasiparticles in superconducting Pb by time-resolved far-infrared spectroscopy using a pulsed synchrotron source. The energy gap shift calculated by Owen and Scalapino [Phys. Rev. Lett. 28, 1559 (1972)] is directly observed, as is the associated reduction in the Cooper pair density. The relaxation process involves a two-component decay; the faster (∼200 ps) is associated with the actual (effective) recombination process, while the slower (∼10 to 100ns) is due to heat transport across the film/substrate interface. The temperature dependence of the recombination process between 0.5T c and 0.85T c is in good agreement with theory

  4. 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

  5. Development of in situ time-resolved Raman spectroscopy facility for dynamic shock loading in materials

    Science.gov (United States)

    Chaurasia, S.; Rastogi, V.; Rao, U.; Sijoy, C. D.; Mishra, V.; Deo, M. N.

    2017-11-01

    The transient state of excitation and relaxation processes in materials under shock compression can be investigated by coupling the laser driven shock facility with Raman spectroscopy. For this purpose, a time resolved Raman spectroscopy setup has been developed to monitor the physical and the chemical changes such as phase transitions, chemical reactions, molecular kinetics etc., under shock compression with nanosecond time resolution. This system consist of mainly three parts, a 2 J/8 ns Nd:YAG laser system used for generation of pump and probe beams, a Raman spectrometer with temporal and spectral resolution of 1.2 ns and 3 cm-1 respectively and a target holder in confinement geometry assembly. Detailed simulation for the optimization of confinement geometry targets is performed. Time resolved measurement of polytetrafluoroethylene (PTFE) targets at focused laser intensity of 2.2 GW/cm2 has been done. The corresponding pressure in the Aluminum and PTFE are 3.6 and 1.7 GPa respectively. At 1.7 GPa in PTFE, a red shift of 5 cm-1 is observed for the CF2 twisting mode (291 cm-1). Shock velocity in PTFE is calculated by measuring rate of change of ratios of the intensity of Raman lines scattered from shocked volume to total volume of sample in the laser focal spot along the laser axis. The calculated shock velocity in PTFE is found to be 1.64 ± 0.16 km/s at shock pressure of 1.7 GPa, for present experimental conditions.

  6. 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.

  7. 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.

  8. Dual time-resolved temperature-jump fluorescence and infrared spectroscopy for the study of fast protein dynamics.

    Science.gov (United States)

    Davis, Caitlin M; Reddish, Michael J; Dyer, R Brian

    2017-05-05

    Time-resolved temperature-jump (T-jump) coupled with fluorescence and infrared (IR) spectroscopy is a powerful technique for monitoring protein dynamics. Although IR spectroscopy of the polypeptide amide I mode is more technically challenging, it offers complementary information because it directly probes changes in the protein backbone, whereas, fluorescence spectroscopy is sensitive to the environment of specific side chains. With the advent of widely tunable quantum cascade lasers (QCL) it is possible to efficiently probe multiple IR frequencies with high sensitivity and reproducibility. Here we describe a dual time-resolved T-jump fluorescence and IR spectrometer and its application to study protein folding dynamics. A Q-switched Ho:YAG laser provides the T-jump source for both time-resolved IR and fluorescence spectroscopy, which are probed by a QCL and Ti:Sapphire laser, respectively. The Ho:YAG laser simultaneously pumps the time-resolved IR and fluorescence spectrometers. The instrument has high sensitivity, with an IR absorbance detection limit of jump induced difference spectrum from 50ns to 0.5ms. This study demonstrates the power of the dual time-resolved T-jump fluorescence and IR spectroscopy to resolve complex folding mechanisms by complementary IR absorbance and fluorescence measurements of protein dynamics. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Time-resolved spectroscopy of the probe fluorescence in the study of human blood protein dynamic structure on SR beam

    International Nuclear Information System (INIS)

    Dobretsov, G.E.; Kurek, N.K.; Syrejshchikova, T.I.; Yakimenko, M.N.; Clarke, D.T.; Jones, G.R.; Munro, I.H.

    2000-01-01

    Time-resolved spectroscopy on the SRS of the Daresbury Laboratory was used for the study of the human serum lipoproteins and human blood albumins with fluorescent probes K-37 and K-35, developed in Russia. The probe K-37 was found sensitive to the difference in dynamic properties of the lipid objects. Two sets of the parameters were used for the description of lipid dynamic structure: (1) time-resolved fluorescence spectra and (2) time-resolved fluorescence depolarization as a function of rotational mobility of lipid molecules. Each measured dynamic parameter reflected the monotonous changes of dynamic properties in the range: lipid spheres-very low density lipoproteins-low density lipoproteins-high density lipoproteins-phospholipid liposomes. The range is characterized by the increase of the ratio polar/ nonpolar lipids. Thus, time-resolved fluorescence could be used to detect some structural modifications in lipoproteins related to atherosclerosis and subsequent cardiovascular diseases development

  10. Time-resolved spectroscopy of nonequilibrium ionization in laser-produced plasmas

    International Nuclear Information System (INIS)

    Marjoribanks, R.S.

    1988-01-01

    The highly transient ionization characteristic of laser-produced plasmas at high energy densities has been investigated experimentally, using x-ray spectroscopy with time resolution of less than 20 ps. Spectroscopic diagnostics of plasma density and temperature were used, including line ratios, line profile broadening and continuum emission, to characterize the plasma conditions without relying immediately on ionization modeling. The experimentally measured plasma parameters were used as independent variables, driving an ionization code, as a test of ionization modeling, divorced from hydrodynamic calculations. Several state-of-the-art streak spectrographs, each recording a fiducial of the laser peak along with the time-resolved spectrum, characterized the laser heating of thin signature layers of different atomic numbers imbedded in plastic targets. A novel design of crystal spectrograph, with a conically curved crystal, was developed. Coupled with a streak camera, it provided high resolution (λ/ΔΛ > 1000) and a collection efficiency roughly 20-50 times that of planar crystal spectrographs, affording improved spectra for quantitative reduction and greater sensitivity for the diagnosis of weak emitters. Experimental results were compared to hydrocode and ionization code simulations, with poor agreement. The conclusions question the appropriateness of describing electron velocity distributions by a temperature parameter during the time of laser illumination and emphasis the importance of characterizing the distribution more generally

  11. Creation of free excitons in solid krypton investigated by time-resolved luminescence spectroscopy

    International Nuclear Information System (INIS)

    Kisand, Vambola; Kirm, Marco; Negodin, Evgeni; Sombrowski, Elke; Steeg, Barbara; Vielhauer, Sebastian; Zimmerer, Georg

    2003-01-01

    The creation and relaxation of secondary excitons in solid Kr was investigated using energy-and time-resolved luminescence spectroscopy in the vacuum ultraviolet region. The spectrally selected emission of the free exciton (FE) was used as a probe for an investigation of the different exciton creation processes. Delayed FE creation via electron-hole recombination and 'prompt' (in terms of the time-resolution of the experiment) creation of excitons were separated. The 'prompt' creation of a FE appears in the region above threshold energy E th , which is equal to the sum of the band gap energy and the free exciton energy. 'Prompt' creation of excitons above E th is ascribed to a superposition of two processes: (i) creation of the electronic polaron complex (one-step process) and (ii) inelastic scattering of photoelectrons described in the framework of the multiple-parabolic-branch band model (two-step process). In addition, the ratio spectrum of the time-integrated FE and self-trapped exciton (STE) emission was analysed. The behaviour of the ratio spectrum is a proof that electron-hole recombination leads to STE states through FE states as precursors

  12. Time-resolved laser fluorescence spectroscopy of organic ligands by europium: Fluorescence quenching and lifetime properties

    Science.gov (United States)

    Nouhi, A.; Hajjoul, H.; Redon, R.; Gagné, J. P.; Mounier, S.

    2018-03-01

    Time-resolved Laser Fluorescence Spectroscopy (TRLFS) has proved its usefulness in the fields of biophysics, life science and geochemistry to characterize the fluorescence probe molecule with its chemical environment. The purpose of this study is to demonstrate the applicability of this powerful technique combined with Steady-State (S-S) measurements. A multi-mode factor analysis, in particular CP/PARAFAC, was used to analyze the interaction between Europium (Eu) and Humic substances (HSs) extracted from Saint Lawrence Estuary in Canada. The Saint Lawrence system is a semi-enclosed water stream with connections to the Atlantic Ocean and is an excellent natural laboratory. CP/PARAFAC applied to fluorescence S-S data allows introspecting ligands-metal interactions and the one-site 1:1 modeling gives information about the stability constants. From the spectral signatures and decay lifetimes data given by TRLFS, one can deduce the fluorescence quenching which modifies the fluorescence and discuss its mechanisms. Results indicated a relatively strong binding ability between europium and humic substances samples (Log K value varies from 3.38 to 5.08 at pH 7.00). Using the Stern-Volmer plot, it has been concluded that static and dynamic quenching takes places in the case of salicylic acid and europium interaction while for HSs interaction only a static quenching is observed.

  13. Improved Fast, Deep Record Length, Time-Resolved Visible Spectroscopy of Plasmas Using Fiber Grids

    Science.gov (United States)

    Brockington, S.; Case, A.; Cruz, E.; Williams, A.; Witherspoon, F. D.; Horton, R.; Klauser, R.; Hwang, D.

    2017-10-01

    HyperV Technologies is developing a fiber-coupled, deep record-length, low-light camera head for performing high time resolution spectroscopy on visible emission from plasma events. By coupling the output of a spectrometer to an imaging fiber bundle connected to a bank of amplified silicon photomultipliers, time-resolved spectroscopic imagers of 100 to 1,000 pixels can be constructed. A second generation prototype 32-pixel spectroscopic imager employing this technique was constructed and successfully tested at the University of California at Davis Compact Toroid Injection Experiment (CTIX). Pixel performance of 10 Megaframes/sec with record lengths of up to 256,000 frames ( 25.6 milliseconds) were achieved. Pixel resolution was 12 bits. Pixel pitch can be refined by using grids of 100 μm to 1000 μm diameter fibers. Experimental results will be discussed, along with future plans for this diagnostic. Work supported by USDOE SBIR Grant DE-SC0013801.

  14. Studies of the reactions of hydrogen atoms by time-resolved E. S. R. spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fessenden, R W; Verma, N C [Carnegie-Mellon Univ., Pittsburgh, Pa. (USA). Dept. of Chemistry

    1977-01-01

    Time-resolved e.s.r. spectroscopy has been used to follow directly the reactions of H atoms produced by pulse radiolysis of acid solutions. Detailed analysis of the time profile of the e.s.r. signal was carried out by means of modified Bloch equations. The increased signal found when a scavenger for OH such as t-butyl alcohol is present is shown to be mainly the result of slower H atom decay by radical-radical reaction. The reaction H + OH does not appear to produce any signal polarization. The decay curves observed in the presence of solute are readily accounted for by the treatment, and good plots of pseudo first-order rate constant against solute concentration are obtained. The absolute rate constants for reaction with H atoms are for methanol 2.5 x10/sup 6/, for ethanol 2.1 X 10/sup 7/, for isopropanol 6.8 x 10/sup 7/, and for succinic acid 3.0 x 10/sup 6/ dm/sup 3/ mol/sup -1/s/sup -1/. These values are in good agreement with the earlier chemical measurements.

  15. Isotope effect on hydrated electron relaxation dynamics studied with time-resolved liquid jet photoelectron spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Elkins, Madeline H.; Williams, Holly L. [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Neumark, Daniel M., E-mail: dneumark@berkeley.edu [Department of Chemistry, University of California, Berkeley, California 94720 (United States); Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)

    2016-05-14

    The excited state relaxation dynamics of the solvated electron in H{sub 2}O and D{sub 2}O are investigated using time-resolved photoelectron spectroscopy in a liquid microjet. The data show that the initial excited state decays on a time scale of 75 ± 12 fs in H{sub 2}O and 102 ± 8 fs in D{sub 2}O, followed by slower relaxation on time scales of 400 ± 70 fs and 390 ± 70 fs that are isotopically invariant within the precision of our measurements. Based on the time evolution of the transient signals, the faster and slower time constants are assigned to p → s internal conversion (IC) of the hydrated electron and relaxation on the ground electronic state, respectively. This assignment is consistent with the non-adiabatic mechanism for relaxation of the hydrated electron and yields an isotope effect of 1.4 ± 0.2 for IC of the hydrated electron.

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

    International Nuclear Information System (INIS)

    Amir, W.

    2003-12-01

    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 2 O for reasons of experimental and theoretical suitability. However this is not water. Pure water H 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. 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.

  18. Hemodynamic measurements in deep brain tissues of humans by near-infrared time-resolved spectroscopy

    Science.gov (United States)

    Suzuki, Hiroaki; Oda, Motoki; Yamaki, Etsuko; Suzuki, Toshihiko; Yamashita, Daisuke; Yoshimoto, Kenji; Homma, Shu; Yamashita, Yutaka

    2014-03-01

    Using near-infrared time-resolved spectroscopy (TRS), we measured the human head in transmittance mode to obtain the optical properties, tissue oxygenation, and hemodynamics of deep brain tissues in 50 healthy adult volunteers. The right ear canal was irradiated with 3-wavelengths of pulsed light (760, 795, and 835nm), and the photons passing through the human head were collected at the left ear canal. Optical signals with sufficient intensity could be obtained from 46 of the 50 volunteers. By analyzing the temporal profiles based on the photon diffusion theory, we successfully obtained absorption coefficients for each wavelength. The levels of oxygenated hemoglobin (HbO2), deoxygenated hemoglobin (Hb), total hemoglobin (tHb), and tissue oxygen saturation (SO2) were then determined by referring to the hemoglobin spectroscopic data. Compared with the SO2 values for the forehead measurements in reflectance mode, the SO2 values of the transmittance measurements of the human head were approximately 10% lower, and tHb values of the transmittance measurements were always lower than those of the forehead reflectance measurements. Moreover, the level of hemoglobin and the SO2 were strongly correlated between the human head measurements in transmittance mode and the forehead measurements in the reflectance mode, respectively. These results demonstrated a potential application of this TRS system in examining deep brain tissues of humans.

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

    Science.gov (United States)

    Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

    2016-02-09

    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.

  20. Transient photoconductivity in InGaN/GaN multiple quantum wells, measured by time-resolved terahertz spectroscopy

    DEFF Research Database (Denmark)

    Porte, Henrik; Turchinovich, Dmitry; Cooke, David

    2009-01-01

    Terahertz conductivity of InGaN/GaN MQWs was studied by time-resolved terahertz spectroscopy. Restoration of the built-in piezoelectric field leads to a nonexponential carrier density decay. Terahertz conductivity spectrum is described by the Drude-Smith......Terahertz conductivity of InGaN/GaN MQWs was studied by time-resolved terahertz spectroscopy. Restoration of the built-in piezoelectric field leads to a nonexponential carrier density decay. Terahertz conductivity spectrum is described by the Drude-Smith...

  1. 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.

  2. Investigations of suspension stability of iron oxide nanoparticles using time-resolved UV–visible spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Vikram, S.; Vasanthakumari, R. [B. S. Abdur Rahman University, Polymer Nanotechnology Centre (India); Tsuzuki, Takuya [Australian National University, Research School of Engineering, College of Engineering and Computer Science (Australia); Rangarajan, Murali, E-mail: r-murali@cb.amrita.edu [Amrita University, Center of Excellence in Advanced Materials and Green Technologies, Amrita School of Engineering Coimbatore (India)

    2016-09-15

    This study examines the suspension stability of iron oxide nanoparticles of different sizes, magnetic susceptibility, and saturation magnetization over long time scales in dilute systems using time-resolved UV–visible spectroscopy. The effects of citric acid as a chelating agent and applied external magnetic field are also studied. UV–visible spectra are obtained at different times for citric-acid-stabilized nanoparticles dispersed in water, and the peak absorbance is tracked with time, in the presence and absence of external magnetic fields. It is seen that the nanoparticles sediment slowly even in the absence of chain formation, with the phenomenon occurring in two-to-three regimes for the systems studied. Sedimentation exhibits either exponential or power-law behavior of maximum absorbance with time. In the dilute dispersions studied, thermal dispersion is about two orders of magnitude stronger than van der Waals interactions, and chain formation is not easy. Yet, it is likely that local anisotropic structures of the nanoparticles form, through which the attractive interactions result in sedimentation. Citric acid gradually stabilizes the aggregating particles; after an initial faster sedimentation, electrostatic repulsion causes the particles to segregate, as observed by a linear increase in the concentration of the nanoparticles at long times. In the presence of magnetic field, stabilization effects are significantly reduced. It is seen that though the attractive force between the nanoparticles and the external field is smaller than Brownian forces, together with van der Waals interactions, these attractive forces likely act as directing agents facilitating sedimentation. This study demonstrates that aggregation-induced sedimentation of magnetic nanoparticles is likely to play a significant role in magnetic drug targeting even when the particles are stabilized with chelating agents.Graphical abstract.

  3. Investigations of suspension stability of iron oxide nanoparticles using time-resolved UV–visible spectroscopy

    International Nuclear Information System (INIS)

    Vikram, S.; Vasanthakumari, R.; Tsuzuki, Takuya; Rangarajan, Murali

    2016-01-01

    This study examines the suspension stability of iron oxide nanoparticles of different sizes, magnetic susceptibility, and saturation magnetization over long time scales in dilute systems using time-resolved UV–visible spectroscopy. The effects of citric acid as a chelating agent and applied external magnetic field are also studied. UV–visible spectra are obtained at different times for citric-acid-stabilized nanoparticles dispersed in water, and the peak absorbance is tracked with time, in the presence and absence of external magnetic fields. It is seen that the nanoparticles sediment slowly even in the absence of chain formation, with the phenomenon occurring in two-to-three regimes for the systems studied. Sedimentation exhibits either exponential or power-law behavior of maximum absorbance with time. In the dilute dispersions studied, thermal dispersion is about two orders of magnitude stronger than van der Waals interactions, and chain formation is not easy. Yet, it is likely that local anisotropic structures of the nanoparticles form, through which the attractive interactions result in sedimentation. Citric acid gradually stabilizes the aggregating particles; after an initial faster sedimentation, electrostatic repulsion causes the particles to segregate, as observed by a linear increase in the concentration of the nanoparticles at long times. In the presence of magnetic field, stabilization effects are significantly reduced. It is seen that though the attractive force between the nanoparticles and the external field is smaller than Brownian forces, together with van der Waals interactions, these attractive forces likely act as directing agents facilitating sedimentation. This study demonstrates that aggregation-induced sedimentation of magnetic nanoparticles is likely to play a significant role in magnetic drug targeting even when the particles are stabilized with chelating agents.Graphical abstract

  4. Generation of pulsed far-infrared radiation and its application for far-infrared time-resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kondo, Yasuhiro [Tohoku Univ., Sendai (Japan). Faculty of Engineering

    1996-07-01

    So-called time-resolved spectroscopy technique has been used from old time as the means for studying the dynamic optical property, light-induced reaction and so on of matters. As an example, there is the method called pump and probe, and here, the wavelength of this probe light is the problem. If the object energy region is limited to about 0.1 eV, fast time-resolved spectroscopy is feasible relatively easily. However, energy region is extended to low energy region, the light source which is available as the pulsed probe light having sufficient intensity is limited. In this paper, the attempt of time-resolved spectroscopy utilizing coherent radiation, which has ended in failure, and the laser pulse-induced far-infrared radiation which can be utilized as new far-infrared probe light are reported. The reason why far-infrared radiation is used is explained. The attempt of time-resolved spectroscopy using NaCl crystals is reported on the equipment, the method of measuring absorption spectra and the results. Laser pulse-induced far-infrared radiation and the method of generating it are described. The multi-channel detector for far-infrared radiation which was made for trial is shown. (K.I.)

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

    NARCIS (Netherlands)

    Welzel, S.; Guaitella, O.; Lazzaroni, C.; Pintassilgo, C.; Rousseau, A.; Röpcke, J.

    2011-01-01

    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

  6. 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

  7. Time-resolved resonance Raman spectroscopy of radiation-chemical processes

    International Nuclear Information System (INIS)

    Tripathi, G.N.R.

    1983-01-01

    A tunable pulsed laser Raman spectrometer for time resolved Raman studies of radiation-chemical processes is described. This apparatus utilizes the state of art optical multichannel detection and analysis techniques for data acquisition and electron pulse radiolysis for initiating the reactions. By using this technique the resonance Raman spectra of intermediates with absorption spectra in the 248-900 nm region, and mean lifetimes > 30 ns can be examined. This apparatus can be used to time resolve the vibrational spectral overlap between transients absorbing in the same region, and to follow their decay kinetics by monitoring the well resolved Raman peaks. For kinetic measurements at millisecond time scale, the Raman technique is preferable over optical absorption method where low frequency noise is quite bothersome. A time resolved Raman study of the pulse radiolytic oxidation of aqueous tetrafluorohydroquinone and p-methoxyphenol is briefly discussed. 15 references, 5 figures

  8. Detecting aromatic compounds on planetary surfaces using ultraviolet time-resolved fluorescence spectroscopy

    Science.gov (United States)

    Eshelman, E.; Daly, M. G.; Slater, G.; Cloutis, E.

    2018-02-01

    Many aromatic organic molecules exhibit strong and characteristic fluorescence when excited with ultraviolet radiation. As laser excitation in the ultraviolet generates both fluorescence and resonantly enhanced Raman scattering of aromatic vibrational modes, combined Raman and fluorescence instruments have been proposed to search for organic compounds on Mars. In this work the time-resolved fluorescence of a suite of 24 compounds composed of 2-5 ringed alternant, non-alternant, and heterocyclic PAHs was measured. Fluorescence instrumentation with similar specifications to a putative flight instrument was capable of observing the fluorescence decay of these compounds with a sub-ns resolution. Incorporating time-resolved capabilities was also found to increase the ability to discriminate between individual PAHs. Incorporating time-resolved fluorescence capabilities into an ultraviolet gated Raman system intended for a rover or lander can increase the ability to detect and characterize PAHs on planetary surfaces.

  9. Detection of rhodopsin dimerization in situ by PIE-FCCS, a time-resolved fluorescence spectroscopy.

    Science.gov (United States)

    Smith, Adam W

    2015-01-01

    Rhodopsin self-associates in the plasma membrane. At low concentrations, the interactions are consistent with a monomer-dimer equilibrium (Comar et al., J Am Chem Soc 136(23):8342-8349, 2014). At high concentrations in native tissue, higher-order clusters have been observed (Fotiadis et al., Nature 421:127-128, 2003). The physiological role of rhodopsin dimerization is still being investigated, but it is clear that a quantitative assessment is essential to determining the function of rhodopsin clusters in vision. To quantify rhodopsin interactions, I will outline the theory and methodology of a specialized time-resolved fluorescence spectroscopy for measuring membrane protein-protein interactions called pulsed-interleaved excitation fluorescence cross-correlation spectroscopy (PIE-FCCS). The strength of this technique is its ability to quantify rhodopsin interactions in situ (i.e., a live cell plasma membrane). There are two reasons for restricting the scope to live cell membranes. First, the compositional heterogeneity of the plasma membrane creates a complex milieu with thousands of lipid, protein, and carbohydrate species. This makes it difficult to infer quaternary interactions from detergent solubilized samples or construct a model phospholipid bilayer that recapitulates all of the interactions present in native membranes. Second, organizational structure and dynamics is a key feature of the plasma membrane, and fixation techniques like formaldehyde cross-linking and vitrification will modulate the interactions. PIE-FCCS is based on two-color fluorescence imaging with time-correlated single-photon counting (TCSPC) (Becker et al., Rev Sci Instrum 70:1835-1841, 1999). By time-tagging every detected photon, the data can be analyzed as a fluorescence intensity distribution, fluorescence lifetime histogram, or fluorescence (cross-)correlation spectra (FCS/FCCS) (Becker, Advanced time-correlated single-photon counting techniques, Springer, Berlin, 2005). These

  10. System for time-resolved laser absorption spectroscopy and its application to high-power impulse magnetron sputtering

    Czech Academy of Sciences Publication Activity Database

    Adámek, Petr; Olejníček, Jiří; Hubička, Zdeněk; Čada, Martin; Kment, Štěpán; Kohout, Michal; Do, H.T.

    2017-01-01

    Roč. 88, č. 2 (2017), 1-8, č. článku 023105. ISSN 0034-6748 R&D Projects: GA TA ČR(CZ) TF01000084; GA ČR(CZ) GA15-00863S Institutional support: RVO:68378271 Keywords : plasma diagnostics * HiPIMS * time resolved measurement * laser absorption spectroscopy Subject RIV: BL - Plasma and Gas Discharge Physics OBOR OECD: Fluids and plasma physics (including surface physics) Impact factor: 1.515, year: 2016

  11. 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.

  12. Ultrafast optical responses of β-carotene and lycopene probed by sub-20-fs time-resolved coherent spectroscopy

    International Nuclear Information System (INIS)

    Fujiwara, M.; Sugisaki, M.; Gall, A.; Robert, B.; Cogdell, R.J.; Hashimoto, H.

    2009-01-01

    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 β-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 β-ionone ring and polyene backbone, whereas the other high-frequency modes do not show such dependency on the structural distortions.

  13. Time-resolved study of formate on Ni( 1 1 1 ) by picosecond SFG spectroscopy

    Science.gov (United States)

    Kusafuka, K.; Noguchi, H.; Onda, K.; Kubota, J.; Domen, K.; Hirose, C.; Wada, A.

    2002-04-01

    Time-resolved vibrational measurements were carried out on formate (HCOO) adsorbed on Ni(1 1 1) surface by combining the sum-frequency generation method and picosecond laser system (time resolution of 6 ps). Rapid intensity decrease (within the time resolution) followed by intensity recovery (time constant of several tens of ps) of CH stretching signal was observed when picosecond 800 nm pulse was irradiated on the sample surface. From the results of temperature and pump fluence dependences of temporal behaviour of signal intensity, we concluded that the observed intensity change was induced by non-thermal process. Mechanism of the temporal intensity change was discussed.

  14. Femtosecond time-resolved vibrational SFG spectroscopy of CO/Ru( 0 0 1 )

    Science.gov (United States)

    Hess, Ch.; Wolf, M.; Roke, S.; Bonn, M.

    2002-04-01

    Vibrational sum-frequency generation (SFG) employing femtosecond infrared (IR) laser pulses is used to study the dynamics of the C-O stretch vibration on Ru(0 0 1). Time-resolved measurements of the free induction decay (FID) of the IR-polarization for 0.33 ML CO/Ru(0 0 1) exhibit single exponential decays over three decades corresponding to dephasing times of T2=1.94 ps at 95 K and T2=1.16 ps at 340 K. This is consistent with pure homogeneous broadening due to anharmonic coupling with the thermally activated low-frequency dephasing mode together with a contribution from saturation of the IR transition. In pump-probe SFG experiments using a strong visible (VIS) pump pulse the perturbation of the FID leads to transient line shifts even at negative delay times, i.e. when the IR-VIS SFG probe pair precedes the pump pulse. Based on an analysis of the time-dependent polarization we discuss the influence of the perturbed FID on time-resolved SFG spectra. We investigate how coherent effects affect the SFG spectra and we examine the time resolution in these experiments, in particular in dependence of the dephasing time.

  15. Characterization of type I, II, III, IV, and V collagens by time-resolved laser-induced fluorescence spectroscopy

    Science.gov (United States)

    Marcu, Laura; Cohen, David; Maarek, Jean-Michel I.; Grundfest, Warren S.

    2000-04-01

    The relative proportions of genetically distinct collagen types in connective tissues vary with tissue type and change during disease progression, development, wound healing, aging. This study aims to 1) characterize the spectro- temporal fluorescence emission of fiber different types of collagen and 2) assess the ability of time-resolved laser- induced fluorescence spectroscopy to distinguish between collagen types. Fluorescence emission of commercially available purified samples was induced with nitrogen laser excitation pulses and detected with a MCP-PMT connected to a digital storage oscilloscope. The recorded time-resolved emission spectra displayed distinct fluorescence emission characteristics for each collagen type. The time domain information complemented the spectral domain intensity data for improved discrimination between different collagen types. Our results reveal that analysis of the fluorescence emission can be used to characterize different species of collagen. Also, the results suggest that time-resolved spectroscopy can be used for monitoring of connective tissue matrix composition changes due to various pathological and non-pathological conditions.

  16. Time-resolved spectroscopy of laser-induced breakdown in water

    Science.gov (United States)

    Thomas, Robert J.; Hammer, Daniel X.; Noojin, Gary D.; Stolarski, David J.; Rockwell, Benjamin A.; Roach, William P.

    1996-05-01

    Laser pulses of 60-ps and 80-ps at a wavelength of 532-nm and 1064-nm respectively were used to produce laser induced breakdown in triple-distilled water. The resulting luminescent flash from the plasma was captured with an imaging spectrograph coupled to a streak camera with a 5-ps time resolution. The wavelength range was 350 to 900-nm. We present the resulting experimental data which gives plasma duration and time-resolved spectral information. Plasma temperature is also computed from the data. All parameters are presented at a pulse energy of 1-mJ and are compared with time-integrated spectra at the same pulse duration and at 5 to 7-ns pulse duration in a similar energy range.

  17. Metalation of positively charged water soluble mesoporphyrins studied via time-resolved SERRS spectroscopy

    Science.gov (United States)

    Procházka, Marek; Hanzliková, Jana; Štěpánek, Josef; Baumruk, Vladimir

    1997-06-01

    Time-resolved SERRS spectra of 5,10,15,20-tetrakis[4-(trimethylammonio)phenyl]21 H,23 H-porphine (TMAP) were recorded (using a multichannel Raman spectrometer) in various SERS-active Ag colloid/porphyrin systems. Data treatment based on a factor analysis was used to decompose all the SERRS spectra into two main components: SERRS spectrum of the free base TMAP and that of its Ag metalated form. The metalation kinetics obtained in this way was found to be highly dependent on the presence of phosphate anions, citrate and/or Triton X-100 in the colloidal system. The results are analogous to those previously obtained for 5,10,15,20-tetrakis(1-methyl-4-pyridyl)21 H,23 H-porphine, a porphyrin with a substantially stronger tendency towards metalation.

  18. Broadband time-resolved elliptical crystal spectrometer for X-ray spectroscopic measurements in laser-produced plasmas

    International Nuclear Information System (INIS)

    Wang Rui-Rong; Jia Guo; Fang Zhi-Heng; Wang Wei; Meng Xiang-Fu; Xie Zhi-Yong; Zhang Fan

    2014-01-01

    The X-ray spectrometer used in high-energy-density plasma experiments generally requires both broad X-ray energy coverage and high temporal, spatial, and spectral resolutions for overcoming the difficulties imposed by the X-ray background, debris, and mechanical shocks. By using an elliptical crystal together with a streak camera, we resolve this issue at the SG-II laser facility. The carefully designed elliptical crystal has a broad spectral coverage with high resolution, strong rejection of the diffuse and/or fluorescent background radiation, and negligible source broadening for extended sources. The spectra that are Bragg reflected (23° < θ < 38°) from the crystal are focused onto a streak camera slit 18 mm long and about 80 μm wide, to obtain a time-resolved spectrum. With experimental measurements, we demonstrate that the quartz(1011) elliptical analyzer at the SG-II laser facility has a single-shot spectral range of (4.64–6.45) keV, a typical spectral resolution of E/ΔE = 560, and an enhanced focusing power in the spectral dimension. For titanium (Ti) data, the lines of interest show a distribution as a function of time and the temporal variations of the He-α and Li-like Ti satellite lines and their spatial profiles show intensity peak red shifts. The spectrometer sensitivity is illustrated with a temporal resolution of better than 25 ps, which satisfies the near-term requirements of high-energy-density physics experiments. (atomic and molecular physics)

  19. Time-resolved UV spectroscopy on ammonia excited by a pulsed CO2 laser

    International Nuclear Information System (INIS)

    Holbach, H.

    1980-07-01

    This work investigates the excitation of ammonia by a pulsed CO 2 laser, in particular the processes associated with collisions with argon. It was prompted by two previous observations: the previously reported infrared multiphoton dissociation of NH 3 under nearly collisionless conditions, and the ill understood excitation mechanism of apparently nonresonant low vibrational levels in the presence of Ar. Based on recent spectroscopic data, all vibrational-rotational levels were determined which are simultaneously excited by different CO 2 laser lines. Transitions between the 1 + and 2 - vibrational levels were also taken into account. The linewidth in these calculations was dominated by power broadening, which generates a half width at half maximum of 0.36 cm -1 at the typical power density of 10 MW/cm 2 . In order to reproduce published experimental absorption data, it proved necessary to take account all transitions within a distance of 20 cm -1 from the laser line. This fact implies in most cases the simultaneous population of a large number of vibrational-rotational levels. The population of levels by absorption or by subsequent collisional processes was probed by time-resolved absorption measurement of vibrational bands and their rotational envelope in the near UV. Time resolution (5...10) was sufficient to observe rotational relaxation within individual vibrational levels. Characteristic differences were found for the various excitation lines. (orig.) [de

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

    International Nuclear Information System (INIS)

    Williams, Kurtis A.; Howell, Steve B.; Liebert, James; Smith, Paul S.; Bellini, Andrea; Rubin, Kate H. R.; Bolte, Michael

    2013-01-01

    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 M WD ≥ 0.68 M ☉ with M WD ≈ 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 ☉ .

  1. Time-resolved photoion imaging spectroscopy: Determining energy distribution in multiphoton absorption experiments

    Science.gov (United States)

    Qian, D. B.; Shi, F. D.; Chen, L.; Martin, S.; Bernard, J.; Yang, J.; Zhang, S. F.; Chen, Z. Q.; Zhu, X. L.; Ma, X.

    2018-04-01

    We propose an approach to determine the excitation energy distribution due to multiphoton absorption in the case of excited systems following decays to produce different ion species. This approach is based on the measurement of the time-resolved photoion position spectrum by using velocity map imaging spectrometry and an unfocused laser beam with a low fluence and homogeneous profile. Such a measurement allows us to identify the species and the origin of each ion detected and to depict the energy distribution using a pure Poisson's equation involving only one variable which is proportional to the absolute photon absorption cross section. A cascade decay model is used to build direct connections between the energy distribution and the probability to detect each ionic species. Comparison between experiments and simulations permits the energy distribution and accordingly the absolute photon absorption cross section to be determined. This approach is illustrated using C60 as an example. It may therefore be extended to a wide variety of molecules and clusters having decay mechanisms similar to those of fullerene molecules.

  2. Exciplex formation in bimolecular photoinduced electron-transfer investigated by ultrafast time-resolved infrared spectroscopy.

    Science.gov (United States)

    Koch, Marius; Letrun, Romain; Vauthey, Eric

    2014-03-12

    The dynamics of bimolecular photoinduced electron-transfer reactions has been investigated with three donor/acceptor (D/A) pairs in tetrahydrofuran (THF) and acetonitrile (ACN) using a combination of ultrafast spectroscopic techniques, including time-resolved infrared absorption. For the D/A pairs with the highest driving force of electron transfer, all transient spectroscopic features can be unambiguously assigned to the excited reactant and the ionic products. For the pair with the lowest driving force, three additional transient infrared bands, more intense in THF than in ACN, with a time dependence that differs from those of the other bands are observed. From their frequency and solvent dependence, these bands can be assigned to an exciplex. Moreover, polarization-resolved measurements point to a relatively well-defined mutual orientation of the constituents and to a slower reorientational time compared to those of the individual reactants. Thanks to the minimal overlap of the infrared signature of all transient species in THF, a detailed reaction scheme including the relevant kinetic and thermodynamic parameters could be deduced for this pair. This analysis reveals that the formation and recombination of the ion pair occur almost exclusively via the exciplex.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kaiser, U.; Jimenez de Aberasturi, D.; Malinowski, R.; Amin, F.; Parak, W. J.; Heimbrodt, W., E-mail: Wolfram.Heimbrodt@physik.uni-marburg.de [Department of Physics and Materials Sciences Center, Philipps-University of Marburg, Renthof 5, D-35032 Marburg (Germany)

    2014-01-27

    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.

  4. Development of time-resolved electron momentum spectroscopy. Toward real-time imaging of frontier electrons in molecular reactions

    International Nuclear Information System (INIS)

    Yamazaki, M.; Takahashi, M.

    2016-01-01

    This report will introduce a new experimental technique to readers, which we would like to propose towards advances in the field of molecular reaction dynamics. It is time-resolved electron momentum spectroscopy and aims to take in momentum space snapshots of the rapid change of molecular orbitals, which is the driving force behind any structural changes occurring in transient molecules. Following a description of the working principle of the technique, some preliminary result will be presented in order to illustrate the current performance of the apparatus. (author)

  5. 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

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

    International Nuclear Information System (INIS)

    Bengtsson, J.

    1992-01-01

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

    Science.gov (United States)

    Niedzwiedzki, Dariusz M; Fuciman, Marcel; Kobayashi, Masayuki; Frank, Harry A; Blankenship, Robert E

    2011-10-01

    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. © Springer Science+Business Media B.V. 2011

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

    Energy Technology Data Exchange (ETDEWEB)

    Stoetzel, Jan Eric

    2012-07-01

    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/Al{sub 2}O{sub 3} catalysts during active catalytic partial oxidation in switching gas atmospheres of methane and

  9. 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...

  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. Temperature Measurements in Reacting Flows Using Time-Resolved Femtosecond Coherent Anti-Stokes Raman Scattering (fs-CARS) Spectroscopy (Postprint)

    National Research Council Canada - National Science Library

    Roy, Sukesh; Kinnius, Paul J; Lucht, Robert P; Gord, James R

    2007-01-01

    Time-resolved femtosecond coherent anti-Stokes Raman scattering (fs-CARS) spectroscopy of the nitrogen molecule is used for the measurement of temperature in atmospheric-pressure, near-adiabatic, hydrogen-air diffusion flames...

  12. Study of the Bulk Charge Carrier Dynamics in Anatase and Rutile TiO2 Single Crystals by Femtosecond Time Resolved Spectroscopy

    KAUST Repository

    Maity, Partha; Mohammed, Omar F.; Katsiev, Khabiboulakh; Idriss, Hicham

    2018-01-01

    as the best model for fundamental studies. Their ultrafast charge carrier dynamics especially on TiO2 anatase single crystal (the most active phase) are unresolved. Here femtosecond time resolved spectroscopy (TRS) was carried out to explore the dynamics

  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. The Fourteenth International Meeting on Time-Resolved Vibrational Spectroscopy (TRVS XIV)

    Science.gov (United States)

    2010-02-03

    conferences covering the use of advanced vibrational spectroscopy for the use of studying time-dependent molecular processes in chemistry, physics ...Netherlands a.huertaviga@uva.nl Neil Hunt Dept of  Physics , University of Strathclyde United Kingdom nhunt@phys.strath.ac Koichi Iwata Gakushuin University...Dasgupta Mark Creelman Sangdeok Shim Biochemical Reaction Dynamics, , , UC B k ler e ey 11:50 AM C W. Zinth, W. J. Schreier, J. Kubon, N. Regner, K

  15. New techniques of time-resolved infrared and Raman spectroscopy using ultrashort laser pulses

    International Nuclear Information System (INIS)

    Laubereau, A.

    1986-01-01

    Considerable progress has been made in recent years in the field of spectroscopic applications of ultrashort laser pulses. This paper examines two approaches toward studying ultrafast relaxation processes in condensed matter: an IR technique which complements coherent Raman scattering; and a Fourier Raman method with high frequency resolution. The time domain IR spectroscopy technique has been applied to various vibration-rotation transitions of pure HCl gas and in mixtures with Ar buffer gas. The advantage of the time domain measurements instead of frequency spectroscopy is readily visualized when one recalls that a frequency resolution of 10 -3 cm -1 corresponds to time observations over 10 -8 , which are readily feasible. As a first demonstration of the FT-Raman technique the author presents experimental data on the Q-branch of the v 1 -vibrational mode of methane. An example for the experimental data obtained approximately 2 mm behind the nozzle is presented; the coherent anti-Stokes Raman signal is plotted versus delay time. A complicated beating structure and the decay of the signal envelope are readily seen. The desired spectroscopic information is obtained by numerical Fourier transformation of the experimental points presented

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

    International Nuclear Information System (INIS)

    Nakaema, Walter Morinobu

    2010-01-01

    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 2 O (polyads 4υ, 4υ + δ) and O 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)

  17. Dissociation dynamics of CH3I in electric spark induced breakdown revealed by time-resolved laser induced breakdown spectroscopy

    International Nuclear Information System (INIS)

    Wang, Yang; Liu, Wei-long; Song, Yun-fei; Duo, Li-ping; Liu, Yu-qiang; Yang, Yan-qiang

    2015-01-01

    Highlights: • Emission of electric spark dissociation of CH 3 I is similar to its fs LIBS. • We use fs laser induced breakdown as a simulation for electric spark dissociation. • The I 2 molecule formation is directly observed in the time-resolved LIBS. • Bimolecular collision of I ∗ and CH 3 I is responsible for the formation of I 2 . - Abstract: The electric discharge spark dissociation of gas CH 3 I is found to be similar to its femtosecond laser photodissociation. The almost identical spectra of the two processes show that their initial ionization conditions are very similar. The initial ionization followed by molecular fragmentation is proposed as the dissociation mechanism, in which the characteristic emissions of I + , CH 3 , CH 2 , CH, H, and I 2 are identified as the dissociation products. The emission band of 505 nm I 2 is clearly observed in the time-resolved laser induced breakdown spectroscopy (LIBS). The dynamic curve indicates that I 2 ∗ molecules are formed after the delay time of ∼4.7 ns. The formation of I 2 ∗ molecule results from the bimolecular collision of the highly excited iodine atom I ∗ ( 4 P) and CH 3 I molecule. This dynamical information can help understand the process of electric discharge spark dissociation of CH 3 I

  18. Time-resolved monitoring of enzyme activity with ultrafast Hyper-CEST spectroscopy.

    Science.gov (United States)

    Döpfert, Jörg; Schnurr, Matthias; Kunth, Martin; Rose, Honor May; Hennig, Andreas; Schröder, Leif

    2017-12-23

    We propose a method to dynamically monitor the progress of an enzymatic reaction using NMR of hyperpolarized 129 Xe in a host-guest system. It is based on a displacement assay originally designed for fluorescence experiments that exploits the competitive binding of the enzymatic product on the one hand and a reporter dye on the other hand to a supramolecular host. Recently, this assay has been successfully transferred to NMR, using xenon as a reporter, cucurbit[6]uril as supramolecular host, and chemical exchange saturation transfer with hyperpolarized Xe (Hyper-CEST) as detection technique. Its advantage is that the enzyme acts on the unmodified substrate and that only the product is detected through immediate inclusion into the host. We here apply a method that drastically accelerates the acquisition of Hyper-CEST spectra in vitro using magnetic field gradients. This allows monitoring the dynamic progress of the conversion of lysine to cadaverine with a temporal resolution of ~30 s. Moreover, the method only requires to sample the very early onset of the reaction (Hyper-CEST results correlate with xenon T 2 measurements performed during the enzymatic reaction. This suggests that ultrafast Hyper-CEST spectroscopy can be used for dynamically monitoring enzymatic activity with NMR. Copyright © 2017 John Wiley & Sons, Ltd.

  19. Variation in LOV Photoreceptor Activation Dynamics Probed by Time Resolved Infrared Spectroscopy

    KAUST Repository

    Iuliano, James N.

    2017-12-14

    The light, oxygen, voltage (LOV) domain proteins are blue light photoreceptors that utilize a non-covalently bound flavin mononucleotide (FMN) cofactor as the chromophore. The modular nature of these proteins has led to their wide adoption in the emerging fields of optogenetics and optobiology, where the LOV domain has been fused to a variety of output domains leading to novel light-controlled applications. In the present work, we extend our studies of the sub-picosecond to several hundred microsecond transient infrared spectroscopy of the isolated LOV domain AsLOV2 to three full-length photoreceptors in which the LOV domain is fused to an output domain: the LOV-STAS protein, YtvA, the LOV-HTH transcription factor, EL222, and the LOV-histidine kinase, LovK. Despite differences in tertiary structure, the overall pathway leading to cysteine adduct formation from the FMN triplet state is highly conserved, although there are slight variations in rate. However significant differences are observed in the vibrational spectra and kinetics after adduct formation, which are directly linked to the specific output function of the LOV domain. While the rate of adduct formation varies by only 3.6-fold amongst the proteins, the subsequent large-scale structural changes in the full-length LOV photoreceptors occur over the micro- to sub-millisecond timescales and vary by orders of magnitude depending on the different output function of each LOV domain.

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

    International Nuclear Information System (INIS)

    Miyashita, Atsumi; Yoda, Osamu; Ohyanagi, T.; Murakami, K.

    1995-01-01

    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/cm 2 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 (C 0 ), C - , C + and C 2+ ions were observed. The absorption peak from C 0 was stronger as the probing position was closer to the sample surface and decreased rapidly with distance from the sample surface. The absorption peak C 2+ 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)

  1. 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.

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

    Science.gov (United States)

    Milne, Chris J.; Pham, Van-Thai; Gawelda, Wojciech; van der Veen, Renske M.; El Nahhas, Amal; Johnson, Steven L.; Beaud, Paul; Ingold, Gerhard; Lima, Frederico; Vithanage, Dimali A.; Benfatto, Maurizio; Grolimund, Daniel; Borca, Camelia; Kaiser, Maik; Hauser, Andreas; Abela, Rafael; Bressler, Christian; Chergui, Majed

    2009-11-01

    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 Å. 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.

  3. Variation in LOV Photoreceptor Activation Dynamics Probed by Time Resolved Infrared Spectroscopy

    KAUST Repository

    Iuliano, James N.; Gil, Agnieszka A.; Laptenok, Sergey P.; Hall, Christopher R.; Tolentino Collado, Jinnette; Lukacs, Andras; Hag Ahmed, Safaa A; Abyad, Jenna; Daryaee, Taraneh; Greetham, Gregory M.; Sazanovich, Igor V.; Illarionov, Boris; Bacher, Adelbert; Fischer, Markus; Towrie, Michael; French, Jarrod B.; Meech, Stephen R.; Tonge, Peter J

    2017-01-01

    The light, oxygen, voltage (LOV) domain proteins are blue light photoreceptors that utilize a non-covalently bound flavin mononucleotide (FMN) cofactor as the chromophore. The modular nature of these proteins has led to their wide adoption in the emerging fields of optogenetics and optobiology, where the LOV domain has been fused to a variety of output domains leading to novel light-controlled applications. In the present work, we extend our studies of the sub-picosecond to several hundred microsecond transient infrared spectroscopy of the isolated LOV domain AsLOV2 to three full-length photoreceptors in which the LOV domain is fused to an output domain: the LOV-STAS protein, YtvA, the LOV-HTH transcription factor, EL222, and the LOV-histidine kinase, LovK. Despite differences in tertiary structure, the overall pathway leading to cysteine adduct formation from the FMN triplet state is highly conserved, although there are slight variations in rate. However significant differences are observed in the vibrational spectra and kinetics after adduct formation, which are directly linked to the specific output function of the LOV domain. While the rate of adduct formation varies by only 3.6-fold amongst the proteins, the subsequent large-scale structural changes in the full-length LOV photoreceptors occur over the micro- to sub-millisecond timescales and vary by orders of magnitude depending on the different output function of each LOV domain.

  4. Ultrafast time-resolved absorption spectroscopy of geometric isomers of xanthophylls

    Science.gov (United States)

    Niedzwiedzki, Dariusz M.; Enriquez, Miriam M.; LaFountain, Amy M.; Frank, Harry A.

    2010-07-01

    This paper presents an ultrafast optical spectroscopic investigation of the excited state energies, lifetimes and spectra of specific geometric isomers of neoxanthin, violaxanthin, lutein, and zeaxanthin. All- trans- and 15,15'- cis-β-carotene were also examined. The spectroscopy was done on molecules purified by HPLC frozen immediately to inhibit isomerization. The spectra were taken at 77 K to maintain the configurations and to provide better spectral resolution than seen at room temperature. The kinetics reveal that for all of the molecules except neoxanthin, the S 1 state lifetime of the cis isomers is shorter than that of the all- trans isomers. The S 1 excited state energies of all the isomers were determined by recording S 1 → S 2 transient absorption spectra. The results obtained in this manner at cryogenic temperatures provide an unprecedented level of precision in the measurement of the S 1 energies of these xanthophylls, which are critical components in light-harvesting pigment-protein complexes of green plants.

  5. Time-Resolved Ultraviolet Spectroscopy of The M-Dwarf GJ 876 Exoplanetary System

    Science.gov (United States)

    France, Kevin; Linsky, Jeffrey L.; 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 on board the Hubble Space Telescope, we have measured the 1150-3140 A spectrum of GJ 876. We have reconstructed the stellar H1 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) equals approximately 0.7). This ratio is approximately 2500x greater than the solar value. We describe the ultraviolet line spectrum and report surprisingly strong fluorescent emission from hot H2 (T(H2) greater than 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 greater than or equal to 10. The strong FUV radiation field of an M-star (and specifically Ly alpha) is important for determining the abundance of O2--and the formation of biomarkers-in the lower atmospheres of Earth-like planets in the habitable zones of low-mass stars.

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

    International Nuclear Information System (INIS)

    France, Kevin; Froning, Cynthia S.; Linsky, Jeffrey L.; Tian, Feng; 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 on board the Hubble Space Telescope, we have measured the 1150-3140 Å spectrum of GJ 876. We have reconstructed the stellar H I Lyα emission line profile, and find that the integrated Lyα flux is roughly equal to the rest of the integrated flux (1150-1210 Å + 1220-3140 Å) in the entire ultraviolet bandpass (F(Lyα)/F(FUV+NUV) ≈ 0.7). This ratio is ∼2500× greater than the solar value. We describe the ultraviolet line spectrum and report surprisingly strong fluorescent emission from hot H 2 (T(H 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 Lyα) is important for determining the abundance of O 2 —and the formation of biomarkers—in the lower atmospheres of Earth-like planets in the habitable zones of low-mass stars.

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

    International Nuclear Information System (INIS)

    Badaut, V.; Schlegel, M.L.; Descostes, M.; Moutiers, G.

    2012-01-01

    The reduction oxidation-reaction between aqueous selenite (SeO 3 2- ) and siderite (FeCO 3 (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)

  8. Direct Structural and Chemical Characterization of the Photolytic Intermediates of Methylcobalamin Using Time-Resolved X-ray Absorption Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Subramanian, Ganesh; Zhang, Xiaoyi; Kodis, Gerdenis; Kong, Qingyu; Liu, Cunming; Chizmeshya, Andrew; Weierstall, Uwe; Spence, John

    2018-04-05

    Cobalt−carbon bond cleavage is crucial to most natural and synthetic applications of the cobalamin class of compounds, and here we present the first direct electronic and geometric structural characteristics of intermediates formed following photoexcitation of methylcobalamin (MeCbl) using time-resolved X-ray absorption spectroscopy (XAS). We catch transients corresponding to two intermediates, in the hundreds of picoseconds and a few microseconds. Highlights of the picosecond intermediate, which is reduced in comparison to the ground state, are elongation of the upper axial Co−C bond and relaxation of the corrin ring. This is not so with the recombining photocleaved products captured at a few microseconds, where the Co−C bond almost (yet not entirely) reverts to its ground state configuration and a substantially elongated lower axial Co−NIm bond is observed. The reduced cobalt site here confirms formation of methyl radical as the photoproduct.

  9. 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.

  10. Time-resolved pump and probe x-ray absorption fine structure spectroscopy at beamline P11 at PETRA III

    Energy Technology Data Exchange (ETDEWEB)

    Göries, D., E-mail: dennis.goeries@desy.de; Roedig, P.; Stübe, N.; Meyer, J.; Warmer, M.; Weckert, E.; Meents, A., E-mail: alke.meents@desy.de [DESY Photon Science, Deutsches Elektronen-Synchrotron (DESY), Notkestraße 85, 22607 Hamburg (Germany); Dicke, B.; Naumova, M.; Rübhausen, M. [Center for Free-Electron Laser Science (CFEL), Luruper Chaussee 149, 22761 Hamburg (Germany); Galler, A.; Gawelda, W.; Geßler, P.; Sotoudi Namin, H.; Beckmann, A. [European XFEL, Albert-Einstein Ring 19, 22761 Hamburg (Germany); Britz, A.; Bressler, C. [European XFEL, Albert-Einstein Ring 19, 22761 Hamburg (Germany); The Hamburg Centre for Ultrafast Imaging, Luruper Chaussee 149, 22761 Hamburg (Germany); Schlie, M. [Institut für Experimentalphysik, University of Hamburg, Luruper Chaussee 149, 22761 Hamburg (Germany)

    2016-05-15

    We report about the development and implementation of a new setup for time-resolved X-ray absorption fine structure spectroscopy at beamline P11 utilizing the outstanding source properties of the low-emittance PETRA III synchrotron storage ring in Hamburg. Using a high intensity micrometer-sized X-ray beam in combination with two positional feedback systems, measurements were performed on the transition metal complex fac-Tris[2-phenylpyridinato-C2,N]iridium(III) also referred to as fac-Ir(ppy){sub 3}. This compound is a representative of the phosphorescent iridium(III) complexes, which play an important role in organic light emitting diode (OLED) technology. The experiment could directly prove the anticipated photoinduced charge transfer reaction. Our results further reveal that the temporal resolution of the experiment is limited by the PETRA III X-ray bunch length of ∼103 ps full width at half maximum (FWHM).

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

    Energy Technology Data Exchange (ETDEWEB)

    Radu, L. [Department of Molecular Genetics and Radiobiology, Babes National Institute, Bucharest (Romania)], E-mail: lilianajradu@yahoo.fr; Mihailescu, I. [Department of Lasers, Laser, Plasma and Radiation Physics Institute, Bucharest (Romania); Radu, S. [Department of Computer Science, Polytechnics University, Bucharest (Romania); Gazdaru, D. [Department of Biophysics, Bucharest University (Romania)

    2007-09-21

    The analysis of chromatin damage produced by a 248 nm excimer laser radiation, for doses of 0.3-3 MJ/m{sup 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.

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

    International Nuclear Information System (INIS)

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

    2007-01-01

    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

  13. Time-Resolved Fluorescence Spectroscopy and Fluorescence Lifetime Imaging Microscopy for Characterization of Dendritic Polymer Nanoparticles and Applications in Nanomedicine

    Directory of Open Access Journals (Sweden)

    Alexander Boreham

    2016-12-01

    Full Text Available The emerging field of nanomedicine provides new approaches for the diagnosis and treatment of diseases, for symptom relief and for monitoring of disease progression. One route of realizing this approach is through carefully constructed nanoparticles. Due to the small size inherent to the nanoparticles a proper characterization is not trivial. This review highlights the application of time-resolved fluorescence spectroscopy and fluorescence lifetime imaging microscopy (FLIM for the analysis of nanoparticles, covering aspects ranging from molecular properties to particle detection in tissue samples. The latter technique is particularly important as FLIM allows for distinguishing of target molecules from the autofluorescent background and, due to the environmental sensitivity of the fluorescence lifetime, also offers insights into the local environment of the nanoparticle or its interactions with other biomolecules. Thus, these techniques offer highly suitable tools in the fields of particle development, such as organic chemistry, and in the fields of particle application, such as in experimental dermatology or pharmaceutical research.

  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. Time-Resolved Fluorescence Spectroscopy and Fluorescence Lifetime Imaging Microscopy for Characterization of Dendritic Polymer Nanoparticles and Applications in Nanomedicine.

    Science.gov (United States)

    Boreham, Alexander; Brodwolf, Robert; Walker, Karolina; Haag, Rainer; Alexiev, Ulrike

    2016-12-24

    The emerging field of nanomedicine provides new approaches for the diagnosis and treatment of diseases, for symptom relief and for monitoring of disease progression. One route of realizing this approach is through carefully constructed nanoparticles. Due to the small size inherent to the nanoparticles a proper characterization is not trivial. This review highlights the application of time-resolved fluorescence spectroscopy and fluorescence lifetime imaging microscopy (FLIM) for the analysis of nanoparticles, covering aspects ranging from molecular properties to particle detection in tissue samples. The latter technique is particularly important as FLIM allows for distinguishing of target molecules from the autofluorescent background and, due to the environmental sensitivity of the fluorescence lifetime, also offers insights into the local environment of the nanoparticle or its interactions with other biomolecules. Thus, these techniques offer highly suitable tools in the fields of particle development, such as organic chemistry, and in the fields of particle application, such as in experimental dermatology or pharmaceutical research.

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

    International Nuclear Information System (INIS)

    Niedzwiedzki, Dariusz M.; Sandberg, Daniel J.; Cong, Hong; Sandberg, Megan N.; Gibson, George N.; Birge, Robert R.; Frank, Harry A.

    2009-01-01

    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

  17. Distortion dependent intersystem crossing: A femtosecond time-resolved photoelectron spectroscopy study of benzene, toluene, and p-xylene

    Directory of Open Access Journals (Sweden)

    Anne B. Stephansen

    2017-07-01

    Full Text Available The competition between ultrafast intersystem crossing and internal conversion in benzene, toluene, and p-xylene is investigated with time-resolved photoelectron spectroscopy and quantum chemical calculations. By exciting to S2 out-of-plane symmetry breaking, distortions are activated at early times whereupon spin-forbidden intersystem crossing becomes (partly allowed. Natural bond orbital analysis suggests that the pinnacle carbon atoms distorting from the aromatic plane change hybridization between the planar Franck-Condon geometry and the deformed (boat-shaped S2 equilibrium geometry. The effect is observed to increase in the presence of methyl-groups on the pinnacle carbon-atoms, where largest extents of σ and π orbital-mixing are observed. This is fully consistent with the time-resolved spectroscopy data: Toluene and p-xylene show evidence for ultrafast triplet formation competing with internal conversion, while benzene appears to only decay via internal conversion within the singlet manifold. For toluene and p-xylene, internal conversion to S1 and intersystem crossing to T3 occur within the time-resolution of our instrument. The receiver triplet state (T3 is found to undergo internal conversion in the triplet manifold within ≈100–150 fs (toluene or ≈180–200 fs (p-xylene as demonstrated by matching rise and decay components of upper and lower triplet states. Overall, the effect of methylation is found to both increase the intersystem crossing probability and direct the molecular axis of the excited state dynamics.

  18. Noninvasive observation of skeletal muscle contraction using near-infrared time-resolved reflectance and diffusing-wave spectroscopy

    Science.gov (United States)

    Belau, Markus; Ninck, Markus; Hering, Gernot; Spinelli, Lorenzo; Contini, Davide; Torricelli, Alessandro; Gisler, Thomas

    2010-09-01

    We introduce a method for noninvasively measuring muscle contraction in vivo, based on near-infrared diffusing-wave spectroscopy (DWS). The method exploits the information about time-dependent shear motions within the contracting muscle that are contained in the temporal autocorrelation function g(1)(τ,t) of the multiply scattered light field measured as a function of lag time, τ, and time after stimulus, t. The analysis of g(1)(τ,t) measured on the human M. biceps brachii during repetitive electrical stimulation, using optical properties measured with time-resolved reflectance spectroscopy, shows that the tissue dynamics giving rise to the speckle fluctuations can be described by a combination of diffusion and shearing. The evolution of the tissue Cauchy strain e(t) shows a strong correlation with the force, indicating that a significant part of the shear observed with DWS is due to muscle contraction. The evolution of the DWS decay time shows quantitative differences between the M. biceps brachii and the M. gastrocnemius, suggesting that DWS allows to discriminate contraction of fast- and slow-twitch muscle fibers.

  19. Factors affecting measurement of optic parameters by time-resolved near-infrared spectroscopy in breast cancer

    Science.gov (United States)

    Yoshizawa, Nobuko; Ueda, Yukio; Mimura, Tetsuya; Ohmae, Etsuko; Yoshimoto, Kenji; Wada, Hiroko; Ogura, Hiroyuki; Sakahara, Harumi

    2018-02-01

    The purpose of this study was to evaluate the effects of the thickness and depth of tumors on hemoglobin measurements in breast cancer by optical spectroscopy and to demonstrate tissue oxygen saturation (SO2) and reduced scattering coefficient (μs‧) in breast tissue and breast cancer in relation to the skin-to-chest wall distance. We examined 53 tumors from 44 patients. Total hemoglobin concentration (tHb), SO2, and μs‧ were measured by time-resolved spectroscopy (TRS). The skin-to-chest wall distance and the size and depth of tumors were measured by ultrasonography. There was a positive correlation between tHb and tumor thickness, and a negative correlation between tHb and tumor depth. SO2 in breast tissue decreased when the skin-to-chest wall distance decreased, and SO2 in tumors tended to be lower than in breast tissue. In breast tissue, there was a negative correlation between μs‧ and the skin-to-chest wall distance, and μs‧ in tumors was higher than in breast tissue. Measurement of tHb in breast cancer by TRS was influenced by tumor thickness and depth. Although SO2 seemed lower and μs‧ was higher in breast cancer than in breast tissue, the skin-to-chest wall distance may have affected the measurements.

  20. Dynamic Time-Resolved Chirped-Pulse Rotational Spectroscopy of Vinyl Cyanide Photoproducts in a Room Temperature Flow Reactor

    Science.gov (United States)

    Zaleski, Daniel P.; Prozument, Kirill

    2017-06-01

    Chirped-pulsed (CP) Fourier transform rotational spectroscopy invented by Brooks Pate and coworkers a decade ago is an attractive tool for gas phase chemical dynamics and kinetics studies. A good reactor for such a purpose would have well-defined (and variable) temperature and pressure conditions to be amenable to accurate kinetic modeling. Furthermore, in low pressure samples with large enough number of molecular emitters, reaction dynamics can be observable directly, rather than mediated by supersonic expansion. In the present work, we are evaluating feasibility of in situ time-resolved CP spectroscopy in a room temperature flow tube reactor. Vinyl cyanide (CH_2CHCN), neat or mixed with inert gasses, flows through the reactor at pressures 1-50 μbar (0.76-38 mTorr) where it is photodissociated by a 193 nm laser. Millimeter-wave beam of the CP spectrometer co-propagates with the laser beam along the reactor tube and interacts with nascent photoproducts. Rotational transitions of HCN, HNC, and HCCCN are detected, with ≥10 μs time-steps for 500 ms following photolysis of CH_2CHCN. The post-photolysis evolution of the photoproducts' rotational line intensities is investigated for the effects of rotational and vibrational thermalization of energized photoproducts. Possible contributions from bimolecular and wall-mediated chemistry are evaluated as well.

  1. 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...

  2. 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

  3. Rare Earth Elements as Potential Biosignatures on Mars in SuperCam Time Resolved Laser Fluorescence Spectroscopy Data

    Science.gov (United States)

    Ollila, A.; Beyssac, O.; Sharma, S. K.; Misra, A. K.; Clegg, S. M.; Gauthier, M.; Wiens, R. C.; Maurice, S.; Gasnault, O.; Lanza, N.

    2017-12-01

    The rare earth elements (REE, La to Lu) are a group of elements with similar chemical properties that are generally present in geologic materials at trace concentrations. REEs may be concentrated via processes such as igneous fractional crystallization in accessory minerals, e.g. apatite, zircon, and titanite. Additionally, however, concentrations of REE may serve to identify regions of high astrobiological interest. For example, Fe-oxyhydroxide deposits in hydrothermal vent systems and biologically related manganese nodules may be enriched in REEs. REEs have not been measured in situ on Mars, therefore their prevalence and distribution on Mars is as yet unknown, except as observed in martian meteorites. SuperCam is a survey instrument that will analyze materials around the Mars 2020 rover using a variety of spectral techniques including laser-induced breakdown spectroscopy (LIBS), Raman, VIS-IR, and time-resolved laser fluorescence (TRLF) spectroscopy. Recently, the SuperCam Engineering Development Unit was tested at the Los Alamos National Laboratory for its capabilities to detect REEs in minerals using TRLF spectroscopy. While this instrument was not designed to precisely replicate the flight model, the spectral resolution and light transmission was sufficient to obtain TRLF spectra on a number of minerals demonstrating a variety of REE luminescent centers. These include apatite (Sm3+, Nd3+, Eu3+, Dy3+), fluorite (Ho3+, Sm3+, Dy3+, Nd3+), and zircon (Er3+, Pr3+, Nd3+). Future work includes expanding this suite to include minerals associated with biological activities, for example Mn-oxides (desert varnish and manganese nodules), hydrothermal Fe-oxides, and stromatolite-associated carbonates. In this way and in combination with its other techniques, SuperCam may direct the rover team to perform further analyses of similar samples by the in situ chemical and mineralogical suite of instruments, or aid in prioritization for sample return.

  4. Photophysical characterization and time-resolved spectroscopy of a anthradithiophene dimer: exploring the role of conformation in singlet fission

    KAUST Repository

    Dean, Jacob C.

    2017-08-18

    Quantitative singlet fission has been observed for a variety of acene derivatives such as tetracene and pentacene, and efforts to extend the library of singlet fission compounds is of current interest. Preliminary calculations suggest anthradithiophenes exhibit significant exothermicity between the first optically-allowed singlet state, S1, and 2 × T1 with an energy difference of >5000 cm−1. Given the fulfillment of this ingredient for singlet fission, here we investigate the singlet fission capability of a difluorinated anthradithiophene dimer (2ADT) covalently linked by a (dimethylsilyl)ethane bridge and derivatized by triisobutylsilylethynyl (TIBS) groups. Photophysical characterization of 2ADT and the single functionalized ADT monomer were carried out in toluene and acetone solution via absorption and fluorescence spectroscopy, and their photo-initiated dynamics were investigated with time-resolved fluorescence (TRF) and transient absorption (TA) spectroscopy. In accordance with computational predictions, two conformers of 2ADT were observed via fluorescence spectroscopy and were assigned to structures with the ADT cores trans or cis to one another about the covalent bridge. The two conformers exhibited markedly different excited state deactivation mechanisms, with the minor trans population being representative of the ADT monomer showing primarily radiative decay, while the dominant cis population underwent relaxation into an excimer geometry before internally converting to the ground state. The excimer formation kinetics were found to be solvent dependent, yielding time constants of ∼1.75 ns in toluene, and ∼600 ps in acetone. While the difference in rates elicits a role for the solvent in stabilizing the excimer structure, the rate is still decidedly long compared to most singlet fission rates of analogous dimers, suggesting that the excimer is neither a kinetic nor a thermodynamic trap, yet singlet fission was still not observed. The result

  5. Probing specific molecular processes and intermediates by time-resolved Fourier transform infrared spectroscopy: application to the bacteriorhodopsin photocycle.

    Science.gov (United States)

    Lórenz-Fonfría, Víctor A; Kandori, Hideki; Padrós, Esteve

    2011-06-23

    We present a general approach for probing the kinetics of specific molecular processes in proteins by time-resolved Fourier transform infrared (IR) spectroscopy. Using bacteriorhodopsin (bR) as a model we demonstrate that by appropriately monitoring some selected IR bands it is possible obtaining the kinetics of the most important events occurring in the photocycle, namely changes in the chromophore and the protein backbone conformation, and changes in the protonation state of the key residues implicated in the proton transfers. Besides confirming widely accepted views of the bR photocycle, our analysis also sheds light into some disputed issues: the degree of retinal torsion in the L intermediate to respect the ground state; the possibility of a proton transfer from Asp85 to Asp212; the relationship between the protonation/deprotonation of Asp85 and the proton release complex; and the timing of the protein backbone dynamics. By providing a direct way to estimate the kinetics of photocycle intermediates the present approach opens new prospects for a robust quantitative kinetic analysis of the bR photocycle, which could also benefit the study of other proteins involved in photosynthesis, in phototaxis, or in respiratory chains.

  6. Sol-to-Gel Transition in Fast Evaporating Systems Observed by in Situ Time-Resolved Infrared Spectroscopy.

    Science.gov (United States)

    Innocenzi, Plinio; Malfatti, Luca; Carboni, Davide; Takahashi, Masahide

    2015-06-22

    The in situ observation of a sol-to-gel transition in fast evaporating systems is a challenging task and the lack of a suitable experimental design, which includes the chemistry and the analytical method, has limited the observations. We synthesise an acidic sol, employing only tetraethylorthosilicate, SiCl4 as catalyst and deuterated water; the absence of water added to the sol allows us to follow the absorption from the external environment and the evaporation of deuterated water. The time-resolved data, obtained by attenuated total reflection infrared spectroscopy on an evaporating droplet, enables us to identify four different stages during evaporation. They are linked to specific hydrolysis and condensation rates that affect the uptake of water from external environment. The second stage is characterized by a decrease in hydroxyl content, a fast rise of condensation rate and an almost stationary absorption of water. This stage has been associated with the sol-to-gel transition. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Interaction of europium and nickel with calcite studied by Rutherford Backscattering Spectrometry and Time-Resolved Laser Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sabau, A. [Agence Nationale pour la gestion des Déchets RAdioactifs, 1-7 rue J. Monnet, Parc de la Croix Blanche, 92298 Châtenay-Malabry Cedex (France); Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Pipon, Y., E-mail: pipon@ipnl.in2p3.fr [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Institut Universitaire de Technologie (IUT) Lyon-1, Université Claude Bernard Lyon 1, 69 622 Villeurbanne Cedex (France); Toulhoat, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); CEA/DEN, Saclay, 91191 Gif sur Yvette (France); Lomenech, C. [Université de Nice Sophia Antipolis, Ecosystèmes Côtiers Marins et Réponses aux Stress (ECOMERS), 28 avenue Valrose, 06108 Nice Cedex 2 (France); Jordan, N. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); Moncoffre, N. [Institut de Physique Nucléaire de Lyon (IPNL), Université Lyon 1, CNRS/IN2P3, 4 rue Enrico Fermi, 69 622 Villeurbanne Cedex (France); Barkleit, A. [Helmholtz Zentrum Dresden Rossendorf (HZDR), Institute of Resource Ecology (IRE) (Germany); and others

    2014-08-01

    This study aims at elucidating the mechanisms regulating the interaction of Eu and Ni with calcite (CaCO{sub 3}). Calcite powders or single crystals (some mm sized) were put into contact with Eu or Ni solutions at concentrations ranging from 10{sup −3} to 10{sup −5} mol L{sup −1} for Eu and 10{sup −3} mol L{sup −1} for Ni. The sorption durations ranged from 1 week to 1 month. Rutherford Backscattering Spectrometry (RBS) well adapted to discriminate incorporation processes such as: (i) adsorption or co precipitation at the mineral surfaces or, (ii) incorporation into the mineral structure (through diffusion for instance), has been carried out. Moreover, using the fluorescence properties of europium, the results have been compared to those obtained by Time-Resolved Laser Fluorescence Spectroscopy (TRLFS) on calcite powders. For the single crystals, complementary SEM observations of the mineral surfaces at low voltage were also performed. Results showed that Ni accumulates at the calcite surface whereas Eu is also incorporated at a greater depth. Eu seems therefore to be incorporated into two different states in calcite: (i) heterogeneous surface accumulation and (ii) incorporation at depth greater than 160 nm after 1 month of sorption. Ni was found to accumulate at the surface of calcite without incorporation.

  8. Time-Resolved Diffuse Optical Spectroscopy and Imaging Using Solid-State Detectors: Characteristics, Present Status, and Research Challenges.

    Science.gov (United States)

    Alayed, Mrwan; Deen, M Jamal

    2017-09-14

    Diffuse optical spectroscopy (DOS) and diffuse optical imaging (DOI) are emerging non-invasive imaging modalities that have wide spread potential applications in many fields, particularly for structural and functional imaging in medicine. In this article, we review time-resolved diffuse optical imaging (TR-DOI) systems using solid-state detectors with a special focus on Single-Photon Avalanche Diodes (SPADs) and Silicon Photomultipliers (SiPMs). These TR-DOI systems can be categorized into two types based on the operation mode of the detector (free-running or time-gated). For the TR-DOI prototypes, the physical concepts, main components, figures-of-merit of detectors, and evaluation parameters are described. The performance of TR-DOI prototypes is evaluated according to the parameters used in common protocols to test DOI systems particularly basic instrumental performance (BIP). In addition, the potential features of SPADs and SiPMs to improve TR-DOI systems and expand their applications in the foreseeable future are discussed. Lastly, research challenges and future developments for TR-DOI are discussed for each component in the prototype separately and also for the entire system.

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

    International Nuclear Information System (INIS)

    Wu, Guorong; Neville, Simon P.; Schalk, Oliver; Sekikawa, Taro; Ashfold, Michael N. R.; Worth, Graham A.; Stolow, Albert

    2016-01-01

    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 2 (πσ ∗ ) state, in agreement with previous studies. Excitation at 217.0 nm prepares the previously neglected B 1 (π3p y ) Rydberg state, followed by prompt internal conversion to the A 2 (πσ ∗ ) state. In contrast with the photoinduced dynamics of pyrrole, the lifetime of the wavepacket in the A 2 (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 A 2 (πσ ∗ ) state, facilitating wavepacket motion around the potential barrier in the N–CH 3 dissociation coordinate

  10. 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.

  11. Site-Specific Measurement of Water Dynamics in the Substrate Pocket of Ketosteroid Isomerase Using Time-Resolved Vibrational Spectroscopy

    Science.gov (United States)

    Jha, Santosh Kumar; Ji, Minbiao; Gaffney, Kelly J.; Boxer, Steven G.

    2012-01-01

    Little is known about the reorganization capacity of water molecules at the active sites of enzymes and how this couples to the catalytic reaction. Here, we study the dynamics of water molecules at the active site of a highly proficient enzyme, Δ5-3-ketosteroid isomerase (KSI), during a light-activated mimic of its catalytic cycle. Photo-excitation of a nitrile containing photo-acid, coumarin183 (C183), mimics the change in charge density that occurs at the active site of KSI during the first step of the catalytic reaction. The nitrile of C183 is exposed to water when bound to the KSI active site, and we used time-resolved vibrational spectroscopy as a site-specific probe to study the solvation dynamics of water molecules in the vicinity of the nitrile. We observed that water molecules at the active site of KSI are highly rigid, during the light-activated catalytic cycle, compared to the solvation dynamics observed in bulk water. Based upon this result we hypothesize that rigid water dipoles at the active site might help in the maintenance of the pre-organized electrostatic environment required for efficient catalysis. The results also demonstrate the utility of nitrile probes in measuring the dynamics of local (H-bonded) water molecules in contrast to the commonly used fluorescence methods which measure the average behavior of primary and subsequent spheres of solvation. PMID:22931297

  12. Studies on Ternary Complex Formation of U(VI)-salicylate by Using Time-resolved Fluorescence Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Cha, Wan Sik; Cho, H. R.; Park, K. K.; Kim, W. H.; Jung, E. C. [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2010-05-15

    Organic ligands containing carboxylic and phenolic functional groups naturally occur in groundwater environment, particularly in forms of polyelectrolytes such as humic and fulvic acids, from microbial degradation of biomass, e.g., plant and animal tissues. These ligands play important roles in dissolution and migration of actinide radionuclide species since they can form stable ternary actinide complexes with common inorganic ions like hydroxides and carbonates. Therefore, model ternary complexes of lanthanides and actinides have been targets of studies to understand their chemical behaviors under near-neutral pH groundwater conditions. Previous model carboxylic ligands include phthalates, maleic acids, or alpha- substituted carboxylic acids. However, majority of previous studies investigated binary systems or used potentiometric titration method that requires high ligand concentration in mM levels. Recently, highly sensitive time-resolved laserinduced fluorescence spectroscopy (TRLFS) has been used to investigate lower concentration (e.g., a few {mu}M levels) reactions of binary complexes between of ligands and metal ions. This technique provides information regarding electronic structures and complexation constants as well as fluorescence quenching mechanism. In the present study, we studied the U(VI)-OH-salicylate (SA) ternary complex formation at higher pH (> 4) via TRLF spectrum and UV-Vis absorbance measurement. Preliminary studies show that the fluorescence (FL) intensity of hydroxouranyl species at pH 4.5 decreases as SA concentration elevates in aqueous solution. Fluorescence quenching mechanism by SA is suggested based on FL intensity (I) and lifetime (tau) measurement via TRLFS

  13. 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.

  14. Time-resolved and steady-state studies of biologically and chemically relevant systems using laser, absorption, and fluorescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Barnes, Charles Ashley [Iowa State Univ., Ames, IA (United States)

    2014-12-20

    In Chapter 2 several experimental and data analysis methods used in this thesis are described. In Chapter 3 steady-state fluorescence spectroscopy was used to determine the concentration of the efflux pump inhibitors (EPIs), pheophorbide a and pyropheophorbide a, in the feces of animals and it was found that their levels far exceed those reported to be inhibitory to efflux pumps. In Chapter 4 the solvation dynamics of 6-Propionyl-2-(N,Ndimethyl) aminonaphthalene (PRODAN) was studied in reverse micelles. The two fluorescent states of PRODAN solvate on different time scales and as such care must be exercised in solvation dynamic studies involving it and its analogs. In Chapter 5 we studied the experimental and theoretical solvation dynamics of coumarin 153 (C153) in wild-type (WT) and modified myoglobins. Based on the nuclear magnetic resonance (NMR) spectroscopy and time-resolved fluorescence studies, we have concluded that it is important to thoroughly characterize the structure of a protein and probe system before comparing the theoretical and experimental results. In Chapter 6 the photophysical and spectral properties of a derivative of the medically relevant compound curcumin called cyclocurcumin was studied. Based on NMR, fluorescence, and absorption studies, the ground- and excited-states of cyclocurcumin are complicated by the existence of multiple structural isomers. In Chapter 7 the hydrolysis of cellulose by a pure form of cellulase in an ionic liquid, HEMA, and its aqueous mixtures at various temperatures were studied with the goal of increasing the cellulose to glucose conversion for biofuel production. It was found that HEMA imparts an additional stability to cellulase and can allow for faster conversion of cellulose to glucose using a pre-treatment step in comparison to only buffer.

  15. Time-resolved diode laser infrared absorption spectroscopy of the nascent HCl in the infrared laser chemistry of 1,2-dichloro-1,1-difluoroethane

    Science.gov (United States)

    Dietrich, Peter; Quack, Martin; Seyfang, George

    1990-04-01

    The IR multiphoton excitation and the frequency, fluence and intensity dependence of the IR-laser chemical yields of CF 2ClCH 2Cl have been studied in the fluence range of 1 to 10 J cm -2 yielding a steady-state constant k(st)/ I=0.74×10 6 s -1 MW -1 cm 2 which is approximately independent of intensity. Time-resolved IR absorption spectroscopy with diode laser sources has been used to observe the nascent HCl during the first few 100 ns indicating a population inversion between the levels ν=1, J=4 and ν=2, J=5. At low reactant pressures ( p⩽10 Pa) the time-resolved measurement gives a steady-state rate constant consistent with the theoretical result adjusted to the static yield measurements. The capability of state-selective and time-resolved IR spectroscopy is thus demonstrated, giving real-time determinations of rate constants.

  16. 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

  17. Determination of blood oxygenation in the brain by time-resolved reflectance spectroscopy: influence of the skin, skull, and meninges

    Science.gov (United States)

    Hielscher, Andreas H.; Liu, Hanli; Wang, Lihong; Tittel, Frank K.; Chance, Britton; Jacques, Steven L.

    1994-07-01

    Near infrared light has been used for the determination of blood oxygenation in the brain but little attention has been paid to the fact that the states of blood oxygenation in arteries, veins, and capillaries differ substantially. In this study, Monte Carlo simulations for a heterogeneous system were conducted, and near infrared time-resolved reflectance measurements were performed on a heterogeneous tissue phantom model. The model was made of a solid polyester resin, which simulates the tissue background. A network of tubes was distributed uniformly through the resin to simulate the blood vessels. The time-resolved reflectance spectra were taken with different absorbing solutions filled in the network. Based on the simulation and experimental results, we investigated the dependence of the absorption coefficient obtained from the heterogeneous system on the absorption of the actual absorbing solution filled in the tubes. We show that light absorption by the brain should result from the combination of blood and blood-free tissue background.

  18. Time-resolved photoelectron spectroscopy of IR-driven electron dynamics in a charge transfer model system.

    Science.gov (United States)

    Falge, Mirjam; Fröbel, Friedrich Georg; Engel, Volker; Gräfe, Stefanie

    2017-08-02

    If the adiabatic approximation is valid, electrons smoothly adapt to molecular geometry changes. In contrast, as a characteristic of diabatic dynamics, the electron density does not follow the nuclear motion. Recently, we have shown that the asymmetry in time-resolved photoelectron spectra serves as a tool to distinguish between these dynamics [Falge et al., J. Phys. Chem. Lett., 2012, 3, 2617]. Here, we investigate the influence of an additional, moderately intense infrared (IR) laser field, as often applied in attosecond time-resolved experiments, on such asymmetries. This is done using a simple model for coupled electronic-nuclear motion. We calculate time-resolved photoelectron spectra and their asymmetries and demonstrate that the spectra directly map the bound electron-nuclear dynamics. From the asymmetries, we can trace the IR field-induced population transfer and both the field-driven and intrinsic (non-)adiabatic dynamics. This holds true when considering superposition states accompanied by electronic coherences. The latter are observable in the asymmetries for sufficiently short XUV pulses to coherently probe the coupled states. It is thus documented that the asymmetry is a measure for phases in bound electron wave packets and non-adiabatic dynamics.

  19. 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)

    Billard, I.; Luetzenkirchen, K.

    2003-01-01

    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.)

  20. Dynamics of Al/Fe{sub 2}O{sub 3} MIC combustion from short single-pulse photothermal initiation and time-resolved spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Stiegman, Albert E.; Park, Chi-Dong; Mileham, Melissa; Van de Burgt, Lambertus J. [Department of Chemistry and Biochemistry, Florida State University Tallahassee, FL (United States); Kramer, Michael P. [AFRL/MNME Eglin AFB, FL (United States)

    2009-08-15

    Time-resolved spectroscopy was used to study the dynamics of the photothermal ignition of Al/Fe{sub 2}O{sub 3} metastable intermolecular composites after single short-pulse laser initiation. The dynamics were recorded in several time domains from nanosecond to microsecond to quantify the dynamics from initial laser excitation to combustion. Time-averaged spectral data were also collected for the overall emission occurring during combustion. (Abstract Copyright [2009], Wiley Periodicals, Inc.)

  1. Time-resolved broadband analysis of slow-light propagation and superluminal transmission of electromagnetic waves in three-dimensional photonic crystals

    NARCIS (Netherlands)

    Gómez Rivas, J.; Farré Benet, A.; Niehusmann, J.; Haring Bolivar, P.; Kurz, H.

    2005-01-01

    A time-resolved analysis of the amplitude and phase of THz pulses propagating through three-dimensional photonic crystals is presented. Single-cycle pulses of THz radiation allow measurements over a wide frequency range, spanning more than an octave below, at and above the bandgap of strongly

  2. 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...... lifetime, allowing the detection of an ultrafast change in bulk solvent density. An analysis approach directly utilizing the spectroscopic data in the XDS analysis effectively reduces the number of free parameters, and both combined permit extraction of information about the ultrafast structural dynamics...

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

    International Nuclear Information System (INIS)

    Smith, Richard J.; Light, Roger A.; Johnston, Nicholas S.; Pitter, Mark C.; Somekh, Mike G.; Sharples, Steve D.

    2010-01-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Richard J.; Light, Roger A.; Johnston, Nicholas S.; Pitter, Mark C.; Somekh, Mike G. [Institute of Biophysics, Imaging and Optical Science, University of Nottingham, Nottinghamshire NG7 2RD (United Kingdom); Sharples, Steve D. [Applied Optics Group, Electrical Systems and Optics Research Division, University of Nottingham, Nottinghamshire NG7 2RD (United Kingdom)

    2010-02-15

    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.

  5. Continuous wave and time resolved spectroscopy of InAsN/GaAsN based quantum dots

    International Nuclear Information System (INIS)

    Taliercio, T.; Valvin, P.; Intartaglia, R.; Guillet, T.; Lefebvre, P.; Bretagnon, T.; Gil, B.; Sallet, V.; Harmand, J.C.

    2005-01-01

    We present a study of the optical properties of quantum dots based on a new family of semiconductors: III-V dilute nitrides such as (In,Ga)(N,As). Continuous wave and time resolved photoluminescence (PL) experiments allowed us to evaluate the impact of N incorporation during the growth of InAs/GaAs quantum dots. Previous work [V. Sallet et al., to be submitted to J. Cryst. Growth (2005); O. Schumann et al., J. Appl. Phys. 96, 2832 (2004)] showed that increasing the flux of N atoms into the growth chamber modifies drastically the size of the dots which leads to a bimodal growth. Two populations of dots with different sizes appear. The quantum dot PL line broadens and a second PL line appears at higher energy. Time resolved PL allows us to identify the nature of this second PL line: second population of quantum dots. A second decay time is observed which we interpret as being the consequence of the perturbation of the electronic states of the quantum dots. (copyright 2005 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  6. Lifetime measurements of odd-parity high-excitation levels of Sn I by time-resolved laser spectroscopy

    International Nuclear Information System (INIS)

    Zhang, Wei; Feng, Yanyan; Xu, Jiaxin; Dai, Zhenwen; Palmeri, Patrick; Quinet, Pascal; Biemont, Emile

    2010-01-01

    Natural radiative lifetimes of 38 odd-parity highly excited levels in neutral tin in the energy range from 43 682.737 to 56 838.68 cm -1 have been measured by a time-resolved laser-induced fluorescence technique in an atomic beam produced by laser ablation on a solid tin sample. All the levels were excited from the metastable 3 P 1, 2 and 1 D 2 levels in the ground configuration. The second and third harmonics of a dye laser were adopted as the tunable exciting source (207-250 nm). The lifetime results obtained in this paper are in the range from 4.6 to 292 ns and will be useful in extending the set of oscillator strengths available in Sn I.

  7. Lifetime measurements of odd-parity high-excitation levels of Sn I by time-resolved laser spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Wei; Feng, Yanyan; Xu, Jiaxin; Dai, Zhenwen [College of Physics, Jilin University and Key Lab of Coherent Light, Atomic and Molecular Spectroscopy, Ministry of Education, Changchun 130021 (China); Palmeri, Patrick; Quinet, Pascal; Biemont, Emile, E-mail: dai@jlu.edu.c [Astrophysique et Spectroscopie, Universite de Mons-UMONS, B-7000 Mons (Belgium)

    2010-10-28

    Natural radiative lifetimes of 38 odd-parity highly excited levels in neutral tin in the energy range from 43 682.737 to 56 838.68 cm{sup -1} have been measured by a time-resolved laser-induced fluorescence technique in an atomic beam produced by laser ablation on a solid tin sample. All the levels were excited from the metastable {sup 3}P{sub 1,} {sub 2} and {sup 1}D{sub 2} levels in the ground configuration. The second and third harmonics of a dye laser were adopted as the tunable exciting source (207-250 nm). The lifetime results obtained in this paper are in the range from 4.6 to 292 ns and will be useful in extending the set of oscillator strengths available in Sn I.

  8. Gauge invariance in the theoretical description of time-resolved angle-resolved pump/probe photoemission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Freericks, J. K.; Krishnamurthy, H. R.; Sentef, M. A.; Devereaux, T. P.

    2015-10-01

    Nonequilibrium calculations in the presence of an electric field are usually performed in a gauge, and need to be transformed to reveal the gauge-invariant observables. In this work, we discuss the issue of gauge invariance in the context of time-resolved angle-resolved pump/probe photoemission. If the probe is applied while the pump is still on, one must ensure that the calculations of the observed photocurrent are gauge invariant. We also discuss the requirement of the photoemission signal to be positive and the relationship of this constraint to gauge invariance. We end by discussing some technical details related to the perturbative derivation of the photoemission spectra, which involve processes where the pump pulse photoexcites electrons due to nonequilibrium effects.

  9. Time resolved emission spectroscopy investigations of pulsed laser ablated plasmas of ZrO2 and Al2O3

    International Nuclear Information System (INIS)

    Hadoko, A D; Lee, P S; Lee, P; Mohanty, S R; Rawat, R S

    2006-01-01

    With the rising trend of synthesizing ultra thin films and/or quantum-confined materials using laser ablation, optimization of deposition parameters plays an essential role in obtaining desired film characteristics. This paper presents the initial step of plasma optimization study by examining temporal distribution of the plasma formation by pulsed laser ablation of materials. The emitted spectra of ZrO 2 and Al 2 O 3 are obtained ∼3mm above the ablated target to derive the ablated plasma characteristics. The plasma temperature is estimated to be at around 2.35 eV, with electron density of 1.14 x 10 16 (cm -3 ). Emission spectra with different gate delay time (40-270 ns) are captured to study the time resolved plume characteristics. Transitory elemental species are identified

  10. 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.

  11. Exploration of CdTe quantum dots as mesoscale pressure sensors via time-resolved shock-compression photoluminescent emission spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Kang, Zhitao [Georgia Tech Research Institute, Georgia Institute of Technology, Atlanta, Georgia 30332-0826 (United States); School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245 (United States); Banishev, Alexandr A.; Christensen, James; Dlott, Dana D. [School of Chemical Sciences and Fredrick Seitz Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801 (United States); Lee, Gyuhyon; Scripka, David A.; Breidenich, Jennifer; Summers, Christopher J.; Thadhani, Naresh N., E-mail: naresh.thadhani@mse.gatech.edu [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0245 (United States); Xiao, Pan [LNM, Institute of Mechanics, Chinese Academy of Sciences, Beijing 100190 (China); George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0405 (United States); Zhou, Min [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0405 (United States)

    2016-07-28

    The nanometer size of CdTe quantum dots (QDs) and their unique optical properties, including size-tunable narrow photoluminescent emission, broad absorption, fast photoluminescence decay, and negligible light scattering, are ideal features for spectrally tagging the shock response of localized regions in highly heterogeneous materials such as particulate media. In this work, the time-resolved laser-excited photoluminescence response of QDs to shock-compression was investigated to explore their utilization as mesoscale sensors for pressure measurements and in situ diagnostics during shock loading experiments. Laser-driven shock-compression experiments with steady-state shock pressures ranging from 2.0 to 13 GPa were performed on nanocomposite films of CdTe QDs dispersed in a soft polyvinyl alcohol polymer matrix and in a hard inorganic sodium silicate glass matrix. Time-resolved photoluminescent emission spectroscopy was used to correlate photoluminescence changes with the history of shock pressure and the dynamics of the matrix material surrounding the QDs. The results revealed pressure-induced blueshifts in emitted wavelength, decreases in photoluminescent emission intensity, reductions in peak width, and matrix-dependent response times. Data obtained for these QD response characteristics serve as indicators for their use as possible time-resolved diagnostics of the dynamic shock-compression response of matrix materials in which such QDs are embedded as in situ sensors.

  12. Exploration of CdTe quantum dots as mesoscale pressure sensors via time-resolved shock-compression photoluminescent emission spectroscopy

    International Nuclear Information System (INIS)

    Kang, Zhitao; Banishev, Alexandr A.; Christensen, James; Dlott, Dana D.; Lee, Gyuhyon; Scripka, David A.; Breidenich, Jennifer; Summers, Christopher J.; Thadhani, Naresh N.; Xiao, Pan; Zhou, Min

    2016-01-01

    The nanometer size of CdTe quantum dots (QDs) and their unique optical properties, including size-tunable narrow photoluminescent emission, broad absorption, fast photoluminescence decay, and negligible light scattering, are ideal features for spectrally tagging the shock response of localized regions in highly heterogeneous materials such as particulate media. In this work, the time-resolved laser-excited photoluminescence response of QDs to shock-compression was investigated to explore their utilization as mesoscale sensors for pressure measurements and in situ diagnostics during shock loading experiments. Laser-driven shock-compression experiments with steady-state shock pressures ranging from 2.0 to 13 GPa were performed on nanocomposite films of CdTe QDs dispersed in a soft polyvinyl alcohol polymer matrix and in a hard inorganic sodium silicate glass matrix. Time-resolved photoluminescent emission spectroscopy was used to correlate photoluminescence changes with the history of shock pressure and the dynamics of the matrix material surrounding the QDs. The results revealed pressure-induced blueshifts in emitted wavelength, decreases in photoluminescent emission intensity, reductions in peak width, and matrix-dependent response times. Data obtained for these QD response characteristics serve as indicators for their use as possible time-resolved diagnostics of the dynamic shock-compression response of matrix materials in which such QDs are embedded as in situ sensors.

  13. Decay time shortening of fluorescence from donor-acceptor pair proteins using ultrafast time-resolved fluorescence resonance energy transfer spectroscopy

    International Nuclear Information System (INIS)

    Baba, Motoyoshi; Suzuki, Masayuki; Ganeev, Rashid A.; Kuroda, Hiroto; Ozaki, Tsuneyuki; Hamakubo, Takao; Masuda, Kazuyuki; Hayashi, Masahiro; Sakihama, Toshiko; Kodama, Tatsuhiko; Kozasa, Tohru

    2007-01-01

    We improved an ultrafast time-resolved fluorescence resonance energy transfer (FRET) spectroscopy system and measured directly the decrease in the fluorescence decay time of the FRET signal, without any entanglement of components in the picosecond time scale from the donor-acceptor protein pairs (such as cameleon protein for calcium ion indicator, and ligand-activated GRIN-Go proteins pair). The drastic decrease in lifetime of the donor protein fluorescence under the FRET condition (e.g. a 47.8% decrease for a GRIN-Go protein pair) proves the deformation dynamics between donor and acceptor fluorescent proteins in an activated state of a mixed donor-acceptor protein pair. This study is the first clear evidence of physical contact of the GRIN-Go proteins pair using time-resolved FRET system. G protein-coupled receptors (GPCRs) are the most important protein family for the recognition of many chemical substances at the cell surface. They are the targets of many drugs. Simultaneously, we were able to observe the time-resolved spectra of luminous proteins at the initial stage under the FRET condition, within 10 ns from excitation. This new FRET system allows us to trace the dynamics of the interaction between proteins at the ligand-induced activated state, molecular structure change and combination or dissociation. It will be a key technology for the development of protein chip technology

  14. Steady state and time-resolved fluorescence spectroscopy of quinine sulfate dication bound to sodium dodecylsulfate micelles: Fluorescent complex formation

    Energy Technology Data Exchange (ETDEWEB)

    Joshi, Sunita; Pant, Debi D., E-mail: ddpant@pilani.bits-pilani.ac.in

    2014-01-15

    Interaction of quinine sulfate dication (QSD) with anionic, sodium dodecylsulphate (SDS) surfactant has been studied at different premicellar, micellar and postmicellar concentrations in aqueous phase using steady state, time-resolved fluorescence and fluorescence anisotropy techniques. At premicellar concentrations of SDS, the decrease in absorbance, appearance of an extra fluorescence band at lower wavelengths and tri-exponential decay behavior of fluorescence, are attributed to complex formation between QSD molecules and surfactant monomers. At postmicellar concentrations the red shift in fluorescence spectrum, increase in quantum yield and increase in fluorescence lifetimes are attributed to incorporation of solute molecules to micelles. At lower concentrations of SDS, a large shift in fluorescence is observed on excitation at the red edge of absorption spectrum and this is explained in terms of distribution of ion pairs of different energies in the ground state and the observed fluorescence lifetime behavior corroborates with this model. The temporal fluorescence anisotropy decay of QSD in SDS micelles allowed determination of restriction on the motion of the fluorophore. All the different techniques used in this study reveal that the photophysics of QSD is very sensitive to the microenvironments of SDS micelles and QSD molecules reside at the water-micelle interface. -- Highlights: • Probe molecule is very sensitive to microenvironment of micelles. • Highly fluorescent ion-pair formation has been observed. • Modulated photophysics of probe molecule in micellar solutions has been observed. • Probe molecules strongly bind with micelles and reside at probe–micelle interface.

  15. 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/

  16. 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

    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......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...

  17. Ionomer Dynamics: Insights from Broadband Dielectric Spectroscopy

    Science.gov (United States)

    Runt, James

    2015-03-01

    Ionomers (polymers containing ionic functionality) have been traditionally used as packaging materials and in molding applications, and are now of increasing interest as candidate single ion conductors for energy storage devices, in energy conversion, and for other electroactive materials applications. The focus of this presentation is on the insight that broadband dielectric (impedance) spectroscopy brings to our understanding of ion and polymer dynamics of this family of materials. As an example of our recent work on relatively conductive ionomers, the first portion of the presentation will focus on anion conducting polyphosphazene ionomers, in which polymer bound cations are quaternized with either short alkyl or short ether oxygen chains. The low Tg, amorphous nature, and cation-solvating backbone distinguish polyphosphazenes as promising materials for ion conduction, the iodide variants being of particular interest in solar cells. In the second part of this overview, the first findings on the molecular dynamics of linear precise polyethylene-based ionomers containing 1-methylimidazolium bromide pendants on exactly every 9th, 15th, or 21st carbon atom will be summarized. In order to develop a robust interpretation of the dynamics of these materials, it is imperative to develop a thorough understanding of microphase separation (e.g. ion aggregation), and each of the above studies is complimented by multiangle X-ray scattering experiments. Supported by the NSF Polymers Program and DOE Basic Energy Sciences.

  18. Electronic resonances in broadband stimulated Raman spectroscopy

    Science.gov (United States)

    Batignani, G.; Pontecorvo, E.; Giovannetti, G.; Ferrante, C.; Fumero, G.; Scopigno, T.

    2016-01-01

    Spontaneous Raman spectroscopy is a formidable tool to probe molecular vibrations. Under electronic resonance conditions, the cross section can be selectively enhanced enabling structural sensitivity to specific chromophores and reaction centers. The addition of an ultrashort, broadband femtosecond pulse to the excitation field allows for coherent stimulation of diverse molecular vibrations. Within such a scheme, vibrational spectra are engraved onto a highly directional field, and can be heterodyne detected overwhelming fluorescence and other incoherent signals. At variance with spontaneous resonance Raman, however, interpreting the spectral information is not straightforward, due to the manifold of field interactions concurring to the third order nonlinear response. Taking as an example vibrational spectra of heme proteins excited in the Soret band, we introduce a general approach to extract the stimulated Raman excitation profiles from complex spectral lineshapes. Specifically, by a quantum treatment of the matter through density matrix description of the third order nonlinear polarization, we identify the contributions which generate the Raman bands, by taking into account for the cross section of each process.

  19. On the course of fusion processes occurring in the plasma focus - an investigation by using time-resolved neutron spectroscopy

    International Nuclear Information System (INIS)

    Schmidt, R.

    1987-01-01

    The plasma focus POSEIDON emits up to 2x10 11 neutrons during some 100 ns, if it is operated with deuterium. This very high neutron production cannot be explained by a thermal neutron production mechanism starting out from the measured values of temperature (about 1 KeV) and deuteron density (10 18 cm -3 ). There is no doubt, that there exist strong ''beam-target''-processes of the deuterons, which cause such a high suprathermal neutron production. The neutron emission of the plasma focus POSEIDON appears in two pulses, which are associated to the two main phases of the hot and dense plasma. The first is the pinch or quiescent phase, in which a stable plasma column over 100 or 150 ns exists. The second phase is characterized by turbulence processes and starts with the end of the stable phase with the on-set of the m=0-instabilities and ends with the decay of the plasma. Both phases of neutron production are studied by time-resolved analysis of the neutron anisotropy factor and by time and spatial-resolved measurements of the neutron emission. Hence it follows, that there exist during both phases different non thermal neutron production processes, which are caused by different deuteron acceleration mechanisms. To get information on these deuteron acceleration mechanisms it is appropriate to analyse the neutron spectra of the plasma focus, because the half-width and the shape of the measured spectra are related to the energy and the angular distribution of the accelerated deuterons. (orig./GG) [de

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

    Energy Technology Data Exchange (ETDEWEB)

    Sanginés, R., E-mail: roberto.sangines@ccadet.unam.mx; 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. - Highlights: • Production of 2 + ions at the earliest stages of plasma evolution • The higher the charge state the inner the location within the ablation plume. • The expansion rate of the second (ablation) plume was measured. • Shock and drag models successfully fit the ablation shock front expansion.

  1. Time-resolved plasma spectroscopy of thin foils heated by a relativistic-intensity short-pulse laser

    International Nuclear Information System (INIS)

    Audebert, P.; Gauthier, J.-C.; Shepherd, R.; Fournier, K.B.; Price, D.; Lee, R.W.; Springer, P.; Peyrusse, O.; Klein, L.

    2002-01-01

    Time-resolved K-shell x-ray spectra are recorded from sub-100 nm aluminum foils irradiated by 150-fs laser pulses at relativistic intensities of Iλ 2 =2x10 18 W μm 2 /cm 2 . The thermal penetration depth is greater than the foil thickness in these targets so that uniform heating takes place at constant density before hydrodynamic motion occurs. The high-contrast, high-intensity laser pulse, broad spectral band, and short time resolution utilized in this experiment permit a simplified interpretation of the dynamical evolution of the radiating matter. The observed spectrum displays two distinct phases. At early time, ≤500 fs after detecting target emission, a broad quasicontinuous spectral feature with strong satellite emission from multiply excited levels is seen. At a later time, the He-like resonance line emission is dominant. The time-integrated data is in accord with previous studies with time resolution greater than 1 ps. The early time satellite emission is shown to be a signature of an initial large area, high density, low-temperature plasma created in the foil by fast electrons accelerated by the intense radiation field in the laser spot. We conclude that, because of this early time phenomenon and contrary to previous predictions, a short, high-intensity laser pulse incident on a thin foil does not create a uniform hot and dense plasma. The heating mechanism has been studied as a function of foil thickness, laser pulse length, and intensity. In addition, the spectra are found to be in broad agreement with a hydrodynamic expansion code postprocessed by a collisional-radiative model based on superconfiguration average rates and on the unresolved transition array formalism

  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. Real-time monitoring of airborne beryllium, at OSHA limit levels, by time-resolved laser-induced breakdown spectroscopy

    International Nuclear Information System (INIS)

    Radziemski, L.J.; Loree, T.R.; Cremers, D.A.

    1982-01-01

    Real-time detection of beryllium particulate is being investigated by the new technique of laser-induced breakdown spectroscopy. For beryllium detection we monitor the 313.1-nm feature of once ionized beryllium (Be II). Numerous publications describe the technique, our beryllium results, and other applications. Here we summarize the important points and describe our experiments with beryllium

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

    NARCIS (Netherlands)

    Welzel, S.; Gatilova, L.; Röpcke, J.; Rousseau, A.

    2007-01-01

    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

  5. Time-resolved X-ray absorption spectroscopy for laser-ablated silicon particles in xenon gas

    International Nuclear Information System (INIS)

    Makimura, Tetsuya; Sakuramoto, Tamaki; Murakami, Kouichi

    1996-01-01

    We developed a laboratory-scale in situ apparatus for soft X-ray absorption spectroscopy with a time resolution of 10 ns and a space resolution of 100 μm. Utilizing this spectrometer, we have investigated the dynamics of silicon atoms formed by laser ablation in xenon gas. It was found that 4d-electrons in the xenon atoms are excited through collision with electrons in the laser-generated silicon plasma. (author)

  6. 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

  7. 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

  8. Time resolved measurement of laser-ablated particles by LAPXAS (Laser Plasma Soft X-ray Absorption Spectroscopy)

    International Nuclear Information System (INIS)

    Miyashita, Atsumi; Yoda, Osamu; Murakami, Kouichi

    1999-01-01

    The time- and spatially-resolved properties of laser ablated carbon, boron and silicon particles were measured by LAPXAS (Laser Plasma Soft X-ray Absorption Spectroscopy). The maximum speed of positively charged ions is higher than those of neutral atoms and negatively charged ions. The spatial distributions of the laser-ablated particles in the localized rare gas environment were measured. In helium gas environment, by the helium cloud generated on the top of ablation plume depressed the ablation plume. There is no formation of silicon clusters till 15 μs after laser ablation in the argon gas environment. (author)

  9. Time-resolved photoemission spectroscopy of electronic cooling and localization in CH3NH3PbI3 crystals

    Science.gov (United States)

    Chen, Zhesheng; Lee, Min-i.; Zhang, Zailan; Diab, Hiba; Garrot, Damien; Lédée, Ferdinand; Fertey, Pierre; Papalazarou, Evangelos; Marsi, Marino; Ponseca, Carlito; Deleporte, Emmanuelle; Tejeda, Antonio; Perfetti, Luca

    2017-09-01

    We measure the surface of CH3NH3PbI3 single crystals by making use of two-photon photoemission spectroscopy. Our method monitors the electronic distribution of photoexcited electrons, explicitly discriminating the initial thermalization from slower dynamical processes. The reported results disclose the fast-dissipation channels of hot carriers (0.25 ps), set an upper bound to the surface-induced recombination velocity (PbI3 samples is consistent with the progressive reduction of photoconversion efficiency in operating devices. Minimizing the density of shallow traps and solving the aging problem may boost the macroscopic efficiency of solar cells to the theoretical limit.

  10. Excitation dynamics of dye doped tris(8-hydroxy quinoline) aluminum films studied using time-resolved photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Read, K.; Karlsson, H. S.; Murnane, M. M.; Kapteyn, H. C.; Haight, R.

    2001-01-01

    In this work, we use excite-probe photoelectron spectroscopy to study the decay of electronic excitation in tris(8-hydroxy quinoline) aluminum (Alq) doped with the organic dye 4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (DCM). Ultrashort laser pulses are used to photoexcite electrons into unoccupied molecular orbitals, and the ensuing decay rate is directly observed using photoelectron spectroscopy. Decay of the electronic excitation is studied as a function of DCM doping percentage and excitation intensity. The decay rate is seen to increase with both doping percentage and excitation intensity. These data are explained using a model including Foerster transfer, stimulated emission, concentration quenching, and bimolecular singlet - singlet exciton annihilation. In this model, we find that it is necessary to include a very fast (faster than predicted in standard Foerster transfer theory) excitation transfer of a fraction of the excitation from the Alq to the DCM, where that fraction corresponds to the approximate nearest-neighbor population. [copyright] 2001 American Institute of Physics

  11. Broadband stimulated Raman spectroscopy in the deep ultraviolet region

    Science.gov (United States)

    Kuramochi, Hikaru; Fujisawa, Tomotsumi; Takeuchi, Satoshi; Tahara, Tahei

    2017-09-01

    We report broadband stimulated Raman measurements in the deep ultraviolet (DUV) region, which enables selective probing of the aromatic amino acid residues inside proteins through the resonance enhancement. We combine the narrowband DUV Raman pump pulse (1000 cm-1) to realize stimulated Raman measurements covering a >1500 cm-1 spectral window. The stimulated Raman measurements for neat solvents, tryptophan, tyrosine, and glucose oxidase are performed using 240- and 290-nm Raman pump, highlighting the high potential of the DUV stimulated Raman probe for femtosecond time-resolved study of proteins.

  12. Review of the theoretical description of time-resolved angle-resolved photoemission spectroscopy in electron-phonon mediated superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Kemper, A.F. [Department of Physics, North Carolina State University, Raleigh, NC (United States); Sentef, M.A. [Max Planck Institute for the Structure and Dynamics of Matter, Center for Free Electron Laser Science, Hamburg (Germany); Moritz, B. [Stanford Institute for Materials and Energy Sciences (SIMES), SLAC National Accelerator Laboratory, Menlo Park, CA (United States); Devereaux, T.P. [Stanford Institute for Materials and Energy Sciences (SIMES), SLAC National Accelerator Laboratory, Menlo Park, CA (United States); Geballe Laboratory for Advanced Materials, Stanford University, Stanford, CA (United States); Freericks, J.K. [Department of Physics, Georgetown University, Washington, DC (United States)

    2017-09-15

    We review recent work on the theory for pump/probe photoemission spectroscopy of electron-phonon mediated superconductors in both the normal and the superconducting states. We describe the formal developments that allow one to solve the Migdal-Eliashberg theory in nonequilibrium for an ultrashort laser pumping field, and explore the solutions which illustrate the relaxation as energy is transferred from electrons to phonons. We focus on exact results emanating from sum rules and approximate numerical results which describe rules of thumb for relaxation processes. In addition, in the superconducting state, we describe how Anderson-Higgs oscillations can be excited due to the nonlinear coupling with the electric field and describe mechanisms where pumping the system enhances superconductivity. (copyright 2017 by WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  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)

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

    2004-01-01

    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 (SmO 2 ) and total haemoglobin concentration (tHb) during dynamic plantar flexion exercise performed at 50% of the maximal voluntary contraction. At rest SmO 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 2 decreased (69.1 ± 1.8 and 63.8 ± 2.1% in MG and LG, respectively; P 2 and tHb

  14. Investigations of lateral and vertical compositional gradients in Cu(In,Ga)Se{sub 2} by highly spatially, spectrally and time resolved cathodoluminescence spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, Mathias; Ribbe, Stefan; Hempel, Thomas; Bertram, Frank; Christen, Juergen [Institute for Experimental Physics, Otto-von-Guericke-University, Magdeburg (Germany); Witte, Wolfram; Hariskos, Dimitrios [Zentrum fuer Sonnenenergie- und Wasserstoff-Forschung Baden-Wuerttemberg (ZSW), Stuttgart (Germany)

    2011-07-01

    Luminescence properties of Cu(In,Ga)Se{sub 2} (CIGS) layers with different thicknesses were investigated by means of highly spatially, spectrally and time resolved cathodoluminescence (CL) spectroscopy at low temperature (T=5 K). A polycrystalline CIGS thin film with a thickness of 2.4 {mu}m was grown using an in-line co-evaporation process with a final Cu-poor composition on top of a sputtered Mo layer on a soda lime glass substrate. The layer thickness was then reduced by highly controlled bromine methanol etching. The typical grainy (d{sub average}=3 {mu}m) structure of the untouched sample develops thin longish structures under the influence of the etchant. Integral CL spectra of the samples are dominated by donor-acceptor pair (DAP) luminescence. The peak energies of these spectra are ranging from 1.13 eV to 1.22 eV with decreasing layer thickness. The lateral distribution of the luminescence is inhomogeneous regarding the intensity as well as the peak energy. Time resolved CL shows a strong dependence of the initial lifetime from the emission energy.

  15. Time-Resolved Quantum Cascade Laser Absorption Spectroscopy of Pulsed Plasma Assisted Chemical Vapor Deposition Processes Containing BCl3

    Science.gov (United States)

    Lang, Norbert; Hempel, Frank; Strämke, Siegfried; Röpcke, Jürgen

    2011-08-01

    In situ measurements are reported giving insight into the plasma chemical conversion of the precursor BCl3 in industrial applications of boriding plasmas. For the online monitoring of its ground state concentration, quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range was applied in a plasma assisted chemical vapor deposition (PACVD) reactor. A compact quantum cascade laser measurement and control system (Q-MACS) was developed to allow a flexible and completely dust-sealed optical coupling to the reactor chamber of an industrial plasma surface modification system. The process under the study was a pulsed DC plasma with periodically injected BCl3 at 200 Pa. A synchronization of the Q-MACS with the process control unit enabled an insight into individual process cycles with a sensitivity of 10-6 cm-1·Hz-1/2. Different fragmentation rates of the precursor were found during an individual process cycle. The detected BCl3 concentrations were in the order of 1014 molecules·cm-3. The reported results of in situ monitoring with QCLAS demonstrate the potential for effective optimization procedures in industrial PACVD processes.

  16. 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.

  17. 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<0.05).We found that the younger group showed right lateral responses with a stronger right than left activation in the frontal pole,whereas the older group showed bilateral responses(P<0.05).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.

  18. 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.

  19. Static and time-resolved mid-infrared spectroscopy of Hg0.95Cd0.05Cr2Se4 spinel.

    Science.gov (United States)

    Barsaume, S; Telegin, A V; Sukhorukov, Yu P; Stavrias, N; Fedorov, V A; Menshchikova, T K; Kimel, A V

    2017-08-16

    Static and time-resolved mid-infrared spectroscopy of ferromagnetic single crystal Hg 0.95 Cd 0.05 Cr 2 Se 4 was performed below the absorption edge, in order to reveal the origin of the electronic transitions contributing to the magneto-optical properties of this material. The mid-infrared spectroscopy reveals a strong absorption peak around 0.236 eV which formerly was assigned to a transition within the selenide-chromium complexes ([Formula: see text] Se -Cr 2+ ). To reveal the sensitivity of the transition to the magnetic order, we performed the studies in a temperature range across the Curie temperature and magnetic fields across the value at which the saturation of ferromagnetic magnetization occurs. Despite the fact that the Curie temperature of this ferromagnetic semiconductor is around 107 K, the intensity of the mid-infrared transition reduces substantially increasing the temperature, so that already at 70 K the absorption peak is hardly visible. Such a dramatic decrease of the oscillator strength is observed simultaneously with the strong red-shift of the absorption edge in the magnetic semiconductor. Employing a time-resolved pump-and-probe technique enabled us to determine the lifetime of the electrons in the excited state of this optical transition. In the temperature range from 7 K to 80 K, the lifetime changes from 3 ps to 6 ps. This behavior agrees with the phenomenon of giant oscillator strength described earlier for weakly bound excitons in nonmagnetic semiconductors.

  20. Novel lanthanide doped micro- and mesoporous solids. Characterization of ion-host-interactions, species distribution and luminescence properties using time-resolved luminescence spectroscopy

    International Nuclear Information System (INIS)

    Gessner, Andre

    2010-12-01

    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 5 D 0 - 7 F 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 mesopores. Lanthanide ions located here, are

  1. Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

    Science.gov (United States)

    Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

    2010-01-14

    The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

  2. Broadband Spectroscopy of Nanoporous-Gold Promoter

    Directory of Open Access Journals (Sweden)

    S. K. Nakatani

    2014-02-01

    Full Text Available The efficiency of UV photocatalysis on TiO2 particles was increased by mixing TiO2 particles with nanoporous gold (NPG with pore diameters of 10–40 nm. This means that NPG acts as a promoter in the photocatalytic reaction of TiO2. Broadband spectroscopic results from millimeter wave to ultra violet of NPG membrane are discussed to estimate plasmonic effect on the catalysis.

  3. Validation of a high-power, time-resolved, near-infrared spectroscopy system for measurement of superficial and deep muscle deoxygenation during exercise.

    Science.gov (United States)

    Koga, Shunsaku; Barstow, Thomas J; Okushima, Dai; Rossiter, Harry B; Kondo, Narihiko; Ohmae, Etsuko; Poole, David C

    2015-06-01

    Near-infrared assessment of skeletal muscle is restricted to superficial tissues due to power limitations of spectroscopic systems. We reasoned that understanding of muscle deoxygenation may be improved by simultaneously interrogating deeper tissues. To achieve this, we modified a high-power (∼8 mW), time-resolved, near-infrared spectroscopy system to increase depth penetration. Precision was first validated using a homogenous optical phantom over a range of inter-optode spacings (OS). Coefficients of variation from 10 measurements were minimal (0.5-1.9%) for absorption (μa), reduced scattering, simulated total hemoglobin, and simulated O2 saturation. Second, a dual-layer phantom was constructed to assess depth sensitivity, and the thickness of the superficial layer was varied. With a superficial layer thickness of 1, 2, 3, and 4 cm (μa = 0.149 cm(-1)), the proportional contribution of the deep layer (μa = 0.250 cm(-1)) to total μa was 80.1, 26.9, 3.7, and 0.0%, respectively (at 6-cm OS), validating penetration to ∼3 cm. Implementation of an additional superficial phantom to simulate adipose tissue further reduced depth sensitivity. Finally, superficial and deep muscle spectroscopy was performed in six participants during heavy-intensity cycle exercise. Compared with the superficial rectus femoris, peak deoxygenation of the deep rectus femoris (including the superficial intermedius in some) was not significantly different (deoxyhemoglobin and deoxymyoglobin concentration: 81.3 ± 20.8 vs. 78.3 ± 13.6 μM, P > 0.05), but deoxygenation kinetics were significantly slower (mean response time: 37 ± 10 vs. 65 ± 9 s, P ≤ 0.05). These data validate a high-power, time-resolved, near-infrared spectroscopy system with large OS for measuring the deoxygenation of deep tissues and reveal temporal and spatial disparities in muscle deoxygenation responses to exercise. Copyright © 2015 the American Physiological Society.

  4. 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

  5. Probing the influence of X-rays on aqueous copper solutions using time-resolved in situ combined video/X-ray absorption near-edge/ultraviolet-visible spectroscopy

    NARCIS (Netherlands)

    Mesu, J. Gerbrand; Beale, Andrew M.; de Groot, Frank M. F.; Weckhuysen, Bert M.

    2006-01-01

    Time-resolved in situ video monitoring and ultraviolet-visible spectroscopy in combination with X-ray absorption near-edge spectroscopy (XANES) have been used for the first time in a combined manner to study the effect of synchrotron radiation on a series of homogeneous aqueous copper solutions in a

  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. Photodissociation of gaseous CH3COSH at 248 nm by time-resolved Fourier-transform infrared emission spectroscopy: Observation of three dissociation channels

    International Nuclear Information System (INIS)

    Hu, En-Lan; Tsai, Po-Yu; Fan, He; Lin, King-Chuen

    2013-01-01

    Upon one-photon excitation at 248 nm, gaseous CH 3 C(O)SH is dissociated following three pathways with the products of (1) OCS + CH 4 , (2) CH 3 SH + CO, and (3) CH 2 CO + H 2 S that are detected using time-resolved Fourier-transform infrared emission spectroscopy. The excited state 1 (n O , π * CO ) has a radiative lifetime of 249 ± 11 ns long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of collision-induced internal conversion is estimated to be 1.1 × 10 −10 cm 3 molecule −1 s −1 . Among the primary dissociation products, a fraction of the CH 2 CO moiety may undergo further decomposition to CH 2 + CO, of which CH 2 is confirmed by reaction with O 2 producing CO 2 , CO, OH, and H 2 CO. Such a secondary decomposition was not observed previously in the Ar matrix-isolated experiments. The high-resolution spectra of CO are analyzed to determine the ro-vibrational energy deposition of 8.7 ± 0.7 kcal/mol, while the remaining primary products with smaller rotational constants are recognized but cannot be spectrally resolved. The CO fragment detected is mainly ascribed to the primary production. A prior distribution method is applied to predict the vibrational distribution of CO that is consistent with the experimental findings.

  8. Solid-phase nano-extraction and laser-excited time-resolved Shpol'skii spectroscopy for the analysis of polycyclic aromatic hydrocarbons in drinking water samples.

    Science.gov (United States)

    Wang, Huiyong; Yu, Shenjiang; Campiglia, Andres D

    2009-02-15

    A unique method for screening polycyclic aromatic hydrocarbons in drinking water samples is reported. Water samples (500 microl) are mixed and centrifuged with 950 microl of a commercial solution of 20 nm gold nanoparticles for pollutants extraction. The precipitate is treated with 2 microl of 1-pentanethiol and 48 microl of n-octane, and the supernatant is then analyzed via laser-excited time-resolved Shpol'skii spectroscopy. Fifteen priority pollutants are directly determined at liquid helium temperature (4.2 K) with the aid of a cryogenic fiber-optic probe. Unambiguous pollutant determination is carried out via spectral and lifetime analysis. Limits of detection are at the parts-per-trillion level. Analytical recoveries are similar to those obtained via high-performance liquid chromatography. The simplicity of the experimental procedure, use of microliters of organic solvent, short analysis time, selectivity, and excellent analytical figures of merit demonstrate the advantages of this environmentally friendly approach for routine analysis of numerous samples.

  9. Chemical sensitivity of InP/In0.48Ga0.52P surface quantum dots studied by time-resolved photoluminescence spectroscopy

    International Nuclear Information System (INIS)

    De Angelis, Roberta; Casalboni, Mauro; De Matteis, Fabio; Hatami, Fariba; Masselink, William T.; Zhang, Hong; Prosposito, Paolo

    2015-01-01

    InP/InGaP surface quantum dots represent an attractive material for optical chemical sensors since they show a remarkable near infra-red emission at room temperature, whose intensity increases rapidly and reversibly depending on the composition of the environmental atmosphere. We show here their emission properties by time resolved photoluminescence spectroscopy investigation. Photoluminescence transients with and without chemical solvent vapours (methanol, clorophorm, acetone and water) were fitted with a 3-exponential decay law with times of about 0.5 ns, 2 ns and 7 ns. The measurements revealed a weak effect on clorophorm, acetone and water, while the initial decay time of InP surface quantum dots increases (up to 15%) upon methanol vapour exposure, indicating that the organic molecules efficiently saturate QD non-radiative surface states. - Highlights: • InP SQDs emission depends on the presence of solvent vapours in the atmosphere. • TR photoluminescence transients were fitted with a 3-exponential decay law. • The initial decay time increases (up to 15%) upon methanol vapour exposure. • Organic molecules efficiently saturate QD non-radiative surface states.

  10. 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

    2013-11-07

    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.

  11. 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)

    Jaeger, E.; Weissbach, A.; Koenig, F.; Paul, T.

    1994-01-01

    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.) [de

  12. Low pressure-induced secondary structure transitions of regenerated silk fibroin in its wet film studied by time-resolved infrared spectroscopy.

    Science.gov (United States)

    He, Zhipeng; Liu, Zhao; Zhou, Xiaofeng; Huang, He

    2018-06-01

    The secondary structure transitions of regenerated silk fibroin (RSF) under different external perturbations have been studied extensively, except for pressure. In this work, time-resolved infrared spectroscopy with the attenuated total reflectance (ATR) accessory was employed to follow the secondary structure transitions of RSF in its wet film under low pressure. It has been found that pressure alone is favorable only to the formation of β-sheet structure. Under constant pressure there is an optimum amount of D 2 O in the wet film (D 2 O : film = 2:1) so as to provide the optimal condition for the reorganization of the secondary structure and to have the largest formation of β-sheet structure. Under constant amount of D 2 O and constant pressure, the secondary structure transitions of RSF in its wet film can be divided into three stages along with time. In the first stage, random coil, α-helix, and β-turn were quickly transformed into β-sheet. In the second stage, random coil and β-turn were relatively slowly transformed into β-sheet and α-helix, and the content of α-helix was recovered to the value prior to the application of pressure. In the third and final stage, no measurable changes can be found for each secondary structure. This study may be helpful to understand the secondary structure changes of silk fibroin in silkworm's glands under hydrostatic pressure. © 2018 Wiley Periodicals, Inc.

  13. Excited state non-adiabatic dynamics of the smallest polyene, trans 1,3-butadiene. I. Time-resolved photoelectron-photoion coincidence spectroscopy

    Science.gov (United States)

    Boguslavskiy, Andrey E.; Schalk, Oliver; Gador, Niklas; Glover, William J.; Mori, Toshifumi; Schultz, Thomas; Schuurman, Michael S.; Martínez, Todd J.; Stolow, Albert

    2018-04-01

    The ultrafast excited state dynamics of the smallest polyene, trans-1,3-butadiene, were studied by femtosecond time-resolved photoelectron-photoion coincidence (TRPEPICO) spectroscopy. The evolution of the excited state wavepacket, created by pumping the bright 1Bu (ππ*) electronic state at its origin of 216 nm, is projected via one- and two-photon ionization at 267 nm onto several ionization continua. The results are interpreted in terms of Koopmans' correlations and Franck-Condon factors for the excited and cationic states involved. The known predissociative character of the cation excited states is utilized to assign photoelectron bands to specific continua using TRPEPICO spectroscopy. This permits us to report the direct observation of the famously elusive S1(21Ag) dark electronic state during the internal conversion of trans 1,3-butadiene. Our phenomenological analysis permits the spectroscopic determination of several important time constants. We report the overall decay lifetimes of the 11Bu and 21Ag states and observe the re-appearance of the hot ground state molecule. We argue that the apparent dephasing time of the S2(11Bu) state, which leads to the extreme breadth of the absorption spectrum, is principally due to large amplitude torsional motion on the 1Bu surface in conjunction with strong non-adiabatic couplings via conical intersections, whereupon nuclear wavepacket revivals to the initial Franck-Condon region become effectively impossible. In Paper II [W. J. Glover et al., J. Chem. Phys. 148, 164303 (2018)], ab initio multiple spawning is used for on-the-fly computations of the excited state non-adiabatic wavepacket dynamics and their associated TRPEPICO observables, allowing for direct comparisons of experiment with theory.

  14. Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Huse, Nils; Kim, Tae Kyu; Jamula, Lindsey; McCusker, James K.; de Groot, Frank M. F.; Schoenlein, Robert W.

    2010-04-30

    Solution-phase photoinduced low-spin to high-spin conversion in the FeII polypyridyl complex [Fe(tren(py)3)]2+ (where tren(py)3 is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following 1A1 --> 1MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L2- and L3-edges were observed concomitant with formation of the transient high-spin 5T2 state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 Angstrom increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.

  15. 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.

  16. Photoinduced charge transfer in a transition metal complex investigated by time-resolved X-ray absorption fine structure spectroscopy. Setup and experiment

    International Nuclear Information System (INIS)

    Goeries, Dennis

    2015-02-01

    In the framework of this thesis the development of a time-resolved X-ray absorption spectroscopy experiment and its application to fac-Ir(ppy) 3 is described. Such experiments require a very stable setup in terms of spatial and temporal accuracy. Therefore, the stability properties of the present installation were investigated in detail and continuously improved, in particular the synchronization of the ultrashort pulse laser system to the storage ring as well as the spatial stability of both X-ray and laser beam. Experiments utilizing the laser pump and X-ray probe configuration were applied on the green phosphorescence emitter complex fac-Ir(ppy) 3 dissolved in dimethyl sulfoxide. Structural and electronic changes were triggered by photoexcitation of the metal-to-ligand charge transfer band with ultrashort laser pulses at a wavelength of 343 nm. The excited triplet state spectrum was extracted from the measured pump-probe X-ray absorption spectrum using an ionic approximation. The results con rm the anticipated metal-to-ligand charge transfer as shown by an ionization potential shift of the iridium atom. The symmetry of the complex was found to be pseudo-octahedral. This allowed the first experimental determination of the bond length of fac-Ir(ppy) 3 in an octahedral approximation and revealed a decrease of bond length of the first coordination shell in the triplet state. The first and second-order decay kinetics of the triplet state were investigated in a combination of X-ray and laser based experiments and revealed self-quenching as well as triplet-triplet annihilation rate constants.

  17. Study of the Bulk Charge Carrier Dynamics in Anatase and Rutile TiO2 Single Crystals by Femtosecond Time Resolved Spectroscopy

    KAUST Repository

    Maity, Partha

    2018-04-02

    Understanding of the fundamentals behind charge carriers of photo-catalytic materials are still illusive hindering progress in our quest for renewable energy. TiO2 anatase and rutile are the most understood phases in photo-catalysis and serve as the best model for fundamental studies. Their ultrafast charge carrier dynamics especially on TiO2 anatase single crystal (the most active phase) are unresolved. Here femtosecond time resolved spectroscopy (TRS) was carried out to explore the dynamics of photo-excited charge carriers’ recombination in anatase single crystal, for the first time using pump fluence effects, and compares it to that of the rutile single crystal. A significant difference in charge carrier recombination rates between both crystals is observed. We found that the time constants for carrier recombination are two orders of magnitude slower for anatase (101) when compared to those of rutile (110). Moreover, bulk defects introduced by reduction of the samples via annealing in ultra-high vacuum resulted in faster recombination rates for both polymorphs. Both states (fresh and reduced) probed by pump fluence dependence measurements revealed that the major recombination channel in fresh and reduced anatase and reduced rutile is the first-order Shockley–Reed mediated. However, for fresh rutile, third-body Auger recombination was observed, attributed to the presence of higher density of intrinsic charge carriers. At all excitation wavelengths and fluence investigated, anatase (101) single crystal show longer charge carrier lifetime when compared to rutile (110) single. This may explain the superiority of the anatase phase for the electron transfer H+ reduction to molecular hydrogen.

  18. Broadband dielectric spectroscopy of oxidized porous silicon

    International Nuclear Information System (INIS)

    Axelrod, Ekaterina; Urbach, Benayahu; Sa'ar, Amir; Feldman, Yuri

    2006-01-01

    Dielectric measurements accompanied by infrared absorption and photoluminescence (PL) spectroscopy were used to investigate the electrical and optical properties of oxidized porous silicon (PS). As opposed to non-oxidized PS, only high temperature relaxation processes could be resolved for oxidized PS. Two relaxation processes have been observed. The first process is related to dc-conductivity that dominates at high temperatures and low frequencies. After subtraction of dc-conductivity we could analyse a second high-temperature relaxation process that is related to interface polarization induced by charge carriers trapped at the host matrix-pore interfaces. We found that, while the main effect of the oxidation on the PL appears to be a size reduction in the silicon nanocrystals that gives rise to a blue shift of the PL spectrum, its main contribution to the dielectric properties turns out to be blocking of transport channels in the host tissue and activation of hopping conductivity between silicon nanocrystals

  19. Broadband dielectric spectroscopy of oxidized porous silicon

    Energy Technology Data Exchange (ETDEWEB)

    Axelrod, Ekaterina [Department of Applied Physics, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel); Urbach, Benayahu [Racah Institute of Physics and the Center for Nanoscience and Nanotechnology, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel); Sa' ar, Amir [Racah Institute of Physics and the Center for Nanoscience and Nanotechnology, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel); Feldman, Yuri [Department of Applied Physics, Hebrew University of Jerusalem, Jerusalem, 91904 (Israel)

    2006-04-07

    Dielectric measurements accompanied by infrared absorption and photoluminescence (PL) spectroscopy were used to investigate the electrical and optical properties of oxidized porous silicon (PS). As opposed to non-oxidized PS, only high temperature relaxation processes could be resolved for oxidized PS. Two relaxation processes have been observed. The first process is related to dc-conductivity that dominates at high temperatures and low frequencies. After subtraction of dc-conductivity we could analyse a second high-temperature relaxation process that is related to interface polarization induced by charge carriers trapped at the host matrix-pore interfaces. We found that, while the main effect of the oxidation on the PL appears to be a size reduction in the silicon nanocrystals that gives rise to a blue shift of the PL spectrum, its main contribution to the dielectric properties turns out to be blocking of transport channels in the host tissue and activation of hopping conductivity between silicon nanocrystals.

  20. 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)

    Bonn, M; Ueba, H; Wolf, M

    2005-01-01

    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

  1. Structure of fenchone by broadband rotational spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Loru, Donatella; Bermúdez, Miguel A.; Sanz, M. Eugenia [Department of Chemistry, King’s College London, London SE1 1DB (United Kingdom)

    2016-08-21

    The bicyclic terpenoid fenchone (C{sub 10}H{sub 16}O, 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 (r{sub s}) and effective (r{sub 0}) 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 C{sub 2}. 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 C{sub 2} drives structural adjustments to minimise ring strain after its introduction.

  2. Time-resolved studies

    International Nuclear Information System (INIS)

    Mills, D.M.

    1992-01-01

    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

  3. Nanosecond retinal structure changes in K-590 during the room-temperature bacteriorhodopsin photocycle: picosecond time-resolved coherent anti-stokes Raman spectroscopy

    OpenAIRE

    Weidlich, O.; Ujj, L.; Jäger, F.; Atkinson, G.H.

    1997-01-01

    Time-resolved vibrational spectra are used to elucidate the structural changes in the retinal chromophore within the K-590 intermediate that precedes the formation of the L-550 intermediate in the room-temperature (RT) bacteriorhodopsin (BR) photocycle. Measured by picosecond time-resolved coherent anti-Stokes Raman scattering (PTR/CARS), these vibrational data are recorded within the 750 cm-1 to 1720 cm-1 spectral region and with time delays of 50-260 ns after the RT/BR photocycle is optical...

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

    International Nuclear Information System (INIS)

    Hooper, C.F. Jr.

    1998-03-01

    This report is comprised of three documents which deal with plasma spectroscopy of laser-produced plasmas. In Appendix A the authors present a discussion of plasma line broadening with emphasis on the effects of accounting for ion-dynamic corrections. For two decades, high power lasers have been used to implode microballoons filled with gases such as neon, argon, deuterium, or mixtures of deuterium and argon. These implosions have generated high-temperature (∼ 1 keV) and high density (∼ 10 23 /cc--10 25 /cc) plasmas. As a result of these experiments, the authors are able to observe the radiative properties of highly charged ions in the presence of a variety of strongly coupled plasmas. Spectral radiation observed from these experiments is frequently in the x-ray region and the radiative properties are greatly influenced by plasma effects. In section 2 of this paper the authors discuss the theoretical techniques employed to interpret these spectra and describe two sets of implosion experiments. In section 3 they list some conclusions. Appendix B presents more research related to ion-dynamic corrections. The authors examine the combined effects of ion dynamics and opacity on line profiles used in the analysis of hot dense plasmas. Specifically, they have calculated Stark broadened line profiles for both resonance and satellite lines in highly stripped Ar ions, both in the quasi-static ion approximation, and including the effects of ion dynamics. Using the results of an NLTE kinetics code, combined with an escape factor formalism to account for the effects of radiative transfer, they have calculated the relative intensities of these lines, as well as the effects of opacity on their profiles. This model spectra is used in the analysis of experimental data. In a series of experiments performed at the Laboratory for Laser Energetics plastic microballoons filled with DD and doped with Ar were imploded using the Omega laser system. Here, the authors use time-resolved K

  5. Structural changes and thermal stability of charged LiNixMnyCozO₂ cathode materials studied by combined in situ time-resolved XRD and mass spectroscopy.

    Science.gov (United States)

    Bak, Seong-Min; Hu, Enyuan; Zhou, Yongning; Yu, Xiqian; Senanayake, Sanjaya D; Cho, Sung-Jin; Kim, Kwang-Bum; Chung, Kyung Yoon; Yang, Xiao-Qing; Nam, Kyung-Wan

    2014-12-24

    Thermal stability of charged LiNixMnyCozO2 (NMC, with x + y + z = 1, x:y:z = 4:3:3 (NMC433), 5:3:2 (NMC532), 6:2:2 (NMC622), and 8:1:1 (NMC811)) cathode materials is systematically studied using combined in situ time-resolved X-ray diffraction and mass spectroscopy (TR-XRD/MS) techniques upon heating up to 600 °C. The TR-XRD/MS results indicate that the content of Ni, Co, and Mn significantly affects both the structural changes and the oxygen release features during heating: the more Ni and less Co and Mn, the lower the onset temperature of the phase transition (i.e., thermal decomposition) and the larger amount of oxygen release. Interestingly, the NMC532 seems to be the optimized composition to maintain a reasonably good thermal stability, comparable to the low-nickel-content materials (e.g., NMC333 and NMC433), while having a high capacity close to the high-nickel-content materials (e.g., NMC811 and NMC622). The origin of the thermal decomposition of NMC cathode materials was elucidated by the changes in the oxidation states of each transition metal (TM) cations (i.e., Ni, Co, and Mn) and their site preferences during thermal decomposition. It is revealed that Mn ions mainly occupy the 3a octahedral sites of a layered structure (R3̅m) but Co ions prefer to migrate to the 8a tetrahedral sites of a spinel structure (Fd3̅m) during the thermal decomposition. Such element-dependent cation migration plays a very important role in the thermal stability of NMC cathode materials. The reasonably good thermal stability and high capacity characteristics of the NMC532 composition is originated from the well-balanced ratio of nickel content to manganese and cobalt contents. This systematic study provides insight into the rational design of NMC-based cathode materials with a desired balance between thermal stability and high energy density.

  6. Processes of the excitation energy migration and transfer in Ce3+-doped alkali gadolinium phosphates studied with time-resolved photoluminescence spectroscopy technique

    International Nuclear Information System (INIS)

    Stryganyuk, G.; Shalapska, T.; Voloshinovskii, A.; Gektin, A.; Krasnikov, A.; Zazubovich, S.

    2011-01-01

    Spectral-kinetic characteristics of Gd 3+ and Ce 3+ luminescence from a series of Ce 3+ -doped alkali gadolinium phosphates of MGdP 4 O 12 type (M=Li, Na, Cs) have been studied within 4.2-300 K temperature range using time-resolved luminescence spectroscopy techniques. The processes of energy migration along the Gd 3+ sub-lattice and energy transfer between the Gd 3+ and Ce 3+ ions have been investigated. Peculiarities of these processes have been compared for MGdP 4 O 12 phosphate hosts with different alkali metal ions. A contribution of different levels from the 6 P j multiplet of the lowest Gd 3+ excited state into the energy migration and transfer processes has been clarified. The phonon-assisted occupation of high-energy 6 P 5/2,3/2 levels by Gd 3+ in the excited 6 P j state has been revealed as a shift of Gd 3+6 P j → 8 S 7/2 emission into the short-wavelength spectral range upon the temperature increase. The relaxation of excited Gd 3+ via phonon-assisted population of Gd 3+6 P 5/2 level (next higher one to the lowest excited 6 P 7/2 ) is supposed to be responsible for the rise in probability of energy migration within the Gd 3+ sub-lattice initiating the Gd 3+ →Ce 3+ energy transfer at T 3+ →Ce 3+ energy transfer at T>150 K is explained by the increase in probability of Gd 3+ relaxation into the highest 6 P 3/2 level of the 6 P j multiplet. An efficient reversed Ce 3+ →Gd 3+ energy transfer has been revealed for the studied phosphates at 4.2 K. - Highlights: →We investigate the Gd 3+ -Ce 3+ energy transfer in alkali gadolinium phosphates. → Thermal population of Gd 3+6 P 5/2 level improves migration along the Gd sub-lattice. → Increasing overlap of Gd 3+ and Ce 3+ states enhances the Gd 3+ -Ce 3+ energy transfer. → In LiGdP 4 O 12 :Ce and NaGdP 4 O 12 :Ce an efficient Ce 3+ -Gd 3+ transfer occurs at 4-300 K. → An effective reverse Gd 3+ -Ce 3+ energy transfer becomes possible at T>150 K.

  7. Structural differences in the two agonist binding sites of the Torpedo nicotinic acetylcholine receptor revealed by time-resolved fluorescence spectroscopy

    DEFF Research Database (Denmark)

    Martinez, K. L.; Corringer, P. J.; Edelstein, S. J.

    2000-01-01

    The nicotinic acetylcholine receptor (nAChR) from Torpedo marmorata carries two nonequivalent agonist binding sites at the αδ and αγ subunit interfaces. These sites have been characterized by time-resolved fluorescence with the partial nicotinic agonist dansyl-C6-choline (Dnscho). When bound...

  8. Gain-assisted broadband ring cavity enhanced spectroscopy

    Science.gov (United States)

    Selim, Mahmoud A.; Adib, George A.; Sabry, Yasser M.; Khalil, Diaa

    2017-02-01

    Incoherent broadband cavity enhanced spectroscopy can significantly increase the effective path length of light-matter interaction to detect weak absorption lines over broad spectral range, for instance to detect gases in confined environments. Broadband cavity enhancement can be based on the decay time or the intensity drop technique. Decay time measurement is based on using tunable laser source that is expensive and suffers from long scan time. Intensity dependent measurement is usually reported based on broadband source using Fabry-Perot cavity, enabling short measurement time but suffers from the alignment tolerance of the cavity and the cavity insertion loss. In this work we overcome these challenges by using an alignment-free ring cavity made of an optical fiber loop and a directional coupler, while having a gain medium pumped below the lasing threshold to improve the finesse and reduce the insertion loss. Acetylene (C2H2) gas absorption is measured around 1535 nm wavelength using a semiconductor optical amplifier (SOA) gain medium. The system is analyzed for different ring resonator forward coupling coefficient and loses, including the 3-cm long gas cell insertion loss and fiber connector losses used in the experimental verification. The experimental results are obtained for a coupler ratio of 90/10 and a fiber length of 4 m. The broadband source is the amplified spontaneous emission of another SOA and the output is measured using a 70pm-resolution optical spectrum analyzer. The absorption depth and the effective interaction length are improved about an order of magnitude compared to the direct absorption of the gas cell. The presented technique provides an engineering method to improve the finesse and, consequently the effective length, while relaxing the technological constraints on the high reflectivity mirrors and free-space cavity alignment.

  9. Time-resolved absorption measurements on OMEGA

    International Nuclear Information System (INIS)

    Jaanimagi, P.A.; DaSilva, L.; Delettrez, J.; Gregory, G.G.; Richardson, M.C.

    1986-01-01

    Time-resolved measurements of the incident laser light that is scattered and/or refracted from targets irradiated by the 24 uv-beam OMEGA laser at LLE, have provided some interesting features related to time-resolved absorption. The decrease in laser absorption characteristic of irradiating a target that implodes during the laser pulse has been observed. The increase in absorption expected as the critical density surface moves from a low to a high Z material in the target has also been noted. The detailed interpretation of these results is made through comparisons with simulation using the code LILAC, as well as with streak data from time-resolved x-ray imaging and spectroscopy. In addition, time and space-resolved imaging of the scattered light yields information on laser irradiation uniformity conditions on the target. The report consists of viewgraphs

  10. Development of soft x-ray time-resolved photoemission spectroscopy system with a two-dimensional angle-resolved time-of-flight analyzer at SPring-8 BL07LSU

    Energy Technology Data Exchange (ETDEWEB)

    Ogawa, Manami; Yamamoto, Susumu; Nakamura, Fumitaka; Yukawa, Ryu; Fukushima, Akiko; Harasawa, Ayumi; Kakizaki, Akito; Matsuda, Iwao [Institute for Solid State Physics, University of Tokyo, 5-1-5 Kashiwanoha, Chiba 277-8581 (Japan); Kousa, Yuka; Kondoh, Hiroshi [Department of Chemistry, Keio University, Yokohama 223-8522 (Japan); Tanaka, Yoshihito [RIKEN/SPring-8 Center, 1-1-1, Kouto, Sayo-cho, Sayo-gun, Hyogo 679-5148 (Japan)

    2012-02-15

    We have developed a soft x-ray time-resolved photoemission spectroscopy system using synchrotron radiation (SR) at SPring-8 BL07LSU and an ultrashort pulse laser system. Two-dimensional angle-resolved measurements were performed with a time-of-flight-type analyzer. The photoemission spectroscopy system is synchronized to light pulses of SR and laser using a time control unit. The performance of the instrument is demonstrated by mapping the band structure of a Si(111) crystal over the surface Brillouin zones and observing relaxation of the surface photo-voltage effect using the pump (laser) and probe (SR) method.

  11. 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)

    Marczynski-Buehlow, Martin

    2012-01-01

    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

  12. 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

  13. Type I photosensitized reactions of oxopurines. Kinetics and thermodynamics of the reaction with triplet benzophenone by time-resolved photoacoustic spectroscopy

    Science.gov (United States)

    Murgida, Daniel H.; Erra Balsells, Rosa; Crippa, Pier Raimondo; Viappiani, Cristiano

    1998-09-01

    Benzophenone photosensitized reactions of caffeine, theophylline and theobromine were investigated in acetonitrile by time-resolved laser-induced photoacoustics. In the three cases global quenching rate constants of triplet benzophenone were measured as a function of temperature and it was observed that this is a non-activated process. Besides, for theobromine and theophylline heats for NH hydrogen abstraction reactions were determined. In agreement with semiempirical calculation predictions, hydrogen abstraction is thermodynamically more favorable and faster for theophylline (Δ H=-265 kJ mol -1, kr=9.6×10 8 M -1 s -1) than for theobromine (Δ H=-168 kJ mol -1, kr=3.7×10 8 M -1 s -1).

  14. Broadband dielectric spectroscopy and calorimetric investigations of D-lyxose.

    Science.gov (United States)

    Singh, Lokendra P; Alegría, A; Colmenero, J

    2011-10-18

    Using broadband dielectric spectroscopy, we have studied different types of relaxation processes, namely, primary (α), secondary (β), and another sub-T(g) process called γ-process, in the supercooled state of D-lyxose, over a wide frequency (10(-2)-10(9) Hz) and temperature range (120-340 K). In addition, the same sample was analyzed by differential scanning calorimeter. The temperature dependence of the relaxation times as well as the dielectric strength of different processes has been critically examined. It has been observed that the slower secondary relaxation (designated as β-) process shifts to lower frequencies with increasing applied pressure, but not the faster one. This pressure dependence indicates that the observed slower secondary relaxation (β-) is Johari-Goldstein relaxation process and faster one (γ-process) is probably the rotation of hydroxymethyl (-CH(2)OH) side group attached to the sugar ring, that is, of intramolecular origin. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2009-06-01

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

  16. Excited-state relaxation dynamics of Re(I) tricarbonyl complexes with macrocyclic phenanthroline ligands studied by time-resolved IR spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Blanco-Rodríguez, A. M.; Towrie, M.; Collin, J.; P.; Záliš, Stanislav; Vlček, Antonín

    -, č. 20 (2009), s. 3941-3949 ISSN 1477-9226 R&D Projects: GA MŠk OC09043; GA MŠk OC 139 Institutional research plan: CEZ:AV0Z40400503 Keywords : Raman spectroscopy * molecular machine prototypes * infrared spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 4.081, year: 2009

  17. Time resolved techniques: An overview

    International Nuclear Information System (INIS)

    Larson, B.C.; Tischler, J.Z.

    1990-06-01

    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

  18. Internal energy of HCl upon photolysis of 2-chloropropene at 193 nm investigated with time-resolved Fourier-transform spectroscopy and quasiclassical trajectories

    International Nuclear Information System (INIS)

    Chang, C.-M.; Huang, Y.-H.; Liu, S.-Y.; Lee, Y.-P.; Pombar-Perez, Marta; Martinez-Nunez, Emilio; Vazquez, Saulo A.

    2008-01-01

    Following photodissociation of 2-chloropropene (H 2 CCClCH 3 ) at 193 nm, vibration-rotationally resolved emission spectra of HCl (υ≤6) in the spectral region of 1900-2900 cm -1 were recorded with a step-scan time-resolved Fourier-transform spectrometer. All vibrational levels show a small low-J component corresponding to ∼400 K and a major high-J component corresponding to 7100-18 700 K with average rotational energy of 39± 3 11 kJ mol -1 . The vibrational population of HCl is inverted at υ=2, and the average vibrational energy is 86±5 kJ mol -1 . Two possible channels of molecular elimination producing HCl+propyne or HCl+allene cannot be distinguished positively based on the observed internal energy distribution of HCl. The observed rotational distributions fit qualitatively with the distributions of both channels obtained with quasiclassical trajectories (QCTs), but the QCT calculations predict negligible populations for states at small J. The observed vibrational distribution agrees satisfactorily with the total QCT distribution obtained as a weighted sum of contributions from both four-center elimination channels. Internal energy distributions of HCl from 2-chloropropene and vinyl chloride are compared.

  19. Quantitative study of energy-transfer mechanism in Eu,O-codoped GaN by time-resolved photoluminescence spectroscopy

    Science.gov (United States)

    Inaba, Tomohiro; Kojima, Takanori; Yamashita, Genki; Matsubara, Eiichi; Mitchell, Brandon; Miyagawa, Reina; Eryu, Osamu; Tatebayashi, Jun; Ashida, Masaaki; Fujiwara, Yasufumi

    2018-04-01

    In order to investigate the excitation processes in Eu,O-codoped GaN (GaN:Eu,O), the time-resolved photoluminescence signal including the rising part is analyzed. A rate equation is developed based upon a model for the excitation processes in GaN:Eu to fit the experimental data. The non-radiative recombination rate of the trap state in the GaN host, the energy transfer rate between the Eu3+ ions and the GaN host, the radiative transition probability of Eu3+ ion, as well as the ratio of the number of luminescent sites (OMVPE 4α and OMVPE 4β), are simultaneously determined. It is revealed and quantified that radiative transition probability of the Eu ion is the bottleneck for the enhancement of light output from GaN:Eu. We also evaluate the effect of the growth conditions on the luminescent efficiency of GaN:Eu quantitatively, and find the correlation between emission intensity of GaN:Eu and the fitting parameters introduced in our model.

  20. The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. II. Homo-arrays of LH2 complexes reconstituted into phospholipid model membranes.

    Science.gov (United States)

    Pflock, Tobias J; Oellerich, Silke; Krapf, Lisa; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

    2011-07-21

    We performed time-resolved spectroscopy on homoarrays of LH2 complexes from the photosynthetic purple bacterium Rhodopseudomonas acidophila. Variations of the fluorescence transients were monitored as a function of the excitation fluence and the repetition rate of the excitation. These parameters are directly related to the excitation density within the array and to the number of LH2 complexes that still carry a triplet state prior to the next excitation. Comparison of the experimental observations with results from dynamic Monte Carlo simulations for a model cluster of LH2 complexes yields qualitative agreement without the need for any free parameter and reveals the mutual relationship between energy transfer and annihilation processes.

  1. Scanning, non-contact, hybrid broadband diffuse optical spectroscopy and diffuse correlation spectroscopy system.

    Science.gov (United States)

    Johansson, Johannes D; Mireles, Miguel; Morales-Dalmau, Jordi; Farzam, Parisa; Martínez-Lozano, Mar; Casanovas, Oriol; Durduran, Turgut

    2016-02-01

    A scanning system for small animal imaging using non-contact, hybrid broadband diffuse optical spectroscopy (ncDOS) and diffuse correlation spectroscopy (ncDCS) is presented. The ncDOS uses a two-dimensional spectrophotometer retrieving broadband (610-900 nm) spectral information from up to fifty-seven source-detector distances between 2 and 5 mm. The ncDCS data is simultaneously acquired from four source-detector pairs. The sample is scanned in two dimensions while tracking variations in height. The system has been validated with liquid phantoms, demonstrated in vivo on a human fingertip during an arm cuff occlusion and on a group of mice with xenoimplanted renal cell carcinoma.

  2. 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.

  3. Large Molecule Structures by Broadband Fourier Transform Molecular Rotational Spectroscopy

    Science.gov (United States)

    Evangelisti, Luca; Seifert, Nathan A.; Spada, Lorenzo; Pate, Brooks

    2016-06-01

    Fourier transform molecular rotational resonance spectroscopy (FT-MRR) using pulsed jet molecular beam sources is a high-resolution spectroscopy technique that can be used for chiral analysis of molecules with multiple chiral centers. The sensitivity of the molecular rotational spectrum pattern to small changes in the three dimensional structure makes it possible to identify diastereomers without prior chemical separation. For larger molecules, there is the additional challenge that different conformations of each diastereomer may be present and these need to be differentiated from the diastereomers in the spectral analysis. Broadband rotational spectra of several larger molecules have been measured using a chirped-pulse FT-MRR spectrometer. Measurements of nootkatone (C15H22O), cedrol (C15H26O), ambroxide (C16H28O) and sclareolide (C16H26O2) are presented. These spectra are measured with high sensitivity (signal-to-noise ratio near 1,000:1) and permit structure determination of the most populated isomers using isotopic analysis of the 13C and 18O isotopologues in natural abundance. The accuracy of quantum chemistry calculations to identify diastereomers and conformers and to predict the dipole moment properties needed for three wave mixing measurements is examined.

  4. 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)

  5. Excited-State Dynamics of a DNA Duplex in a Deep Eutectic Solvent Probed by Femtosecond Time-Resolved IR Spectroscopy.

    Science.gov (United States)

    de La Harpe, Kimberly; Kohl, Forrest R; Zhang, Yuyuan; Kohler, Bern

    2018-03-08

    To better understand how the solvent influences excited-state deactivation in DNA strands, femtosecond time-resolved IR (fs-TRIR) pump-probe measurements were performed on a d(AT) 9 ·d(AT) 9 duplex dissolved in a deep eutectic solvent (DES) made from choline chloride and ethylene glycol in a 1:2 mol ratio. This solvent, known as ethaline, is a member of a class of ionic liquids capable of solubilizing DNA with minimal disruption to its secondary structure. UV melting analysis reveals that the duplex studied here melts at 18 °C in ethaline compared to 50 °C in aqueous solution. Ethaline has an excellent transparency window that facilitates TRIR measurements in the double-bond stretching region. Transient spectra recorded in deuterated ethaline at room temperature indicate that photoinduced intrastrand charge transfer occurs from A to T, yielding the same exciplex state previously detected in aqueous solution. This state decays via charge recombination with a lifetime of 380 ± 10 ps compared to the 300 ± 10 ps lifetime measured earlier in D 2 O solution. The TRIR data strongly suggest that the long-lived exciplex forms exclusively in the solvated duplex, and not in the denatured single strands, which appear to have little, if any, base stacking. The longer lifetime of the exciplex state in the DES compared to aqueous solution is suggested to arise from reduced stabilization of the charge transfer state, resulting in slower charge recombination on account of Marcus inverted behavior.

  6. Vibrational spectrum of the K-590 intermediate in the bacteriorhodopsin photocycle at room temperature: picosecond time-resolved resonance coherent anti-Raman spectroscopy

    Science.gov (United States)

    Ujj, L.; Jäger, F.; Popp, A.; Atkinson, G. H.

    1996-12-01

    The vibrational spectrum of the K-590 intermediate, thought to contribute significantly to the energy storage and transduction mechanism in the bacteriorhodopsin (BR) photocycle, is measured at room temperature using picosecond time-resolved resonance coherent anti-Stokes Raman scattering (PTR/CARS). The room-temperature BR photocycle is initiated by the 3 ps, 570 nm excitation of the ground-state species, BR-570, prepared in both H 2O and D 2O suspensions of BR. PTR/CARS data, recorded 50 ps after BR-570 excitation, at which time only BR-570 and K-590 are present, have an excellent S/N which provides a significantly more detailed view of the K-590 vibrational degrees of freedom than previously available. Two picosecond (6 ps FWHM) laser pulses, ω1 (633.4 nm) and ωS (675-700 nm), are used to record PTR/CARS data via electronic resonance enhancement in both BR-570 and K-590, each of which contains a distinct retinal structure (assigned as 13- rans, 15- anti, 13- cis, respectively). To obtain the vibrational spectrum of K-590 separately, the PTR/CARS spectra from the mixture of isomeric retinals is quantitatively analyzed in terms of third-order susceptibility ( η(3)) relationships. PTR/CARS spectra of K-590 recorded from both H 2O and D 2O suspensions of BR are compared with the analogous vibrational data obtained via spontaneous resonance Raman (RR) scattering at both low (77 K) and room temperature. Analyses of these vibrational spectra identify temperature-dependent effects and changes assignable to the substitution of deuterium at the Schiff-base nitrogen not previously reported.

  7. 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...

  8. 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.

  9. 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

  10. 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

  11. 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 ; The oretical Chemistry Impact factor: 2.861, year: 2010

  12. 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 - others: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

  13. Time-resolved terahertz spectroscopy reveals the influence of charged sensitizing quantum dots on the electron dynamics in ZnO

    Czech Academy of Sciences Publication Activity Database

    Bamini, S.N.; Němec, Hynek; Žídek, Karel; Abdellah, M.; Al-Marri, M.J.; Chábera, P.; Ponseca, C.; Zheng, K.; Pullerits, T.

    2017-01-01

    Roč. 19, č. 8 (2017), s. 6006-6012 ISSN 1463-9076 R&D Projects: GA ČR GA17-03662S Institutional support: RVO:68378271 ; RVO:61389021 Keywords : sensitized semiconductors * ultrafast dynamics * terahertz spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism OBOR OECD: Condensed matter physics (including formerly solid state physics , supercond.) Impact factor: 4.123, year: 2016

  14. Relaxations and fast dynamics of the plastic crystal cyclo-octanol investigated by broadband dielectric spectroscopy

    OpenAIRE

    Lunkenheimer, Peter

    1997-01-01

    Relaxations and fast dynamics of the plastic crystal cyclo-octanol investigated by broadband dielectric spectroscopy / R. Brand, P. Lunkenheimer, A. Loidl. - In: Physical review. B. 56. 1997. S. R5713-R5716

  15. Semiconductor Nonlinear Dynamics Study by Broadband Terahertz Spectroscopy

    Science.gov (United States)

    Ho, I.-Chen

    Semiconductor nonlinearity in the terahertz (THz) frequency range has been attracting considerable attention due to the recent development of high-power semiconductor-based nanodevices. However, the underlying physics concerning carrier dynamics in the presence of high-field THz transients is still obscure. This thesis introduces an ultrafast, time-resolved THz pump/THz probe approach to the study of semiconductor properties in the nonlinear regime. The carrier dynamics regarding two mechanisms, intervalley scattering and impact ionization, is observed for doped InAs on a sub-picosecond time scale. In addition, polaron modulation driven by intense THz pulses is experimentally and theoretically investigated. The observed polaron dynamics verifies the interaction between energetic electrons and a phonon field. In contrast to previous work which reports optical phonon responses, acoustic phonon modulations are addressed in this study. A further understanding of the intense field interacting with solid materials will accelerate the development of semiconductor devices. This thesis starts with the design and performance of a table-top THz spectrometer which has the advantages of ultra-broad bandwidth (one order higher bandwidth compared to a conventional ZnTe sensor) and high electric field strength (>100 kV/cm). Unlike the conventional THz time-domain spectroscopy, the spectrometer integrates a novel THz air-biased-coherent-detection (THz-ABCD) technique and utilizes selected gases as THz emitters and sensors. In comparison with commonly used electro-optic (EO) crystals or photoconductive (PC) dipole antennas, the gases have the benefits of no phonon absorption as existing in EO crystals and no carrier life time limitation as observed in PC dipole antennas. The newly development THz-ABCD spectrometer with a strong THz field strength capability provides a platform for various research topics especially on the nonlinear carrier dynamics of semiconductors. Two mechanisms

  16. Femtosecond time-resolved optical and Raman spectroscopy of photoinduced spin crossover: temporal resolution of low-to-high spin optical switching.

    Science.gov (United States)

    Smeigh, Amanda L; Creelman, Mark; Mathies, Richard A; McCusker, James K

    2008-10-29

    A combination of femtosecond electronic absorption and stimulated Raman spectroscopies has been employed to determine the kinetics associated with low-spin to high-spin conversion following charge-transfer excitation of a FeII spin-crossover system in solution. A time constant of tau = 190 +/- 50 fs for the formation of the 5T2 ligand-field state was assigned based on the establishment of two isosbestic points in the ultraviolet in conjunction with changes in ligand stretching frequencies and Raman scattering amplitudes; additional dynamics observed in both the electronic and vibrational spectra further indicate that vibrational relaxation in the high-spin state occurs with a time constant of ca. 10 ps. The results set an important precedent for extremely rapid, formally forbidden (DeltaS = 2) nonradiative relaxation as well as defining the time scale for intramolecular optical switching between two electronic states possessing vastly different spectroscopic, geometric, and magnetic properties.

  17. Time-resolved measurement of emission profiles in pulsed radiofrequency glow discharge optical emission spectroscopy: Investigation of the pre-peak

    International Nuclear Information System (INIS)

    Alberts, D.; Horvath, P.; Nelis, Th.; Pereiro, R.; Bordel, N.; Michler, J.; Sanz-Medel, A.

    2010-01-01

    Radiofrequency glow discharge coupled to optical emission spectroscopy has been used in pulsed mode in order to perform a detailed study of the measured temporal emission profiles for a wide range of copper transitions. Special attention has been paid to the early emission peak (or so-called pre-peak), observed at the beginning of the emission pulse profile. The effects of the important pulse parameters such as frequency, duty cycle, pulse width and power-off time, have been studied upon the Cu pulse emission profiles. The influence of discharge parameters, such as pressure and power, was studied as well. Results have shown that the intensity observed in the pre-peak can be 10 times as large as the plateau value for resonant lines and up to 5 times in case of transitions to the metastable levels. Increasing pressure or power increased the pre-peak intensity while its appearance in time changed. The pre-peak decreased when the discharge off-time was shorter than 100 μs. According to such results, the presence of the pre-peak could be probably due to the lack of self-absorption during the first 50 μs, and not to the ignition of the plasma. Under the selected operation conditions, the use of the pre-peak emission as analytical signals increases the linearity of calibration curves for resonant lines subjected to self-absorption at high concentrations.

  18. Time-resolved measurement of emission profiles in pulsed radiofrequency glow discharge optical emission spectroscopy: Investigation of the pre-peak

    Energy Technology Data Exchange (ETDEWEB)

    Alberts, D. [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain); Horvath, P. [Swiss Federal Laboratories for Materials Testing and Research (EMPA), Feuerwerkerstrasse 39, 3602 Thun (Switzerland); Nelis, Th. [LAPLACE, Universite Paul Sabatier, 118 rte de Narbonne, Bat3R2, 31062 Toulouse Cedex (France); CU Jean Francois Champollion, Place de Verdun 81012 Albi Cedex 9 (France); Pereiro, R. [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain); Bordel, N. [Department of Physics, Faculty of Science, University of Oviedo, Calvo Sotelo, 33007 Oviedo (Spain); Michler, J. [Swiss Federal Laboratories for Materials Testing and Research (EMPA), Feuerwerkerstrasse 39, 3602 Thun (Switzerland); Sanz-Medel, A., E-mail: asm@uniovi.e [Department of Physical and Analytical Chemistry, Faculty of Chemistry, University of Oviedo, Julian Claveria 8, 33006 Oviedo (Spain)

    2010-07-15

    Radiofrequency glow discharge coupled to optical emission spectroscopy has been used in pulsed mode in order to perform a detailed study of the measured temporal emission profiles for a wide range of copper transitions. Special attention has been paid to the early emission peak (or so-called pre-peak), observed at the beginning of the emission pulse profile. The effects of the important pulse parameters such as frequency, duty cycle, pulse width and power-off time, have been studied upon the Cu pulse emission profiles. The influence of discharge parameters, such as pressure and power, was studied as well. Results have shown that the intensity observed in the pre-peak can be 10 times as large as the plateau value for resonant lines and up to 5 times in case of transitions to the metastable levels. Increasing pressure or power increased the pre-peak intensity while its appearance in time changed. The pre-peak decreased when the discharge off-time was shorter than 100 {mu}s. According to such results, the presence of the pre-peak could be probably due to the lack of self-absorption during the first 50 {mu}s, and not to the ignition of the plasma. Under the selected operation conditions, the use of the pre-peak emission as analytical signals increases the linearity of calibration curves for resonant lines subjected to self-absorption at high concentrations.

  19. Characterization of Microsolvated Crown Ethers from Broadband Rotational Spectroscopy

    Science.gov (United States)

    Perez, Cristobal; Schnell, Melanie; Blanco, Susana; Lopez, Juan Carlos

    2016-06-01

    Since they were first synthetized, crown ethers have been extensively used in organometallic chemistry due to their unparalleled binding selectivity with alkali metal cations. From a structural point of view, crown ethers are heterocycles containing oxygen and/or other heteroatoms, although the most common ones are formed from ethylene oxide unit. Crown ethers are conventionally seen as being hydrophilic inside and hydrophobic outside when the structures found for the metal cation complexes are considered. However, crown ethers are extremely flexible and in isolation may present a variety of stable conformations so that their structure may be easily adapted in presence of a strong ligand as an alkali metal cation minimize the energy of the resulting complex. Water can be considered a soft ligand which interacts with crown ethers through moderate hydrogen bonds. It is thus interesting to investigate which conformers are selected by water to form complexes, the preferred interaction sites and the possible conformational changes due to the presence of one or more water molecules. Previous studies identified microsolvated crown ethers but in all cases with a chromophore group attached to the structure. Here we present a broadband rotational spectroscopy study of microsolvated crown ethers produced in a pulsed molecular jet expansion. Several 1:1 and 1:2 crown ether:water aggregates are presented for 12-crown-4, 15-crown-5 and 18-crown-6. Unambiguous identification of the structures has been achieved using isotopic substitution within the water unit. The subtle changes induced in the structures of the crown ether monomer upon complexation and the hydrogen-bonding network that hold them together will be also discussed. F. Gámez, B. Martínez-Haya, S. Blanco,J. C. López and J. L. Alonso, Phys. Chem. Chem. Phys. 2014, 14 12912-12918 V. A. Shubert, C.W. Müller and T. Zwier, J. Phys. Chem. A 2009, 113 8067-8079

  20. The electronically excited states of LH2 complexes from Rhodopseudomonas acidophila strain 10050 studied by time-resolved spectroscopy and dynamic Monte Carlo simulations. I. Isolated, non-interacting LH2 complexes.

    Science.gov (United States)

    Pflock, Tobias J; Oellerich, Silke; Southall, June; Cogdell, Richard J; Ullmann, G Matthias; Köhler, Jürgen

    2011-07-21

    We have employed time-resolved spectroscopy on the picosecond time scale in combination with dynamic Monte Carlo simulations to investigate the photophysical properties of light-harvesting 2 (LH2) complexes from the purple photosynthetic bacterium Rhodopseudomonas acidophila. The variations of the fluorescence transients were studied as a function of the excitation fluence, the repetition rate of the excitation and the sample preparation conditions. Here we present the results obtained on detergent solubilized LH2 complexes, i.e., avoiding intercomplex interactions, and show that a simple four-state model is sufficient to grasp the experimental observations quantitatively without the need for any free parameters. This approach allows us to obtain a quantitative measure for the singlet-triplet annihilation rate in isolated, noninteracting LH2 complexes.

  1. Positron annihilation response and broadband dielectric spectroscopy: salol.

    Science.gov (United States)

    Bartoš, J; Iskrová, M; Köhler, M; Wehn, R; Sauša, O; Lunkenheimer, P; Krištiak, J; Loidl, A

    2011-09-01

    A phenomenological analysis of the ortho-positronium (o-Ps) annihilation from positron annihilation lifetime spectroscopy (PALS) and the dynamics from broadband dielectric spectroscopy (BDS) are reported on a small molecular glass former of intermediate H-bonding and fragility: salol. The dielectric spectra extend over a very broad frequency range of about 2 × 10(-2)-3.5 × 10(11) Hz, providing information on the α-relaxation, the secondary relaxation giving rise to the excess wing, and the shallow high-frequency minimum in the micro- to milli-meter wave range. A number of empirical correlations between the o-Ps lifetime, τ(3)(T), and the various spectral and relaxation features have been observed. Thus, the phenomenological evaluation of the τ(3)(T) dependence of the PALS response of the amorphous sample reveals three characteristic PALS temperatures: T(g)(PALS), T(b1)(L) = 1.15T(g)(PALS) and T(b2)(L) = 1.25T(g)(PALS), which are discussed in relation to similar findings for some typical small molecular vdW- and H-bonded glass formers. A slighter change of the slope at T(b1)(L) appears to be related to the transition from excess wing to the primary α-process-dominated behavior, with the secondary process dominating in the deeply supercooled liquid state below T(b1)(L). The high-temperature plateau effect in the τ (3)(T) plot occurs at T(b2)(L) and agrees with the characteristic Stickel temperature, T(B)(ST), marking a qualitative change of the primary α process, but it does not follow the relation T(b2)(L) application of the two-order parameter (TOP) model to the structural relaxation as represented by the primary α relaxation times from BDS leads to the characteristic TOP temperature, T(m)(c), close to T(b1) from PALS. Within this model the phenomenological interpretation is offered based on changes in the probability of occurrence of solid-like and liquid-like domains to explain the dynamic as well as PALS responses. In summary, all the empirical

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

    Science.gov (United States)

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

    2015-04-21

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

  3. Multicomponent gas analysis using broadband quantum cascade laser spectroscopy

    NARCIS (Netherlands)

    Reyes Reyes, A.; Hou, Z.; Van Mastrigt, E.; Horsten, R.C.; De Jongste, J.C.; 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

  4. 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)

  5. Complexation of Cm(III) and Eu(III) with 2,6-bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine and 2-bromohexanoic acid studied by time-resolved laser fluorescence spectroscopy

    International Nuclear Information System (INIS)

    Bremer, A.; Panak, P.J.; Heidelberg Univ.; Geist, A.

    2013-01-01

    The complexation of Cm(III) and Eu(III) with 2,6-bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine (C5-BPP) and 2-bromohexanoic acid as lipophilic anion has been investigated by time-resolved laser fluorescence spectroscopy. Upon increasing ligand concentration three different Cm(III)-C5-BPP species with emission bands at 604.1 nm, 607.9 nm and 611.4 nm, respectively, are found and attributed to complexes with one, two and three C5-BPP molecules in the inner coordination sphere. Comparison with results of TRLFS experiments without 2-bromohexanoic acid shows that the C5-BPP ligand is able to completely displace the lipophilic anion from the inner coordination sphere, forming [Cm(C5-BPP) 3 ] 3+ complexes. This complex is also found in the organic phase of an extraction experiment performed with Cm(III), demonstrating that the lipophilic anion required for the extraction is not directly coordinated to the metal ion in the species formed during extraction. In case of Eu(III) the number of different species formed cannot be determined accurately. Nevertheless, the formation of the complex [EU(C5-BPP) 3 ] 3+ in the presence of 2-bromohexanoic acid is confirmed. (orig.)

  6. Broadband dielectric and conductivity spectroscopy of inhomogeneous and composite conductors

    Czech Academy of Sciences Publication Activity Database

    Petzelt, Jan; Nuzhnyy, Dmitry; Bovtun, Viktor; Savinov, Maxim; Kempa, Martin; Rychetský, Ivan

    2013-01-01

    Roč. 210, č. 11 (2013), s. 2259-2271 ISSN 1862-6300 R&D Projects: GA ČR GAP204/12/0232; GA MŠk LD12025 Institutional support: RVO:68378271 Keywords : effective medium approximation * infrared spectroscopy * THz spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.525, year: 2013

  7. Broadband sample holder for microwave spectroscopy of superconducting qubits

    International Nuclear Information System (INIS)

    Averkin, A. S.; Karpov, A.; Glushkov, E.; Abramov, N.; Shulga, K.; Huebner, U.; Il'ichev, E.; Ustinov, A. V.

    2014-01-01

    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 mm 2 . 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

  8. Analysis of co-eluted isomers of high-molecular weight polycyclic aromatic hydrocarbons in high performance liquid chromatography fractions via solid-phase nanoextraction and time-resolved Shpol'skii spectroscopy.

    Science.gov (United States)

    Wilson, Walter B; Campiglia, Andres D

    2011-09-28

    We present an accurate method for the determination of isomers of high-molecular weight polycyclic aromatic hydrocarbons co-eluted in HPLC fractions. The feasibility of this approach is demonstrated with two isomers of molecular weight 302 with identical mass fragmentation patterns, namely dibenzo[a,i]pyrene and naphtho[2,3-a]pyrene. Qualitative and quantitative analysis is carried out via laser-excited time-resolved Shpol'skii spectroscopy at liquid helium temperature. Unambiguous identification of co-eluted isomers is based on their characteristic 4.2 K line-narrowed spectra in n-octane as well as their fluorescence lifetimes. Pre-concentration of HPLC fractions prior to spectroscopic analysis is performed with the aid of gold nanoparticles via an environmentally friendly procedure. In addition to the two co-eluted isomers, the analytical figures of merit of the entire procedure were evaluated with dibenzo[a,l]pyrene, dibenzo[a,h]pyrene and dibenzo[a,e]pyrene. The analytical recoveries from drinking water samples varied between 98.2±5.5 (dibenzo[a,l]pyrene) and 102.7±3.2% (dibenzo[a,i]pyrene). The limits of detection ranged from 51.1 ng L(-1) (naphtho[2,3-a]pyrene) to 154 ng L(-1) (dibenzo[a,e]pyrene). The excellent analytical figures of merit associated to its HPLC compatibility makes this approach an attractive alternative for the analysis of co-eluted isomers with identical mass spectra. Copyright © 2011 Elsevier B.V. All rights reserved.

  9. Broadband dielectric spectroscopy of inhomogeneous and composite weak conductors

    Czech Academy of Sciences Publication Activity Database

    Petzelt, Jan; Nuzhnyy, Dmitry

    2016-01-01

    Roč. 89, 7-8 (2016), 651-666 ISSN 0141-1594 R&D Projects: GA ČR GA15-08389S Institutional support: RVO:68378271 Keywords : dielectric spectroscopy * effective medium approximation * coreshell composite * giant permittivity effects * negative permittivity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.060, year: 2016

  10. Broadband terahertz spectroscopy: principles, fundamental research and potential for industrial applications

    International Nuclear Information System (INIS)

    Zouaghi, W; Thomson, M D; Rabia, K; Hahn, R; Blank, V; Roskos, H G

    2013-01-01

    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)

  11. Frequency-comb-assisted broadband precision spectroscopy with cascaded diode lasers

    DEFF Research Database (Denmark)

    Liu, Junqiu; Brasch, Victor; Pfeiffer, Martin H. P.

    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 us to extend the measurement bandwidth to 37.4 THz (1355-1630 nm) at megahertz 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 us to characterize the dispersion...

  12. Time-resolved photoelectron spectrometry of a dephasing process in pyrazine

    International Nuclear Information System (INIS)

    Pavlov, R.L.; Pavlov, L.I.; Delchev, Ya.I.; Pavlova, S.I.

    2001-01-01

    The first femtosecond time-resolved photoelectron imaging (PEI) is presented. The method is characterized by photoionization of NO and further applied to ultrafast dephasing in pyrazine. Intermediate case behaviour in radiationless transition is clearly observed in time-resolved photoelectron kinetic energy distribution. Femtosecond PEI is with much improved efficiency than conventional photoelectron spectroscopies. It is anticipated that the unifield approach of time-resolved photoelectron and photoion imaging opens the possibility of observing photon-induced dynamics in real time

  13. Kinetics and branching ratios of the reactions NH2+NO2->N2O+H2O and NH2+NO2->H2NO+NO studied by pulse radiolysis combined with time-resolved infrared diode laser spectroscopy

    DEFF Research Database (Denmark)

    Meunier, H.; Pagsberg, Palle Bjørn; Sillesen, A.

    1996-01-01

    studied by monitoring the decay of NH2 and the simultaneous formation of N2O and NO by time-resolved infrared diode laser spectroscopy. The decay rate of NH2 was studied as a function of NO2 concentration to obtain an overall rate constant k(NH2 + NO2) = (1.35 +/- 0.15) X 10(-11) molecule(-1) cm(3) s(-1...

  14. Underresolved absorption spectroscopy of OH radicals in flames using broadband UV LEDs

    Science.gov (United States)

    White, Logan; Gamba, Mirko

    2018-04-01

    A broadband absorption spectroscopy diagnostic based on underresolution of the spectral absorption lines is evaluated for the inference of species mole fraction and temperature in combustion systems from spectral fitting. The approach uses spectrally broadband UV light emitting diodes and leverages low resolution, small form factor spectrometers. Through this combination, the method can be used to develop high precision measurement sensors. The challenges of underresolved spectroscopy are explored and addressed using spectral derivative fitting, which is found to generate measurements with high precision and accuracy. The diagnostic is demonstrated with experimental measurements of gas temperature and OH mole fraction in atmospheric air/methane premixed laminar flat flames. Measurements exhibit high precision, good agreement with 1-D flame simulations, and high repeatability. A newly developed model of uncertainty in underresolved spectroscopy is applied to estimate two-dimensional confidence regions for the measurements. The results of the uncertainty analysis indicate that the errors in the outputs of the spectral fitting procedure are correlated. The implications of the correlation between uncertainties for measurement interpretation are discussed.

  15. Broadband integrated mid infrared light sources as enabling technology for point of care mid-infrared spectroscopy

    Science.gov (United States)

    2017-08-20

    AFRL-AFOSR-JP-TR-2017-0061 Broadband integrated mid-infrared light sources as enabling technology for point-of-care mid- infrared spectroscopy Alex...mid-infrared light sources as enabling technology for point-of-care mid-infrared spectroscopy 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA2386-16-1-4037...Broadband integrated mid-infrared light sources as enabling technology for point-of-care mid- infrared spectroscopy ” Date: 16th August 2017 Name

  16. 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 ke...

  17. 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

  18. 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

    -domain spectrometer employing air-photonics for the generation and detection of single-cycle sub-50 fs THz transients. The time domain measurements provide direct access to both the absorption and refractive index spectra. The polymers LDPE and TOPAS® demonstrate negligible absorption and spectrally-flat refractive...... index across the entire spectroscopy window, revealing the high potential of these polymers for applications in THz photonics such as ultra-broadband polymer-based dielectric mirrors, waveguides, and fibers. Resonant high-frequency polar vibrational modes are observed and assigned in polymers PA6...... and PTFE, and their dielectric functions in the complete frequency window 2-15 THz are theoretically reproduced. Our results demonstrate the potential of ultrabroadband air-photonics-based THz time domain spectroscopy as a valuable analytic tool for materials science....

  19. Interest in broadband dielectric spectroscopy to study the electronic transport in materials for lithium batteries

    Energy Technology Data Exchange (ETDEWEB)

    Badot, Jean-Claude, E-mail: jc.badot@chimie-paristech.fr [Institut de Recherche de Chimie Paris, UMR CNRS 8247, Réseau sur le Stockage Electrochimique de l' Energie (RS2E), Chimie Paris Tech, PSL*, 11 rue P. et M. Curie, 75231 Cedex 05 Paris (France); Lestriez, Bernard [Institut des Matériaux Jean Rouxel, UMR CNRS 6502, Université de Nantes, 2 rue de la Houssinière, BP32229, 44322 Nantes (France); Dubrunfaut, Olivier [GeePs | Group of electrical engineering – Paris, UMR CNRS 8507, CentraleSupélec, Univ. Paris-Sud, Université Paris-Saclay, Sorbonne Universités, UPMC Univ Paris 06, 3 & 11 rue Joliot-Curie, Plateau de Moulon, 91192 Gif-sur-Yvette CEDEX, Paris (France)

    2016-11-15

    Highlights: • Broadband dielectric spectroscopy measures the multiscale electronic conductivity from macroscopic to interatomic sizes. • There is an influence of the surface states on the electronic transfer of powdered materials (e.g. thin insulating layer of Li{sub 2}CO{sub 3} on LiNiO{sub 2} and carbon coating on LiFePO{sub 4}). • Electrical relaxations resulting from the interfacial polarizations at the different scales of the carbon black network are evidenced. - Abstract: Broadband dielectric spectroscopy (BDS) is used to measure complex permittivity and conductivity of conducting materials for lithium batteries at frequencies from a few Hz to several GHz with network and impedance analysers. Under the influence of an electric field, there will be charge density fluctuations in the conductor mainly due to electronic transfer. These fluctuations result in dielectric relaxations for frequencies below 100 GHz. The materials are compacted powders in which each element (particles, agglomerates of particles) can have different sizes and morphologies. In the present review, studies are reported on the influence of surface states in LiNiO{sub 2} (ageing and degradation in air) and LiFePO{sub 4} (carbon coating thin layer), and on a composite electrode based on the lithium trivanadate (Li{sub 1.1}V{sub 3}O{sub 8}) active material. The results have shown that the BDS technique is very sensitive to the different scales of materials architectures involved in electronic transport, from interatomic distances to macroscopic sizes.

  20. Broadband spectroscopy of magnetic response in a nano-scale magnetic wire

    International Nuclear Information System (INIS)

    Yamaguchi, A.; Motoi, K.; Miyajima, H.; Utsumi, Y.

    2014-01-01

    We measure the broadband spectra of magnetic response in a single layered ferromagnetic nano-scale wire in order to investigate the size effect on the ferromagnetic resonance. We found that the resonance frequency difference between 300-nm- and 5-μm-wide wires was varied by about 5 GHz due to the shape anisotropy. Furthermore, we experimentally detected the magnetization precession induced by the thermal fluctuation via the rectification of a radio-frequency (rf) current by incorporating an additional direct current (dc) by using Wheatstone bridge circuit. Our investigation renders that the shape anisotropy is of great importance to control the resonance frequency and to provide thermal stability of the microwave devices. - Highlights: • We describe an experimental investigation of the magnetic response of a single layered ferromagnetic nano-scale wire. • We present the conventional broadband microwave spectroscopy with a vector network analyzer and rectifying spectroscopy obtained with a Wheatstone bridge technique. • The investigation enables us to characterize the size effect on the ferromagnetic response and also to detect the magnetization precession induced by the thermal fluctuations

  1. Interest in broadband dielectric spectroscopy to study the electronic transport in materials for lithium batteries

    International Nuclear Information System (INIS)

    Badot, Jean-Claude; Lestriez, Bernard; Dubrunfaut, Olivier

    2016-01-01

    Highlights: • Broadband dielectric spectroscopy measures the multiscale electronic conductivity from macroscopic to interatomic sizes. • There is an influence of the surface states on the electronic transfer of powdered materials (e.g. thin insulating layer of Li_2CO_3 on LiNiO_2 and carbon coating on LiFePO_4). • Electrical relaxations resulting from the interfacial polarizations at the different scales of the carbon black network are evidenced. - Abstract: Broadband dielectric spectroscopy (BDS) is used to measure complex permittivity and conductivity of conducting materials for lithium batteries at frequencies from a few Hz to several GHz with network and impedance analysers. Under the influence of an electric field, there will be charge density fluctuations in the conductor mainly due to electronic transfer. These fluctuations result in dielectric relaxations for frequencies below 100 GHz. The materials are compacted powders in which each element (particles, agglomerates of particles) can have different sizes and morphologies. In the present review, studies are reported on the influence of surface states in LiNiO_2 (ageing and degradation in air) and LiFePO_4 (carbon coating thin layer), and on a composite electrode based on the lithium trivanadate (Li_1_._1V_3O_8) active material. The results have shown that the BDS technique is very sensitive to the different scales of materials architectures involved in electronic transport, from interatomic distances to macroscopic sizes.

  2. Deflection evaluation using time-resolved radiography

    International Nuclear Information System (INIS)

    Fry, D.A.; Lucero, J.P.

    1990-01-01

    Time-resolved radiography is the creation of an x-ray image for which both the start-exposure and stop-exposure times are known with respect to the event under study. The combination of image and timing are used to derive information about the event. The authors have applied time-resolved radiography to evaluate motions of explosive-driven events. In the particular application discussed in this paper, the author's intent is to measure maximum deflections of the components involved. Exposures are made during the time just before to just after the event of interest occurs. A smear or blur of motion out to its furthest extent is recorded on the image. Comparison of the dynamic images with static images allows deflection measurements to be made

  3. 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.

  4. Time-resolved studies. Ch. 9

    International Nuclear Information System (INIS)

    Mills, Dennis M.; Argonne National Lab., IL

    1991-01-01

    Synchrotron radiation, with its unique properties, offers 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. Wide-bandpass 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 'parallel data collection' 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 data-collection time. Perhaps the most exciting advances in time-resolved X-ray studies will be made by those methods that exploit the pulsed nature of the radiation emitted from storage rings. Pulsed techniques have had an enormous impact in the study of the temporal evolution of transient phenomena. The extension from continuous to modulated sources for use in time-resolved work has been carried over in a host of fields that use both pulsed particle and pulsed electro-magnetic beams. In this chapter the new experimental techniques are reviewed and illustrated with some experiments. (author). 98 refs.; 20 figs.; 5 tabs

  5. Time-resolved x-ray diagnostics

    International Nuclear Information System (INIS)

    Lyons, P.B.

    1981-01-01

    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

  6. Broadband Dielectric Spectroscopy and Quasi-Elastic Neutron Scattering on Single-Ion Polymer Conductors

    Science.gov (United States)

    Soles, Christopher; Peng, Hua-Gen; Page, Kirt; Snyder, Chad; Pandy, Ashoutosh; Jeong, Youmi; Runt, James; NIST Collaboration; Pennsylvania Collaboration

    2011-03-01

    The application of solid polymer electrolytes in rechargeable batteries has not been fully realized after decades of research due to its low conductivity. Dramatic increases of the ion conductivity are needed and this progress requires the understanding of conduction mechanism. We address this topic in two fronts, namely, the effect of plasticizer additives and geometric confinement on the charge transfer mechanism. To this end, we combine broadband dielectric spectroscopy (BDS) to characterize the ion mobility and quasi-elastic neutron scattering (QENS) to quantify segmental motion on a single-ion model polymer electrolyte. Deuterated small molecules were used as plasticizers so that the segmental motion of the polymer electrolyte could be monitored by QENS to understand the mechanism behind the increased conductivity. Anodic aluminum oxide (AAO) membranes with well defined channel sizes are used as the matrix to study the transport of ions solvated in a 1D polymer electrolyte.

  7. 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)

    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 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

  8. 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

  9. Josephson admittance spectroscopy application for frequency analysis of broadband THz antennas

    International Nuclear Information System (INIS)

    Volkov, O Yu; Divin, Yu Yu; Gubankov, V N; Gundareva, I I; Pavlovskiy, V V

    2010-01-01

    Application of Josephson admittance spectroscopy for the spectral analysis of a broad-band log-periodic superconducting antenna was demonstrated at the frequency range from 50 to 700 GHz. The [001]-tilt YBa 2 Cu 3 O 7-x bicrystal Josephson junctions, integrated with sinuous log-periodic YBa 2 Cu 3 O 7-x antennas, were fabricated on NdGaO 3 bicrystal substrates. A real part of the antenna admittance ReY(f) as a function of the frequency f was reconstructed from the modification of the dc current-voltage characteristic of the junction, induced by the antenna. Resonance features were observed in the recovered ReY(f)-spectra with a periodicity in the logarithmic frequency scale, corresponding to log-periodic geometry of the antenna. The ReY(f)-spectra, recovered by Josephson spectroscopy, were compared with the ReY(f)-spectra, obtained by CAD simulation, and both spectra were shown to be similar in their main features. A value of 23 was obtained for an effective permittivity of the NdGaO3 bicrystal substrates by fitting simulated data to those obtained from Josephson spectroscopy.

  10. 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.

  11. Ultra-Broadband Infrared Pulses from a Potassium-Titanyl Phosphate Optical Parametric Amplifier for VIS-IR-SFG Spectroscopy

    Science.gov (United States)

    Isaienko, Oleksandr; Borguet, Eric

    A non-collinear KTP-OPA to provide ultra-broadband mid-infrared pulses was designed and characterized. With proper pulse-front and phase correction, the system has a potential for high-time resolution vibrational VIS-IR-SFG spectroscopy.

  12. Femtosecond Time-resolved Optical Polarigraphy (FTOP)

    International Nuclear Information System (INIS)

    Aoshima, S.; Fujimoto, M.; Hosoda, M.; Tsuchiya, Y.

    2000-01-01

    A novel time-resolved imaging technique named FTOP (Femtosecond Time-resolved Optical Polarigraphy) for visualizing the ultrafast propagation dynamics of intense light pulses in a medium has been proposed and demonstrated. Femtosecond snapshot images can be created with a high spatial resolution by imaging only the polarization components of the probe pulse; these polarization components change due to the instantaneous birefringence induced by the pump pulse in the medium. Ultrafast temporal changes in the two-dimensional spatial distribution of the optical pulse intensity were clearly visualized in consecutive images by changing the delay between the pump and probe. We observe that several filaments appear and then come together before the vacuum focus due to nonlinear effects in air. We also prove that filamentation dynamics such as the formation position and the propagation behavior are complex and are strongly affected by the pump energy. The results collected clearly show that this method FTOP succeeds for the first time in directly visualizing the ultrafast dynamics of the self-modulated nonlinear propagation of light. (author)

  13. Time Resolved Deposition Measurements in NSTX

    International Nuclear Information System (INIS)

    Skinner, C.H.; Kugel, H.; Roquemore, A.L.; Hogan, J.; Wampler, W.R.

    2004-01-01

    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 2 of deposition, however surprisingly, 15.9 (micro)g/cm 2 of material loss occurred at 7 discharges. The net deposited mass of 13.3 (micro)g/cm 2 matched the mass of 13.5 (micro)g/cm 2 measured independently by ion beam analysis. Monte Carlo modeling suggests that transient processes are likely to dominate the deposition

  14. Time-resolved brightness measurements by streaking

    Science.gov (United States)

    Torrance, Joshua S.; Speirs, Rory W.; McCulloch, Andrew J.; Scholten, Robert E.

    2018-03-01

    Brightness is a key figure of merit for charged particle beams, and time-resolved brightness measurements can elucidate the processes involved in beam creation and manipulation. Here we report on a simple, robust, and widely applicable method for the measurement of beam brightness with temporal resolution by streaking one-dimensional pepperpots, and demonstrate the technique to characterize electron bunches produced from a cold-atom electron source. We demonstrate brightness measurements with 145 ps temporal resolution and a minimum resolvable emittance of 40 nm rad. This technique provides an efficient method of exploring source parameters and will prove useful for examining the efficacy of techniques to counter space-charge expansion, a critical hurdle to achieving single-shot imaging of atomic scale targets.

  15. Time-resolved measurements of luminescence

    Energy Technology Data Exchange (ETDEWEB)

    Collier, Bradley B. [Department of Biomedical Engineering, 408 Mechanical Engineering Office Building, Spence Street, Texas A and M University, College Station, TX 77843 (United States); McShane, Michael J., E-mail: mcshane@tamu.edu [Department of Biomedical Engineering, 408 Mechanical Engineering Office Building, Spence Street, Texas A and M University, College Station, TX 77843 (United States); Materials Science and Engineering Program, 408 Mechanical Engineering Office Building, Spence Street, Texas A and M University, College Station, TX 77843 (United States)

    2013-12-15

    Luminescence sensing and imaging has become more widespread in recent years in a variety of industries including the biomedical and environmental fields. Measurements of luminescence lifetime hold inherent advantages over intensity-based response measurements, and advances in both technology and methods have enabled their use in a broader spectrum of applications including real-time medical diagnostics. This review will focus on recent advances in analytical methods, particularly calculation techniques, including time- and frequency-domain lifetime approaches as well as other time-resolved measurements of luminescence. -- Highlights: • Developments in technology have led to widespread use of luminescence lifetime. • Growing interest for sensing and imaging applications. • Recent advances in approaches to lifetime calculations are reviewed. • Advantages and disadvantages of various methods are weighed. • Other methods for measurement of luminescence lifetime also described.

  16. Time-resolved measurements of luminescence

    International Nuclear Information System (INIS)

    Collier, Bradley B.; McShane, Michael J.

    2013-01-01

    Luminescence sensing and imaging has become more widespread in recent years in a variety of industries including the biomedical and environmental fields. Measurements of luminescence lifetime hold inherent advantages over intensity-based response measurements, and advances in both technology and methods have enabled their use in a broader spectrum of applications including real-time medical diagnostics. This review will focus on recent advances in analytical methods, particularly calculation techniques, including time- and frequency-domain lifetime approaches as well as other time-resolved measurements of luminescence. -- Highlights: • Developments in technology have led to widespread use of luminescence lifetime. • Growing interest for sensing and imaging applications. • Recent advances in approaches to lifetime calculations are reviewed. • Advantages and disadvantages of various methods are weighed. • Other methods for measurement of luminescence lifetime also described

  17. Time - resolved thermography at Tokamak T-10

    International Nuclear Information System (INIS)

    Grunow, C.; Guenther, K.; Lingertat, J.; Chicherov, V.M.; Evstigneev, S.A.; Zvonkov, S.N.

    1987-01-01

    Thermographic experiments were performed at T-10 tokamak to investigate the thermic coupling of plasma and the limiter. The limiter is an internal equipment of the vacuum vessel of tokamak-type fusion devices and the interaction of plasma with limiter results a high thermal load of limiter for short time. In according to improve the limiter design the temperature distribution on the limiter surface was measured by a time-resolved thermographic method. Typical isotherms and temperature increment curves are presented. This measurement can be used as a systematic plasma diagnostic method because the limiter is installed in the tokamak whereas special additional probes often disturb the plasma discharge. (D.Gy.) 3 refs.; 7 figs

  18. Kinetically controlled glass transition measurement of organic aerosol thin films using broadband dielectric spectroscopy

    Directory of Open Access Journals (Sweden)

    Y. Zhang

    2018-06-01

    Full Text Available Glass transitions from liquid to semi-solid and solid phase states have important implications for reactivity, growth, and cloud-forming (cloud condensation nuclei and ice nucleation capabilities of secondary organic aerosols (SOAs. The small size and relatively low mass concentration of SOAs in the atmosphere make it difficult to measure atmospheric SOA glass transitions using conventional methods. To circumvent these difficulties, we have adapted a new technique for measuring glass-forming properties of atmospherically relevant organic aerosols. Aerosol particles to be studied are deposited in the form of a thin film onto an interdigitated electrode (IDE using electrostatic precipitation. Dielectric spectroscopy provides dipole relaxation rates for organic aerosols as a function of temperature (373 to 233 K that are used to calculate the glass transition temperatures for several cooling or heating rates. IDE-enabled broadband dielectric spectroscopy (BDS was successfully used to measure the kinetically controlled glass transition temperatures of aerosols consisting of glycerol and four other compounds with selected cooling and heating rates. The glass transition results agree well with available literature data for these five compounds. The results indicate that the IDE-BDS method can provide accurate glass transition data for organic aerosols under atmospheric conditions. The BDS data obtained with the IDE-BDS technique can be used to characterize glass transitions for both simulated and ambient organic aerosols and to model their climate effects.

  19. Determining the nature of excitonic dephasing in high-quality GaN/AlGaN quantum wells through time-resolved and spectrally resolved four-wave mixing spectroscopy

    Science.gov (United States)

    Gallart, M.; Ziegler, M.; Crégut, O.; Feltin, E.; Carlin, J.-F.; Butté, R.; Grandjean, N.; Hönerlage, B.; Gilliot, P.

    2017-07-01

    Applying four-wave mixing spectroscopy to a high-quality GaN/AlGaN single quantum well, we report on the experimental determination of excitonic dephasing times at different temperatures and exciton densities in III-nitride heterostructures. By comparing the evolution with the temperature of the dephasing and the spin-relaxation rate, we conclude that both processes are related to the rate of excitonic collisions. When spin relaxation occurs in the motional-narrowing regime, it remains constant over a large temperature range as the spin-precession frequency increases linearly with temperature, hence compensating for the observed decrease in the dephasing time. From those measurements, a value of the electron-hole exchange interaction strength of 0.45 meV at T =10 K is inferred.

  20. Time resolved ion beam induced charge collection

    International Nuclear Information System (INIS)

    Sexton W, Frederick; Walsh S, David; Doyle L, Barney; Dodd E, Paul

    2000-01-01

    Under this effort, a new method for studying the single event upset (SEU) in microelectronics has been developed and demonstrated. Called TRIBICC, for Time Resolved Ion Beam Induced Charge Collection, this technique measures the transient charge-collection waveform from a single heavy-ion strike with a -.03db bandwidth of 5 GHz. Bandwidth can be expanded up to 15 GHz (with 5 ps sampling windows) by using an FFT-based off-line waveform renormalization technique developed at Sandia. The theoretical time resolution of the digitized waveform is 24 ps with data re-normalization and 70 ps without re-normalization. To preserve the high bandwidth from IC to the digitizing oscilloscope, individual test structures are assembled in custom high-frequency fixtures. A leading-edge digitized waveform is stored with the corresponding ion beam position at each point in a two-dimensional raster scan. The resulting data cube contains a spatial charge distribution map of up to 4,096 traces of charge (Q) collected as a function of time. These two dimensional traces of Q(t) can cover a period as short as 5 ns with up to 1,024 points per trace. This tool overcomes limitations observed in previous multi-shot techniques due to the displacement damage effects of multiple ion strikes that changed the signal of interest during its measurement. This system is the first demonstration of a single-ion transient measurement capability coupled with spatial mapping of fast transients

  1. Enzyme reactions and their time resolved measurements

    International Nuclear Information System (INIS)

    Hajdu, Janos

    1990-01-01

    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.)

  2. Time resolved ion beam induced charge collection

    Energy Technology Data Exchange (ETDEWEB)

    SEXTON,FREDERICK W.; WALSH,DAVID S.; DOYLE,BARNEY L.; DODD,PAUL E.

    2000-04-01

    Under this effort, a new method for studying the single event upset (SEU) in microelectronics has been developed and demonstrated. Called TRIBICC, for Time Resolved Ion Beam Induced Charge Collection, this technique measures the transient charge-collection waveform from a single heavy-ion strike with a {minus}.03db bandwidth of 5 GHz. Bandwidth can be expanded up to 15 GHz (with 5 ps sampling windows) by using an FFT-based off-line waveform renormalization technique developed at Sandia. The theoretical time resolution of the digitized waveform is 24 ps with data re-normalization and 70 ps without re-normalization. To preserve the high bandwidth from IC to the digitizing oscilloscope, individual test structures are assembled in custom high-frequency fixtures. A leading-edge digitized waveform is stored with the corresponding ion beam position at each point in a two-dimensional raster scan. The resulting data cube contains a spatial charge distribution map of up to 4,096 traces of charge (Q) collected as a function of time. These two dimensional traces of Q(t) can cover a period as short as 5 ns with up to 1,024 points per trace. This tool overcomes limitations observed in previous multi-shot techniques due to the displacement damage effects of multiple ion strikes that changed the signal of interest during its measurement. This system is the first demonstration of a single-ion transient measurement capability coupled with spatial mapping of fast transients.

  3. Interrogating the vibrational relaxation of highly excited polyatomics with time-resolved diode laser spectroscopy: C6H6, C6D6, and C6F6+CO2

    International Nuclear Information System (INIS)

    Sedlacek, A.J.; Weston, R.E. Jr.; Flynn, G.W.

    1991-01-01

    The vibrational relaxation of highly excited ground state benzene, benzene d 6 , and hexafluorobenzene by CO 2 has been investigated with high resolution diode laser spectroscopy. The vibrationally hot polyatomics are formed by single photon 248 nm excitation to the S 1 state followed by rapid radiationless transitions. It has been found that in all cases less than 1% of the energy initially present in the polyatomics is deposited into the high frequency mode of CO 2 (ν 3 ). An investigation of the CO 2 (00 0 1) nascent rotational distribution under single collision conditions reveals that very little rotational excitation accompanies vibrational energy transfer to the ν 3 mode. The CO 2 (ν 3 ) rotational states can be described by temperatures, T rot , as follows: C 6 H 6 , T rot =360±30 K; C 6 D 6 , T rot =350±35 K and C 6 F 6 , T rot =340±23 K. An estimate of left-angle ΔE right-angle ν3 , the mean energy transferred to the CO 2 ν 3 mode per collision, suggests that as the availability of low frequency modes in the excited molecule increases, less energy is deposited into the high frequency mode of CO 2 . Finally, evidence is presented suggesting that even at moderate laser fluences, the two-photon ionization of benzene can lead to substantial CO 2 ν 3 excitation via electron+CO 2 inelastic collisions

  4. Vibrational dynamics of aqueous hydroxide solutions probed using broadband 2DIR spectroscopy

    International Nuclear Information System (INIS)

    Mandal, Aritra; Tokmakoff, Andrei

    2015-01-01

    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

  5. 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.

  6. 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.

  7. Polymer chain dynamics in epoxy based composites as investigated by broadband dielectric spectroscopy

    Directory of Open Access Journals (Sweden)

    Mohammad K. Hassan

    2016-03-01

    Full Text Available Epoxy networks of the diglycidyl ether of bisphenol A (DGEBA were prepared using 3,3′- and 4,4′-diaminodiphenyl sulfone isomer crosslinkers. Secondary relaxations and the glass transitions of resultant networks were probed using broadband dielectric spectroscopy (BDS. A sub-Tg γ relaxation peak for both networks shifts to higher frequencies (f with increasing temperature in Arrhenius fashion, both processes having the same activation energy and being assigned to phenyl ring flipping in DGEBA chains. A β relaxation is assigned to local motions of dipoles that were created during crosslinking reactions. 4,4′-based networks exhibited higher Tg relative to 3,3′-based networks as per dynamic mechanical as well as BDS analyses. The Vogel–Fulcher–Tammann–Hesse equation fitted well to relaxation time vs. temperature data and comparison of Vogel temperatures suggests lower free volume per mass for the 3,3′-based network. The Kramers–Krönig transformation was used to directly calculate dc-free ɛ″ vs. f data from experimental ɛ′ vs. f data. Distribution of relaxation times (DRT curves are bi-modal for the 3,3′-crosslinked resin suggesting large-scale microstructural heterogeneity as opposed to homogeneity for the 4,4′-based network whose DRT consists of a single peak.

  8. Ultra-Broadband Two-Dimensional Electronic Spectroscopy and Pump-Probe Microscopy of Molecular Systems

    Science.gov (United States)

    Spokoyny, Boris M.

    Ultrafast spectroscopy offers an unprecedented view on the dynamic nature of chemical reactions. From charge transfer in semiconductors to folding and isomerization of proteins, these all important processes can now be monitored and in some instances even controlled on real, physical timescales. One of the biggest challenges of ultrafast science is the incredible energetic complexity of most systems. It is not uncommon to encounter macromolecules or materials with absorption spectra spanning significant portions of the visible spectrum. Monitoring a multitude of electronic and vibrational transitions, all dynamically interacting with each other on femtosecond timescales poses a truly daunting experimental task. The first part of this thesis deals with the development of a novel Two-Dimensional Electronic Spectroscopy (2DES) and its associated, advanced detection methodologies. Owing to its ultra-broadband implementation, this technique enables us to monitor femtosecond chemical dynamics that span the energetic landscape of the entire visible spectrum. In order to demonstrate the utility of our method, we apply it to two laser dye molecules, IR-144 and Cresyl Violet. Variation of photophysical properties on a microscopic scale in either man-made or naturally occurring systems can have profound implications on how we understand their macroscopic properties. Recently, inorganic hybrid perovskites have been tapped as the next generation solar energy harvesting materials. Their remarkable properties include low exciton binding energy, low exciton recombination rates and long carrier diffusion lengths. Nevertheless, considerable variability in device properties made with nearly identical preparation methods has puzzled the community. In the second part of this thesis we use non-linear pump probe microscopy to study the heterogeneous nature of femtosecond carrier dynamics in thin film perovskites. We show that the local morphology of the perovskite thin films has a

  9. Ultrafast photo-initiated molecular quantum dynamics in the DNA dinucleotide d(ApG) revealed by broadband transient absorption spectroscopy.

    Science.gov (United States)

    Stuhldreier, Mayra C; Temps, Friedrich

    2013-01-01

    The ultrafast photo-initiated quantum dynamics of the adenine-guanine dinucleotide d(ApG) in aqueous solution (pH 7) has been studied by femtosecond time-resolved spectroscopy after excitation at lambda = 260 nm. The results reveal a hierarchy of processes on time scales from tau 100 ps. Characteristic spectro-temporal signatures are observed indicating the transformation of the molecules in the electronic relaxation from the photo-excited state to a long-lived exciplex. In particular, broadband UV/VIS excited-state absorption (ESA) measurements detected a distinctive absorption by the excited dinucleotide around lambda = 335 nm, approximately 0.5 eV to the blue compared to the maximum of the broad and unstructured ESA spectrum after excitation of an equimolar mixture of the mononucleotides dAMP and dGMP. A similar feature has been identified as signature of the excimer in the dynamics of the adenine dinucleotide d(ApA). The lifetime of the d(ApG) exciplex was found to be tau = 124 +/- 4 ps both from the ESA decay time and from the ground-state recovery time, far longer than the sub-picosecond lifetimes of excited dAMP or dGMP. Fluorescence-time profiles measured by the up-conversion technique indicate that the exciplex state is reached around approximately 6 ps after excitation. Very weak residual fluorescence at longer times red-shifted to the emission from the photo-excited state shows that the exciplex is almost optically dark, but still has enough oscillator strength to give rise to the dual fluorescence of the dinucleotide in the static fluorescence spectrum.

  10. Broadband sub-THz spectroscopy modules integrated in 65-nm CMOS technology

    NARCIS (Netherlands)

    Matters-Kammerer, M.K.; van Goor, D.; Tripodi, L.

    2017-01-01

    The design and characterization of a broadband 20-480 GHz continuously tuneable on-chip spectrometer based on non-linear transmission lines in 65-nm CMOS technology is presented. The design procedure of the sampler that detects the ultra-broadband signal from the transmitter in time and frequency

  11. Toward noninvasive detection and monitoring of malaria with broadband diffuse optical spectroscopy

    Science.gov (United States)

    Campbell, Chris; Tromberg, Bruce J.; O'Sullivan, Thomas D.

    2018-02-01

    Despite numerous advances, malaria continues to kill nearly half a million people globally every year. New analytical methods and diagnostics are critical to understanding how treatments under development affect the lifecycle of malaria parasites. A biomarker that has been gaining interest is the "malaria pigment" hemozoin. This byproduct of hemoglobin digestion by the parasite has a unique spectral signature but is difficult to differentiate from hemoglobin and other tissue chromophores. Hemozoin can be detected in blood samples, but only utilizing approaches that require specialized training and facilities. Diffuse optical spectroscopy (DOS) is a noninvasive sensing technique that is sensitive to near-infrared absorption and scattering and capable of probing centimeter-deep volumes of tissue in vivo. DOS is relatively low-cost, does not require specialized training and thus potentially suitable for use in low-resource settings. In this work, we assess the potential of DOS to detect and quantify the presence of hemozoin noninvasively and at physiologically relevant levels. We suspended synthetic hemozoin in Intralipid-based tissue-simulating phantoms in order to mimic malaria infection in multiply-scattering tissue. Using a fiber probe that combines frequency-domain and continuous-wave broadband DOS (650-1000 nm), we detected hemozoin concentrations below 250 ng/ml, which corresponds to parasitemia sensitivities comparable to modern rapid diagnostic tests. We used the experimental variability to simulate and estimate the sensitivity of DOS to hemozoin in tissue that includes hemoglobin, water, and lipid under various tissue oxygen saturation levels. The results indicate that with increased precision, it may be possible to detect Hz noninvasively with DOS.

  12. Conductivity relaxation and charge transport of trihexyl tetradecyl phosphonium dicyanamide ionic liquid by broadband dielectric spectroscopy

    Science.gov (United States)

    Thasneema K., K.; Thayyil, M. Shahin; Krishna Kumar N., S.; Govindaraj, G.; Saheer, V. C.

    2018-04-01

    Usually ionic liquids consists of a large organic cation with low symmetry such as imidazolium, pyridinium, quaternary ammonium or phosponium etc combined with enormously wide range of inorganic or organic symmetric anion with melting point below 100. Ionic liquids existing in an extremely large number of possible ion pair combinations. It offers a very wide range of thermo physical properties led to the concept of designer solvents for specific applications. Due to the features of high chemical and thermal stability, low vapor pressure non flammability high ionic conductivity, and they show a good solvent ability towards a great variety of organic or inorganic compounds, ionic liquids have a widespread use in many areas such as batteries, fuel cell, solar cells, super capacitors etc. The main focus of this work is the study of molecular dynamics and conductivity relaxation of amorphous Trihexyl tetradecyl phosphonium dicyanamide ([P14,6,6,6][N(CN)2]) ionic liquid which is proved as a better electrolyte in super capacitors, over a wide frequency 10-2 Hz to 107 Hz and the temperature range between 123k and 265 k by means of Broadband Dielectric Spectroscopy. We observe alpha conductivity relaxation and secondary relaxation above and below Glass Transition Temperature. The experimental results were analyzed using electric modulus representation. The analysis emphasis the inter molecular interaction and the nature of glass forming system, whether it is fragile or strong system. The ionic liquid shows a fragile behavior and the fragility index m=123.59. TGA result of the sample exhibit a good resistance to thermal decomposition, up to 300°C.

  13. GHz Yb:KYW oscillators in time-resolved spectroscopy

    Science.gov (United States)

    Li, Changxiu; Krauß, Nico; Schäfer, Gerhard; Ebner, Lukas; Kliebisch, Oliver; Schmidt, Johannes; Winnerl, Stephan; Hettich, Mike; Dekorsy, Thomas

    2018-02-01

    A high-speed asynchronous optical sampling system (ASOPS) based on Yb:KYW oscillators with 1-GHz repetition rate is reported. Two frequency-offset-stabilized diode-pumped Yb:KYW oscillators are employed as pump and probe source, respectively. The temporal resolution of this system within 1-ns time window is limited to 500 fs and the noise floor around 10-6 (ΔR/R) close to the shot-noise level is obtained within an acquisition time of a few seconds. Coherent acoustic phonons are investigated by measuring multilayer semiconductor structures with multiple quantum wells and aluminum/silicon membranes in this ASOPS system. A wavepacket-like phonon sequence at 360 GHz range is detected in the semiconductor structures and a decaying sequence of acoustic oscillations up to 200 GHz is obtained in the aluminum/silicon membranes. Coherent acoustic phonons generated from semiconductor structures are further manipulated by a double pump scheme through pump time delay control.

  14. Time-Resolved Synchronous Fluorescence for Biomedical Diagnosis

    Science.gov (United States)

    Zhang, Xiaofeng; Fales, Andrew; Vo-Dinh, Tuan

    2015-01-01

    This article presents our most recent advances in synchronous fluorescence (SF) methodology for biomedical diagnostics. The SF method is characterized by simultaneously scanning both the excitation and emission wavelengths while keeping a constant wavelength interval between them. Compared to conventional fluorescence spectroscopy, the SF method simplifies the emission spectrum while enabling greater selectivity, and has been successfully used to detect subtle differences in the fluorescence emission signatures of biochemical species in cells and tissues. The SF method can be used in imaging to analyze dysplastic cells in vitro and tissue in vivo. Based on the SF method, here we demonstrate the feasibility of a time-resolved synchronous fluorescence (TRSF) method, which incorporates the intrinsic fluorescent decay characteristics of the fluorophores. Our prototype TRSF system has clearly shown its advantage in spectro-temporal separation of the fluorophores that were otherwise difficult to spectrally separate in SF spectroscopy. We envision that our previously-tested SF imaging and the newly-developed TRSF methods will combine their proven diagnostic potentials in cancer diagnosis to further improve the efficacy of SF-based biomedical diagnostics. PMID:26404289

  15. Advances in high-order harmonic generation sources for time-resolved investigations

    Energy Technology Data Exchange (ETDEWEB)

    Reduzzi, Maurizio [Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Carpeggiani, Paolo [Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Kühn, Sergei [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Calegari, Francesca [Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Nisoli, Mauro; Stagira, Salvatore [Dipartimento di Fisica, Politecnico di Milano, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Vozzi, Caterina [Institute of Photonics and Nanotechnologies, CNR-IFN, Piazza Leonardo da Vinci 32, 20133 Milano (Italy); Dombi, Peter [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Wigner Research Center for Physics, 1121 Budapest (Hungary); Kahaly, Subhendu [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Tzallas, Paris; Charalambidis, Dimitris [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Foundation for Research and Technology – Hellas, Institute of Electronic Structure and Lasers, P.O. Box 1527, GR-711 10 Heraklion, Crete (Greece); Varju, Katalin [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); Department of Optics and Quantum Electronics, University of Szeged, Dóm tér 9, 6720 Szeged (Hungary); Osvay, Karoly [ELI-ALPS, ELI-Hu Kft., Dugonics ter 13, H-6720 Szeged (Hungary); and others

    2015-10-15

    We review the main research directions ongoing in the development of extreme ultraviolet sources based on high-harmonic generation for the synthesization and application of trains and isolated attosecond pulses to time-resolved spectroscopy. A few experimental and theoretical works will be discussed in connection to well-established attosecond techniques. In this context, we present the unique possibilities offered for time-resolved investigations on the attosecond timescale by the new Extreme Light Infrastructure Attosecond Light Pulse Source, which is currently under construction.

  16. Advances in high-order harmonic generation sources for time-resolved investigations

    International Nuclear Information System (INIS)

    Reduzzi, Maurizio; Carpeggiani, Paolo; Kühn, Sergei; Calegari, Francesca; Nisoli, Mauro; Stagira, Salvatore; Vozzi, Caterina; Dombi, Peter; Kahaly, Subhendu; Tzallas, Paris; Charalambidis, Dimitris; Varju, Katalin; Osvay, Karoly

    2015-01-01

    We review the main research directions ongoing in the development of extreme ultraviolet sources based on high-harmonic generation for the synthesization and application of trains and isolated attosecond pulses to time-resolved spectroscopy. A few experimental and theoretical works will be discussed in connection to well-established attosecond techniques. In this context, we present the unique possibilities offered for time-resolved investigations on the attosecond timescale by the new Extreme Light Infrastructure Attosecond Light Pulse Source, which is currently under construction.

  17. Effects of cations and cholesterol with sphingomyelin membranes investigated by high-resolution broadband sum frequency vibrational spectroscopy

    Science.gov (United States)

    Zhang, Zhen; Feng, Rong-juan; Li, Yi-yi; Liu, Ming-hua; Guo, Yuan

    2017-08-01

    Sphingomyelin(SM) is specifically enriched in the plasma membrane of mammalian cells. Its molecular structure is compose by N-acyl-Derythro-sphingosylphosphorylcholine. The function of the SM related to membrane signaling and protein trafficking are relied on the interactions of the SM, cations, cholesterol and proteins. In this report, the interaction of three different nature SMs, cations and cholesterol at air/aqueous interfaces studied by high-resolution broadband sum frequency vibrational spectroscopy, respectively. Our results shed lights on understanding the relationship between SMs monolayer, cholesterol and Cations.

  18. 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

  19. Time-resolved Femtosecond Photon Echo Probes Bimodal Solvent Dynamics

    NARCIS (Netherlands)

    Pshenichnikov, M.S; Duppen, K.; Wiersma, D. A.

    1995-01-01

    We report on time-resolved femtosecond photon echo experiments of a dye molecule in a polar solution. The photon echo is time resolved by mixing the echo with a femtosecond gate pulse in a nonlinear crystal. It is shown that the temporal profile of the photon echo allows separation of the

  20. Time-resolved materials science opportunities using synchrotron x-ray sources

    International Nuclear Information System (INIS)

    Larson, B.C.; Tischler, J.Z.

    1995-06-01

    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

  1. 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

    Chemical reactions are manifestations of the dynamics of molecular valence electrons and their couplings to atomic motions. Emerging methods in attosecond science can probe purely electronic dynamics in atomic and molecular systems(1-6). By contrast, time-resolved structural-dynamics methods...... 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......,17): in both cases, this sensitivity derives from the ionization-matrix element(18,19). Here we demonstrate a time-resolved molecular-frame photoelectron-angular-distribution (TRMFPAD) method for imaging the purely valence-electron dynamics during a chemical reaction. Specifically, the TRMFPADs measured during...

  2. Ultrafast Time-Resolved Photoluminescence Studies of Gallium-Arsenide

    Science.gov (United States)

    Johnson, Matthew Bruce

    This thesis concerns the study of ultrafast phenomena in GaAs using time-resolved photoluminescence (PL). The thesis consists of five chapters. Chapter one is an introduction, which discusses the study of ultrafast phenomena in semiconductors. Chapter two is a description of the colliding-pulse mode-locked (CPM) ring dye laser, which is at the heart of the experimental apparatus used in this thesis. Chapter three presents a detailed experimental and theoretical investigation of photoluminescence excitation correlation spectroscopy (PECS), the novel technique which is used to time-resolve ultrafast PL phenomena. Chapters 4 and 5 discuss two applications of the PECS technique. In Chapter 4 the variation of PL intensity in In-alloyed GaAs substrate material is studied, while Chapter 5 discusses the variation of carrier lifetimes in ion-damaged GaAs used in photo-conductive circuit elements (PCEs). PECS is a pulse-probe technique that measures the cross correlation of photo-excited carrier populations. The theoretical model employed in this thesis is based upon the rate equation for a simple three-level system consisting of valence and conduction bands and a single trap level. In the limit of radiative band-to-band dominated recombination, no PECS signal should be observed; while in the capture -dominated recombination limit, the PECS signal from the band-to-band PL measures the cross correlation of the excited electron and hole populations and thus, the electron and hole lifetimes. PECS is experimentally investigated using a case study of PL in semi-insulating (SI) GaAs and In -alloyed GaAs. At 77 K, the PECS signal is characteristic of a capture-dominated system, yielding an electron-hole lifetime of about 200 ps. However, at 5 K the behavior is more complicated and shows saturation effects due to the C acceptor level, which is un-ionized at 5 K. As a first application, PECS is used to investigate the large band-to-band PL contrast observed near dislocations in In

  3. Insights into the Structural Changes Occurring upon Photoconversion in the Orange Carotenoid Protein from Broadband Two-Dimensional Electronic Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    De Re, Eleonora; Schlau-Cohen, Gabriela S.; Leverenz, Ryan L.; Huxter, Vanessa M.; Oliver, Thomas A. A.; Mathies, Richard A.; Fleming, Graham R.

    2014-05-22

    Carotenoids play an essential role in photoprotection, interacting with other pigments to safely dissipate excess absorbed energy as heat. In cyanobacteria, the short time scale photoprotective mechanisms involve the photoactive orange carotenoid protein (OCP), which binds a single carbonyl carotenoid. Blue-green light induces the photoswitching of OCP from its ground state form (OCPO) to a metastable photoproduct (OCPR). OCPR can bind to the phycobilisome antenna and induce fluorescence quenching. The photoswitching is accompanied by structural and functional changes at the level of the protein and of the bound carotenoid. In this study, we use broadband two-dimensional electronic spectroscopy to look at the differences in excited state dynamics of the carotenoid in the two forms of OCP. Our results provide insight into the origin of the pronounced vibrational lineshape and oscillatory dynamics observed in linear absorption and 2D electronic spectroscopy of OCPO and the large inhomogeneous broadening in OCPR, with consequences for the chemical function of the two forms.

  4. 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.

  5. 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

  6. Time-resolved biophysical approaches to nucleocytoplasmic transport

    Directory of Open Access Journals (Sweden)

    Francesco Cardarelli

    Full Text Available Molecules are continuously shuttling across the nuclear envelope barrier that separates the nucleus from the cytoplasm. Instead of being just a barrier to diffusion, the nuclear envelope is rather a complex filter that provides eukaryotes with an elaborate spatiotemporal regulation of fundamental molecular processes, such as gene expression and protein translation. Given the highly dynamic nature of nucleocytoplasmic transport, during the past few decades large efforts were devoted to the development and application of time resolved, fluorescence-based, biophysical methods to capture the details of molecular motion across the nuclear envelope. These methods are here divided into three major classes, according to the differences in the way they report on the molecular process of nucleocytoplasmic transport. In detail, the first class encompasses those methods based on the perturbation of the fluorescence signal, also known as ensemble-averaging methods, which average the behavior of many molecules (across many pores. The second class comprises those methods based on the localization of single fluorescently-labelled molecules and tracking of their position in space and time, potentially across single pores. Finally, the third class encompasses methods based on the statistical analysis of spontaneous fluorescence fluctuations out of the equilibrium or stationary state of the system. In this case, the behavior of single molecules is probed in presence of many similarly-labelled molecules, without dwelling on any of them. Here these three classes, with their respective pros and cons as well as their main applications to nucleocytoplasmic shuttling will be briefly reviewed and discussed. Keywords: Fluorescence recovery after photobleaching, Single particle tracking, Fluorescence correlation spectroscopy, Diffusion, Transport, GFP, Nuclear pore complex, Live cell, Confocal microscopy

  7. Broad-band dielectric spectroscopy of tetragonal PLZT x/40/60

    Czech Academy of Sciences Publication Activity Database

    Buixaderas, Elena; Noujni, Dmitri; Veljko, Sergiy; Savinov, Maxim; Vaněk, Přemysl; Kamba, Stanislav; Petzelt, Jan; Kosec, M.

    2006-01-01

    Roč. 79, 6-7 (2006), s. 415-426 ISSN 0141-1594 R&D Projects: GA ČR(CZ) GA202/06/0403; GA ČR GA202/04/0993 Institutional research plan: CEZ:AV0Z10100520 Keywords : ferroelectrics * relaxors * dielectric behaviour * lattice dynamics dielectric spectroscopy * IR spectroscopy * THz spectroscopy Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 0.830, year: 2006

  8. Time-resolved far-infrared experiments at the National Synchrotron Light Source. Final report

    International Nuclear Information System (INIS)

    Tanner, D.B.; Reitze, D.H.; Carr, G.L.

    1999-01-01

    A facility for time-resolved infrared and far-infrared spectroscopy has been built and commissioned at the National Synchrotron Light Source. This facility permits the study of time dependent phenomena over a frequency range from 2-8000cm -1 (0.25 meV-1 eV). Temporal resolution is approximately 200 psec and time dependent phenomena in the time range out to 100 nsec can be investigated

  9. Broadband pump-probe spectroscopy with sub-10-fs resolution for probing ultrafast internal conversion and coherent phonons in carotenoids

    International Nuclear Information System (INIS)

    Polli, D.; Antognazza, M.R.; Brida, D.; Lanzani, G.; Cerullo, G.; De Silvestri, S.

    2008-01-01

    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

  10. SUZAKU BROADBAND SPECTROSCOPY OF SWIFT J1753.5-0127 IN THE LOW-HARD STATE

    International Nuclear Information System (INIS)

    Reynolds, Mark T.; Miller, Jon M.; Homan, Jeroen; Miniutti, Giovanni

    2010-01-01

    We present Suzaku observations of the Galactic black hole candidate Swift J1753.5-0127 in the low-hard state (LHS). The broadband coverage of Suzaku enables us to detect the source over the energy range 0.6-250 keV. The broadband spectrum (2-250 keV) is found to be consistent with a simple power-law (Γ ∼ 1.63). In agreement with previous observations of this system, a significant excess of soft X-ray flux is detected consistent with the presence of a cool accretion disk. Estimates of the disk inner radius infer a value consistent with the innermost stable circular orbit (ISCO; R in ∼ g , for certain values of, e.g., N H , i), although we cannot conclusively rule out the presence of an accretion disk truncated at larger radii (R in ∼ 10-50R g ). A weak, relativistically broadened iron line is also detected, in addition to disk reflection at higher energy. However, the iron-K line profile favors an inner radius larger than the ISCO (R in ∼ 10-20R g ). The implications of these observations for models of the accretion flow in the LHS are discussed.

  11. High-speed combustion diagnostics in a rapid compression machine by broadband supercontinuum absorption spectroscopy.

    Science.gov (United States)

    Werblinski, Thomas; Fendt, Peter; Zigan, Lars; Will, Stefan

    2017-05-20

    The first results under fired internal combustion engine conditions based on a supercontinuum absorption spectrometer are presented and discussed. Temperature, pressure, and water mole fraction are inferred simultaneously from broadband H 2 O absorbance spectra ranging from 1340 nm to 1440 nm. The auto-ignition combustion process is monitored for two premixed n-heptane/air mixtures with 10 kHz in a rapid compression machine. Pressure and temperature levels during combustion exceed 65 bar and 1900 K, respectively. To allow for combustion measurements, the robustness of the spectrometer against beam steering has been improved compared to its previous version. Additionally, the detectable wavelength range has been extended further into the infrared region to allow for the acquisition of distinct high-temperature water transitions located in the P-branch above 1410 nm. Based on a theoretical study, line-of-sight (LOS) effects introduced by temperature stratification on the broadband fitting algorithm in the complete range from 1340 nm to 1440 nm are discussed. In this context, the recorded spectra during combustion were evaluated only within a narrower spectral region exhibiting almost no interference from low-temperature molecules (here, P-branch from 1410 nm to 1440 nm). It is shown that this strategy mitigates almost all of the LOS effects introduced by cold molecules and the evaluation of the spectrum in the entirely recorded wavelength range at engine combustion conditions.

  12. [A new measurement method of time-resolved spectrum].

    Science.gov (United States)

    Shi, Zhi-gang; Huang, Shi-hua; Liang, Chun-jun; Lei, Quan-sheng

    2007-02-01

    A new method for measuring time-resolved spectrum (TRS) is brought forward. Programming with assemble language controlled the micro-control-processor (AT89C51), and a kind of peripheral circuit constituted the drive circuit, which drived the stepping motor to run the monochromator. So the light of different kinds of expected wavelength could be obtained. The optical signal was transformed to electrical signal by optical-to-electrical transform with the help of photomultiplier tube (Hamamatsu 1P28). The electrical signal of spectrum data was transmitted to the oscillograph. Connecting the two serial interfaces of RS232 between the oscillograph and computer, the electrical signal of spectrum data could be transmitted to computer for programming to draw the attenuation curve and time-resolved spectrum (TRS) of the swatch. The method for measuring time-resolved spectrum (TRS) features parallel measurement in time scale but serial measurement in wavelength scale. Time-resolved spectrum (TRS) and integrated emission spectrum of Tb3+ in swatch Tb(o-BBA)3 phen were measured using this method. Compared with the real time-resolved spectrum (TRS). It was validated to be feasible, credible and convenient. The 3D spectra of fluorescence intensity-wavelength-time, and the integrated spectrum of the swatch Tb(o-BBA)3 phen are given.

  13. A time-resolved image sensor for tubeless streak cameras

    Science.gov (United States)

    Yasutomi, Keita; Han, SangMan; Seo, Min-Woong; Takasawa, Taishi; Kagawa, Keiichiro; Kawahito, Shoji

    2014-03-01

    This paper presents a time-resolved CMOS image sensor with draining-only modulation (DOM) pixels for tube-less streak cameras. Although the conventional streak camera has high time resolution, the device requires high voltage and bulky system due to the structure with a vacuum tube. The proposed time-resolved imager with a simple optics realize a streak camera without any vacuum tubes. The proposed image sensor has DOM pixels, a delay-based pulse generator, and a readout circuitry. The delay-based pulse generator in combination with an in-pixel logic allows us to create and to provide a short gating clock to the pixel array. A prototype time-resolved CMOS image sensor with the proposed pixel is designed and implemented using 0.11um CMOS image sensor technology. The image array has 30(Vertical) x 128(Memory length) pixels with the pixel pitch of 22.4um. .

  14. Broadband Access

    Indian Academy of Sciences (India)

    First page Back Continue Last page Overview Graphics. Broadband Access. Worldwide market for broadband access $30 Billion! Over 200 million broadband subscribers worldwide! Various Competing Broadband access. Digital Subscriber line; Wireless; Optical Fiber.

  15. Time-resolved emission from laser-ablated uranium

    International Nuclear Information System (INIS)

    Stoffels, E.; Mullen, J. van der; Weijer, P. van de

    1991-01-01

    Time-resolved emission spectra from the plasma, induced by laser ablation of uranium samples have been studied. The dependence of the emission intensity on time is strongly affected by the nature and pressure of the buffer gas. Air and argon have been used in the pressure range 0.002 to 5 mbar. The emission intensity as a function of time displays three maxima, indicating that three different processes within the expanding plasma plume are involved. On basis of the time-resolved spectra we propose a model that explains qualitatively the phenomena that are responsible for this time behaviour. (author)

  16. Broadband high-resolution two-photon spectroscopy with laser frequency combs

    OpenAIRE

    Hipke, Arthur; Meek, Samuel A.; Ideguchi, Takuro; Hänsch, Theodor W.; Picqué, Nathalie

    2013-01-01

    Two-photon excitation spectroscopy with broad spectral span is demonstrated at Doppler-limited resolution. We describe first Fourier transform two-photon spectroscopy of an atomic sample with two mode-locked laser oscillators in a dual-comb technique. Each transition is uniquely identified by the modulation imparted by the interfering comb excitations. The temporal modulation of the spontaneous two-photon fluorescence is monitored with a single photodetector, and the spectrum is revealed by a...

  17. Broadband Doppler-limited two-photon and stepwise excitation spectroscopy with laser frequency combs

    Science.gov (United States)

    Hipke, Arthur; Meek, Samuel A.; Ideguchi, Takuro; Hänsch, Theodor W.; Picqué, Nathalie

    2014-07-01

    Multiplex two-photon excitation spectroscopy is demonstrated at Doppler-limited resolution. We describe first Fourier-transform two-photon spectroscopy of an atomic sample with two mode-locked laser oscillators in a dual-comb technique. Each transition is uniquely identified by the modulation imparted by the interfering comb excitations. The temporal modulation of the spontaneous two-photon fluorescence is monitored with a single photodetector, and the spectrum of all excited transitions is revealed by a Fourier transform.

  18. Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

    Science.gov (United States)

    Barho, Franziska B.; Gonzalez-Posada, Fernando; Milla, Maria-Jose; Bomers, Mario; Cerutti, Laurent; Tournié, Eric; Taliercio, Thierry

    2017-11-01

    Tailored plasmonic nanoantennas are needed for diverse applications, among those sensing. Surface-enhanced infrared absorption (SEIRA) spectroscopy using adapted nanoantenna substrates is an efficient technique for the selective detection of molecules by their vibrational spectra, even in small quantity. Highly doped semiconductors have been proposed as innovative materials for plasmonics, especially for more flexibility concerning the targeted spectral range. Here, we report on rectangular-shaped, highly Si-doped InAsSb nanoantennas sustaining polarization switchable longitudinal and transverse plasmonic resonances in the mid-infrared. For small array periodicities, the highest reflectance intensity is obtained. Large periodicities can be used to combine localized surface plasmon resonances (SPR) with array resonances, as shown in electromagnetic calculations. The nanoantenna arrays can be efficiently used for broadband SEIRA spectroscopy, exploiting the spectral overlap between the large longitudinal or transverse plasmonic resonances and narrow infrared active absorption features of an analyte molecule. We demonstrate an increase of the vibrational line intensity up to a factor of 5.7 of infrared-active absorption features of vanillin in the fingerprint spectral region, yielding enhancement factors of three to four orders of magnitude. Moreover, an optimized readout for SPR sensing is proposed based on slightly overlapping longitudinal and transverse localized SPR.

  19. Highly doped semiconductor plasmonic nanoantenna arrays for polarization selective broadband surface-enhanced infrared absorption spectroscopy of vanillin

    Directory of Open Access Journals (Sweden)

    Barho Franziska B.

    2017-11-01

    Full Text Available Tailored plasmonic nanoantennas are needed for diverse applications, among those sensing. Surface-enhanced infrared absorption (SEIRA spectroscopy using adapted nanoantenna substrates is an efficient technique for the selective detection of molecules by their vibrational spectra, even in small quantity. Highly doped semiconductors have been proposed as innovative materials for plasmonics, especially for more flexibility concerning the targeted spectral range. Here, we report on rectangular-shaped, highly Si-doped InAsSb nanoantennas sustaining polarization switchable longitudinal and transverse plasmonic resonances in the mid-infrared. For small array periodicities, the highest reflectance intensity is obtained. Large periodicities can be used to combine localized surface plasmon resonances (SPR with array resonances, as shown in electromagnetic calculations. The nanoantenna arrays can be efficiently used for broadband SEIRA spectroscopy, exploiting the spectral overlap between the large longitudinal or transverse plasmonic resonances and narrow infrared active absorption features of an analyte molecule. We demonstrate an increase of the vibrational line intensity up to a factor of 5.7 of infrared-active absorption features of vanillin in the fingerprint spectral region, yielding enhancement factors of three to four orders of magnitude. Moreover, an optimized readout for SPR sensing is proposed based on slightly overlapping longitudinal and transverse localized SPR.

  20. BROADBAND X-RAY IMAGING AND SPECTROSCOPY OF THE CRAB NEBULA AND PULSAR WITH NuSTAR

    International Nuclear Information System (INIS)

    Madsen, Kristin K.; Harrison, Fiona; Grefenstette, Brian W.; Reynolds, Stephen; An, Hongjun; Boggs, Steven; Craig, William W.; Zoglauer, Andreas; Christensen, Finn E.; Fryer, Chris L.; Hailey, Charles J.; Nynka, Melania; Markwardt, Craig; Zhang, William; Stern, Daniel

    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 the spectral photon index of the torus structure with a steepening characterized by ΔΓ ∼ 0.25. We also confirm a previously reported steepening in the pulsed spectrum, and quantify it with a broken power law with break energy at ∼12 keV and ΔΓ ∼ 0.27. We present spectral maps of the inner 100'' of the remnant and measure the size of the nebula as a function of energy in seven bands. These results find that the rate of shrinkage with energy of the torus size can be fitted by a power law with an index of γ = 0.094 ± 0.018, consistent with the predictions of Kennel and Coroniti. The change in size is more rapid in the NW direction, coinciding with the counter-jet where we find the index to be a factor of two larger. NuSTAR observed the Crab during the latter part of a γ-ray flare, but found no increase in flux in the 3-78 keV energy band

  1. Multi-frame pyramid correlation for time-resolved PIV

    NARCIS (Netherlands)

    Sciacchitano, A.; Scarano, F.; Wieneke, B.

    2012-01-01

    A novel technique is introduced to increase the precision and robustness of time-resolved particle image velocimetry (TR-PIV) measurements. The innovative element of the technique is the linear combination of the correlation signal computed at different separation time intervals. The domain of the

  2. Time-resolved fluorescence analysis of the mobile flavin cofactor

    Indian Academy of Sciences (India)

    Conformational heterogeneity of the FAD cofactor in -hydroxybenzoate hydroxylase (PHBH) was investigated with time-resolved polarized flavin fluorescence. For binary enzyme/substrate (analogue) complexes of wild-type PHBH and Tyr222 mutants, crystallographic studies have revealed two distinct flavin conformations ...

  3. An x-ray detector for time-resolved studies

    International Nuclear Information System (INIS)

    Rodricks, B.; Brizard, C.; Clarke, R.; Lowe, W.

    1992-01-01

    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

  4. Time-Resolved Small-Angle X-Ray Scattering

    NARCIS (Netherlands)

    ten Elshof, Johan E.; Besselink, R.; Stawski, Tomasz; Castricum, H.L.; Levy, D.; Zayat, M.

    2015-01-01

    This chapter focuses on time-resolved studies of nanostructure development in sol-gel liquids, that is, diluted sols, wet gels, and drying thin fffilms. The most commonly investigated classes of sol-gel materials are silica, organically modified silica, template-directed mesostructured silica,

  5. 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 ...

  6. Numerical simulations of time-resolved quantum electronics

    International Nuclear Information System (INIS)

    Gaury, Benoit; Weston, Joseph; Santin, Matthieu; Houzet, Manuel; Groth, Christoph; Waintal, Xavier

    2014-01-01

    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

  7. Turbulent Statistics From Time-Resolved PIV Measurements of a Jet Using Empirical Mode Decomposition

    Science.gov (United States)

    Dahl, Milo D.

    2013-01-01

    Empirical mode decomposition is an adaptive signal processing method that when applied to a broadband signal, such as that generated by turbulence, acts as a set of band-pass filters. This process was applied to data from time-resolved, particle image velocimetry measurements of subsonic jets prior to computing the second-order, two-point, space-time correlations from which turbulent phase velocities and length and time scales could be determined. The application of this method to large sets of simultaneous time histories is new. In this initial study, the results are relevant to acoustic analogy source models for jet noise prediction. The high frequency portion of the results could provide the turbulent values for subgrid scale models for noise that is missed in large-eddy simulations. The results are also used to infer that the cross-correlations between different components of the decomposed signals at two points in space, neglected in this initial study, are important.

  8. 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

    2016-04-08

    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.

  9. High-resolution broadband terahertz spectroscopy via electronic heterodyne detection of photonically generated terahertz frequency comb.

    Science.gov (United States)

    Pavelyev, D G; Skryl, A S; Bakunov, M I

    2014-10-01

    We report an alternative approach to the terahertz frequency-comb spectroscopy (TFCS) based on nonlinear mixing of a photonically generated terahertz pulse train with a continuous wave signal from an electronic synthesizer. A superlattice is used as a nonlinear mixer. Unlike the standard TFCS technique, this approach does not require a complex double-laser system but retains the advantages of TFCS-high spectral resolution and wide bandwidth.

  10. High-performance broad-band spectroscopy for breast cancer risk assessment

    Science.gov (United States)

    Pawluczyk, Olga; Blackmore, Kristina; Dick, Samantha; Lilge, Lothar

    2005-09-01

    Medical diagnostics and screening are becoming increasingly demanding applications for spectroscopy. Although for many years the demand was satisfied with traditional spectrometers, analysis of complex biological samples has created a need for instruments capable of detecting small differences between samples. One such application is the measurement of absorbance of broad spectrum illumination by breast tissue, in order to quantify the breast tissue density. Studies have shown that breast cancer risk is closely associated with the measurement of radiographic breast density measurement. Using signal attenuation in transillumination spectroscopy in the 550-1100nm spectral range to measure breast density, has the potential to reduce the frequency of ionizing radiation, or making the test accessible to younger women; lower the cost and make the procedure more comfortable for the patient. In order to determine breast density, small spectral variances over a total attenuation of up to 8 OD have to be detected with the spectrophotometer. For this, a high performance system has been developed. The system uses Volume Phase Holographic (VPH) transmission grating, a 2D detector array for simultaneous registration of the whole spectrum with high signal to noise ratio, dedicated optical system specifically optimized for spectroscopic applications and many other improvements. The signal to noise ratio exceeding 50,000 for a single data acquisition eliminates the need for nitrogen cooled detectors and provides sufficient information to predict breast tissue density. Current studies employing transillumination breast spectroscopy (TIBS) relating to breast cancer risk assessment and monitoring are described.

  11. Programming for time resolved spectrum in pulse radiolysis experiments

    International Nuclear Information System (INIS)

    Betty, C.A.; Panajkar, M.S.; Shirke, N.D.

    1993-01-01

    A user friendly program in Pascal has been developed for data acquisition and subsequent processing of time resolved spectra of transient species produced in pulse radiolysis experiments. The salient features of the program are (i) thiocyanate dosimetry and (ii) spectrum acquisition. The thiocyanate dosimetry is carried out to normalize experimental conditions to a standard value as determined by computing absorbance of the transient signal CNS -2 that is produced from thiocyanate solution by a 7 MeV electron pulse. Spectrum acquisition allows the acquisition of the time resolved data at 20 different times points and subsequent display of the plots of absorbance vs. wavelength for the desired time points during the experiment. It is also possible to plot single time point spectrum as well as superimposed spectra for different time points. Printing, editing and merging facilities are also provided. (author). 2 refs., 7 figs

  12. Time-resolved crystallography using the Hadamard Transform

    Science.gov (United States)

    Yorke, Briony A.; Beddard, Godfrey S.; Owen, Robin L.; Pearson, Arwen R.

    2014-01-01

    A new method for performing time-resolved X-ray crystallographic experiments based on the Hadamard Transform is proposed and demonstrated. The time-resolution is defined by the underlying periodicity of the probe pulse sequence and the signal to noise is greatly improved compared to the fastest experiments depending on a single pulse. This approach is general and equally applicable to any spectroscopic or imaging measurement where the probe can be encoded. PMID:25282611

  13. Time-resolved spectral measurements above 80 A

    International Nuclear Information System (INIS)

    Kauffman, R.L.; Ceglio, N.; Medecki, H.

    1983-01-01

    We have made time-resolved spectral measurements above 80 A from laser-produced plasmas. These are made using a transmission grating spectrograph whose primary components are a cylindrically-curved x-ray mirror for light collection, a transmission grating for spectral dispersions, and an x-ray streak camera for temporal resolution. A description of the instrument and an example of the data are given

  14. The RATIO method for time-resolved Laue crystallography

    International Nuclear Information System (INIS)

    Coppens, P.; Pitak, M.; Gembicky, M.; Messerschmidt, M.; Scheins, S.; Benedict, J.; Adachi, S.-I.; Sato, T.; Nozawa, S.; Ichiyanagi, K.; Chollet, M.; Koshihara, S.-Y.

    2009-01-01

    A RATIO method for analysis of intensity changes in time-resolved pump-probe Laue diffraction experiments is described. The method eliminates the need for scaling the data with a wavelength curve representing the spectral distribution of the source and removes the effect of possible anisotropic absorption. It does not require relative scaling of series of frames and removes errors due to all but very short term fluctuations in the synchrotron beam.

  15. 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...... 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 systems simultaneously illuminated by x rays and a laser beam....

  16. Time-resolved CT angiography in aortic dissection

    International Nuclear Information System (INIS)

    Meinel, Felix G.; Nikolaou, Konstantin; Weidenhagen, Rolf; Hellbach, Katharina; Helck, Andreas; Bamberg, Fabian; Reiser, Maximilian F.; Sommer, Wieland H.

    2012-01-01

    Objectives: We performed this study to assess feasibility and additional diagnostic value of time-resolved CT angiography of the entire aorta in patients with aortic dissection. Materials and methods: 14 consecutive patients with known or suspected aortic dissection (aged 60 ± 9 years) referred for aortic CT angiography were scanned on a dual-source CT scanner (Somatom Definition Flash; Siemens, Forchheim, Germany) using a shuttle mode for multiphasic image acquisition (range 48 cm, time resolution 6 s, 6 phases, 100 kV, 110 mAs/rot). Effective radiation doses were calculated from recorded dose length products. For all phases, CT densities were measured in the aortic lumen and renal parenchyma. From the multiphasic data, 3 phases corresponding to a triphasic standard CT protocol, served as a reference and were compared against findings from the time-resolved datasets. Results: Mean effective radiation dose was 27.7 ± 3.5 mSv. CT density of the true lumen peaked at 355 ± 53 HU. Compared to the simulated triphasic protocol, time-resolved CT angiography added diagnostic information regarding a number of important findings: the enhancement delay between true and false lumen (n = 14); the degree of membrane oscillation (n = 14); the perfusion delay in arteries originating from the false lumen (n = 9). Other additional information included true lumen collapse (n = 4), quantitative assessment of renal perfusion asymmetry (n = 2), and dynamic occlusion of aortic branches (n = 2). In 3/14 patients (21%), these additional findings of the multiphasic protocol altered patient management. Conclusions: Multiphasic, time-resolved CT angiography covering the entire aorta is feasible at a reasonable effective radiation dose and adds significant diagnostic information with therapeutic consequences in patients with aortic dissection.

  17. Thermo-oxidative degradation study of melt-processed polyethylene and its blend with polyamide using time-resolved rheometry

    CSIR Research Space (South Africa)

    Salehiyan, Reza

    2017-05-01

    Full Text Available Time-resolved mechanical spectroscopy (TRMS) was conducted to study the thermo-oxidative degradation of linear low density polyethylene (LLDPE) samples with different thermal histories and their blends with a polyamide (PA6) in the melt state. Neat...

  18. Time-resolved cathodoluminescence microscopy with sub-nanosecond beam blanking for direct evaluation of the local density of states

    NARCIS (Netherlands)

    Moerland, R.J.; Weppelman, I.G.C.; Garming, M.W.H.; Kruit, P.; Hoogenboom, J.P.

    2016-01-01

    We show cathodoluminescence-based time-resolved electron beam spectroscopy in order to directly probe the spontaneous emission decay rate that is modified by the local density of states in a nanoscale environment. In contrast to dedicated laser-triggered electron-microscopy setups, we use commercial

  19. Broadband Ftmw Spectroscopy of the Urea-Argon and Thiourea-Argon Complexes

    Science.gov (United States)

    Medcraft, Chris; Bittner, Dror M.; Cooper, Graham A.; Mullaney, John C.; Walker, Nick

    2017-06-01

    The rotational spectra complexes of argon-urea, argon-thiourea and water-thiourea have been measured by chirped-pulse Fourier transform microwave spectroscopy from 2-18.5 GHz. The sample was produced via laser vaporisation of a rod containing copper and the organic sample as a stream of argon was passed over the surface and subsequently expanded into the vacuum chamber cooling the sample. Argon was found to bind to π system of the carbonyl bond for both the urea and thiourea complexes.

  20. Broadband strip-line ferromagnetic resonance spectroscopy of soft magnetic CoFeTaZr patterned thin films

    Science.gov (United States)

    Gupta, S.; Kumar, D.; Jin, T. L.; Nongjai, R.; Asokan, K.; Ghosh, A.; Aparnadevi, M.; Suri, P.; Piramanayagam, S. N.

    2018-05-01

    In this paper, magnetic and magnetization dynamic properties of compositionally patterned Co46Fe40Ta9Zr5 thin films are investigated. A combination of self-assembly and ion-implantation was employed to locally alter the composition of Co46Fe40Ta9Zr5 thin film in a periodic manner. 20 keV O+ and 60 keV N+ ions were implanted at different doses in order to modify the magnetization dynamic properties of the samples in a controlled fashion. Magnetic hysteresis loop measurements revealed significant changes in the coercivity for higher influences of 5 × 1016 ions per cm2. In particular, N+ implantation was observed to induce two phase formation with high and low coercivities. Broadband strip-line ferromagnetic resonance spectroscopy over wide range of frequency (8 - 20 GHz) was used to study the magnetization dynamics as a function of ion-beam dosage. With higher fluences, damping constant showed a continuous increase from 0.0103 to 0.0430. Such control of magnetic properties at nano-scale using this method is believed to be useful for spintronics and microwave device applications.

  1. Near-infrared incoherent broadband cavity enhanced absorption spectroscopy (NIR-IBBCEAS) for detection and quantification of natural gas components.

    Science.gov (United States)

    Prakash, Neeraj; Ramachandran, Arun; Varma, Ravi; Chen, Jun; Mazzoleni, Claudio; Du, Ke

    2018-06-28

    The principle of near-infrared incoherent broadband cavity enhanced absorption spectroscopy was employed to develop a novel instrument for detecting natural gas leaks as well as for testing the quality of natural gas mixtures. The instrument utilizes the absorption features of methane, butane, ethane, and propane in the wavelength region of 1100 nm to 1250 nm. The absorption cross-section spectrum in this region for methane was adopted from the HITRAN database, and those for the other three gases were measured in the laboratory. A singular-value decomposition (SVD) based analysis scheme was employed for quantifying methane, butane, ethane, and propane by performing a linear least-square fit. The developed instrument achieved a detection limit of 460 ppm, 141 ppm, 175 ppm and 173 ppm for methane, butane, ethane, and propane, respectively, with a measurement time of 1 second and a cavity length of 0.59 m. These detection limits are less than 1% of the Lower Explosive Limit (LEL) for each gas. The sensitivity can be further enhanced by changing the experimental parameters (such as cavity length, lamp power etc.) and using longer averaging intervals. The detection system is a low-cost and portable instrument suitable for performing field monitorings. The results obtained on the gas mixture emphasize the instrument's potential for deployment at industrial facilities dealing with natural gas, where potential leaks pose a threat to public safety.

  2. Timely resolved measurements on CdSe nanoparticles

    International Nuclear Information System (INIS)

    Holt, B.E. von

    2006-01-01

    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 1S e 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 1S 3/2 -1S-e and 1P 3/2 -1P e but not the intermediately lyingt transition 2S 3/2 -1S e 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 1S e and 1P e . 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 1S 3/2 -1S e and the 1P 3

  3. Alignment of time-resolved data from high throughput experiments.

    Science.gov (United States)

    Abidi, Nada; Franke, Raimo; Findeisen, Peter; Klawonn, Frank

    2016-12-01

    To better understand the dynamics of the underlying processes in cells, it is necessary to take measurements over a time course. Modern high-throughput technologies are often used for this purpose to measure the behavior of cell products like metabolites, peptides, proteins, [Formula: see text]RNA or mRNA at different points in time. Compared to classical time series, the number of time points is usually very limited and the measurements are taken at irregular time intervals. The main reasons for this are the costs of the experiments and the fact that the dynamic behavior usually shows a strong reaction and fast changes shortly after a stimulus and then slowly converges to a certain stable state. Another reason might simply be missing values. It is common to repeat the experiments and to have replicates in order to carry out a more reliable analysis. The ideal assumptions that the initial stimulus really started exactly at the same time for all replicates and that the replicates are perfectly synchronized are seldom satisfied. Therefore, there is a need to first adjust or align the time-resolved data before further analysis is carried out. Dynamic time warping (DTW) is considered as one of the common alignment techniques for time series data with equidistant time points. In this paper, we modified the DTW algorithm so that it can align sequences with measurements at different, non-equidistant time points with large gaps in between. This type of data is usually known as time-resolved data characterized by irregular time intervals between measurements as well as non-identical time points for different replicates. This new algorithm can be easily used to align time-resolved data from high-throughput experiments and to come across existing problems such as time scarcity and existing noise in the measurements. We propose a modified method of DTW to adapt requirements imposed by time-resolved data by use of monotone cubic interpolation splines. Our presented approach

  4. Ultrafast time-resolved faraday rotation in EuO thin films.

    Science.gov (United States)

    Liu, F; Makino, T; Yamasaki, T; Ueno, K; Tsukazaki, A; Fukumura, T; Kong, Y; Kawasaki, M

    2012-06-22

    We have investigated the ultrafast spin dynamics in EuO thin films by time-resolved Faraday rotation spectroscopy. The photoinduced magnetization is found to be increased in a transient manner, accompanied with subsequent demagnetization. The dynamical magnetization enhancement showed a maximum slightly below the Curie temperature with prolonged tails toward both lower and higher temperatures and dominates the demagnetization counterpart at 55 K. The magnetization enhancement component decays in ~1 ns. The realization of the transient collective ordering is attributable to the enhancement of the f-d exchange interaction.

  5. Unfolding of Ubiquitin Studied by Picosecond Time-Resolved Fluorescence of the Tyrosine Residue

    OpenAIRE

    Noronha, Melinda; Lima, João C.; Bastos, Margarida; Santos, Helena; Maçanita, António L.

    2004-01-01

    The photophysics of the single tyrosine in bovine ubiquitin (UBQ) was studied by picosecond time-resolved fluorescence spectroscopy, as a function of pH and along thermal and chemical unfolding, with the following results: First, at room temperature (25°C) and below pH 1.5, native UBQ shows single-exponential decays. From pH 2 to 7, triple-exponential decays were observed and the three decay times were attributed to the presence of tyrosine, a tyrosine-carboxylate hydrogen-bonded complex, and...

  6. Time resolved IR-LIGS experiments for gas-phase trace detection and temperature measurements

    Energy Technology Data Exchange (ETDEWEB)

    Fantoni, R.; Giorgi, M. [ENEA, Centro Ricerche Frascati, Rome (Italy). Dip. Innovazione; Snels, M. [CNR, Tito Scalo, Potenza (Italy). Istituto per i Materiali Speciali; Latzel, H.

    1997-01-01

    Time resolved Laser Induced Grating Spectroscopy (LIGS) has been performed to detect different gases in mixtures at atmospheric pressure or higher. The possibility of trace detection of minor species and of temperature measurements has been demonstrated for various molecular species either of environmental interest or involved in combustion processes. In view of the application of tracing unburned hydrocarbons in combustion chambers, the coupling of the IR-LIGS technique with imaging detection has been considered and preliminary results obtained in small size ethylene/air flames are shown.

  7. Relationship between time-resolved and non-time-resolved Beer-Lambert law in turbid media.

    Science.gov (United States)

    Nomura, Y; Hazeki, O; Tamura, M

    1997-06-01

    The time-resolved Beer-Lambert law proposed for oxygen monitoring using pulsed light was extended to the non-time-resolved case in a scattered medium such as living tissues with continuous illumination. The time-resolved Beer-Lambert law was valid for the phantom model and living tissues in the visible and near-infrared regions. The absolute concentration and oxygen saturation of haemoglobin in rat brain and thigh muscle could be determined. The temporal profile of rat brain was reproduced by Monte Carlo simulation. When the temporal profiles of rat brain under different oxygenation states were integrated with time, the absorbance difference was linearly related to changes in the absorption coefficient. When the simulated profiles were integrated, there was a linear relationship within the absorption coefficient which was predicted for fractional inspiratory oxygen concentration from 10 to 100% and, in the case beyond the range of the absorption coefficient, the deviation from linearity was slight. We concluded that an optical pathlength which is independent of changes in the absorption coefficient is a good approximation for near-infrared oxygen monitoring.

  8. Lucas–Kanade fluid trajectories for time-resolved PIV

    International Nuclear Information System (INIS)

    Yegavian, Robin; Leclaire, Benjamin; Illoul, Cédric; Losfeld, Gilles; Champagnat, Frédéric

    2016-01-01

    We introduce a new method for estimating fluid trajectories in time-resolved PIV. It relies on a Lucas–Kanade paradigm and consists in a simple and direct extension of a two-frame estimation with FOLKI-PIV (Champagnat et al 2011 Exp. Fluids 50 1169–82). The so-called Lucas–Kanade Fluid Trajectories (LKFT) are assumed to be polynomial in time, and are found as the minimizer of a global functional, in which displacements are sought so as to match the intensities of a series of images pairs in the sequence, in the least-squares sense. All pairs involve the central image, similar to other recent time-resolved approaches (FTC (Lynch and Scarano 2013 Meas. Sci. Technol . 24 035305) and FTEE (Jeon et al 2014 Exp. Fluids 55 1–16)). As switching from a two-frame to a time-resolved objective simply amounts to adding terms in a functional, no significant additional algorithmic element is required. Similar to FOLKI-PIV the method is very well suited for GPU acceleration, which is an important feature as computational complexity increases with the image sequence size. Tests on synthetic data exhibiting peak-locking show that increasing the image sequence size strongly reduces both associated bias and random error, and that LKFT has a remaining total error comparable to that of FTEE on this case. Results on case B of the third PIV challenge (Stanislas et al 2008 Exp. Fluids 45 27–71) also show its ability to drastically reduce the error in situations with low signal-to-noise ratio. These results are finally confirmed on experimental images acquired in the near-field of a low Reynolds number jet. Strong reductions in peak-locking, spatial and temporal noise compared to two-frame estimation are also observed, on the displacement components themselves, as well as on spatial or temporal derivatives, such as vorticity and material acceleration. (paper)

  9. Time Resolved X-Ray Scattering of molecules in Solution

    DEFF Research Database (Denmark)

    Brandt van Driel, Tim

    The dissertation describes the use of Time-Resolved X-ray Diffuse Scattering (TR-XDS) to study photo-induced structural changes in molecules in solution. The application of the technique is exemplified with experiments on two bimetallic molecules. The main focus is on the data-flow and process......)42+ obtained at European Synchrotron Radiation Facility (ESRF) are presented to exemplify TR-XDS at synchrotrons. Similarly, measurements on Ir2(dimen)42+ are used to show the XFEL data-flow and how it deviates from the prior. A method to identify and account for systematic fluctuations...

  10. Time-resolved explosion of intense-laser-heated clusters.

    Science.gov (United States)

    Kim, K Y; Alexeev, I; Parra, E; Milchberg, H M

    2003-01-17

    We investigate the femtosecond explosive dynamics of intense laser-heated argon clusters by measuring the cluster complex transient polarizability. The time evolution of the polarizability is characteristic of competition in the optical response between supercritical and subcritical density regions of the expanding cluster. The results are consistent with time-resolved Rayleigh scattering measurements, and bear out the predictions of a recent laser-cluster interaction model [H. M. Milchberg, S. J. McNaught, and E. Parra, Phys. Rev. E 64, 056402 (2001)

  11. Time-resolved explosion of intense-laser-heated clusters

    International Nuclear Information System (INIS)

    Kim, K.Y.; Alexeev, I.; Parra, E.; Milchberg, H.M.

    2003-01-01

    We investigate the femtosecond explosive dynamics of intense laser-heated argon clusters by measuring the cluster complex transient polarizability. The time evolution of the polarizability is characteristic of competition in the optical response between supercritical and subcritical density regions of the expanding cluster. The results are consistent with time-resolved Rayleigh scattering measurements, and bear out the predictions of a recent laser-cluster interaction model [H. M. Milchberg, S. J. McNaught, and E. Parra, Phys. Rev. E 64, 056402 (2001)

  12. Hyperbolic-cosine waveguide tapers and oversize rectangular waveguide for reduced broadband insertion loss in W-band electron paramagnetic resonance spectroscopy. II. Broadband characterization

    Energy Technology Data Exchange (ETDEWEB)

    Sidabras, Jason W.; Anderson, James R.; Mainali, Laxman; Hyde, James S. [Department of Biophysics, Medical College of Wisconsin, Milwaukee, Wisconsin 53226 (United States); Strangeway, Robert A. [Department of Biophysics, Medical College of Wisconsin, Milwaukee, Wisconsin 53226 (United States); Department of Electrical Engineering and Computer Science, Milwaukee School of Engineering, Milwaukee, Wisconsin 53201 (United States); Mett, Richard R. [Department of Biophysics, Medical College of Wisconsin, Milwaukee, Wisconsin 53226 (United States); Department of Chemistry and Physics, Milwaukee School of Engineering, Milwaukee, Wisconsin 53201 (United States)

    2016-03-15

    Experimental results have been reported on an oversize rectangular waveguide assembly operating nominally at 94 GHz. It was formed using commercially available WR28 waveguide as well as a pair of specially designed tapers with a hyperbolic-cosine shape from WR28 to WR10 waveguide [R. R. Mett et al., Rev. Sci. Instrum. 82, 074704 (2011)]. The oversize section reduces broadband insertion loss for an Electron Paramagnetic Resonance (EPR) probe placed in a 3.36 T magnet. Hyperbolic-cosine tapers minimize reflection of the main mode and the excitation of unwanted propagating waveguide modes. Oversize waveguide is distinguished from corrugated waveguide, overmoded waveguide, or quasi-optic techniques by minimal coupling to higher-order modes. Only the TE{sub 10} mode of the parent WR10 waveguide is propagated. In the present work, a new oversize assembly with a gradual 90° twist was implemented. Microwave power measurements show that the twisted oversize waveguide assembly reduces the power loss in the observe and pump arms of a W-band bridge by an average of 2.35 dB and 2.41 dB, respectively, over a measured 1.25 GHz bandwidth relative to a straight length of WR10 waveguide. Network analyzer measurements confirm a decrease in insertion loss of 2.37 dB over a 4 GHz bandwidth and show minimal amplitude distortion of approximately 0.15 dB. Continuous wave EPR experiments confirm these results. The measured phase variations of the twisted oversize waveguide assembly, relative to an ideal distortionless transmission line, are reduced by a factor of two compared to a straight length of WR10 waveguide. Oversize waveguide with proper transitions is demonstrated as an effective way to increase incident power and the return signal for broadband EPR experiments. Detailed performance characteristics, including continuous wave experiment using 1 μM 2,2,6,6-tetramethylpiperidine-1-oxyl in aqueous solution, provided here serve as a benchmark for other broadband low-loss probes in

  13. Hyperbolic-cosine waveguide tapers and oversize rectangular waveguide for reduced broadband insertion loss in W-band electron paramagnetic resonance spectroscopy. II. Broadband characterization

    International Nuclear Information System (INIS)

    Sidabras, Jason W.; Anderson, James R.; Mainali, Laxman; Hyde, James S.; Strangeway, Robert A.; Mett, Richard R.

    2016-01-01

    Experimental results have been reported on an oversize rectangular waveguide assembly operating nominally at 94 GHz. It was formed using commercially available WR28 waveguide as well as a pair of specially designed tapers with a hyperbolic-cosine shape from WR28 to WR10 waveguide [R. R. Mett et al., Rev. Sci. Instrum. 82, 074704 (2011)]. The oversize section reduces broadband insertion loss for an Electron Paramagnetic Resonance (EPR) probe placed in a 3.36 T magnet. Hyperbolic-cosine tapers minimize reflection of the main mode and the excitation of unwanted propagating waveguide modes. Oversize waveguide is distinguished from corrugated waveguide, overmoded waveguide, or quasi-optic techniques by minimal coupling to higher-order modes. Only the TE 10 mode of the parent WR10 waveguide is propagated. In the present work, a new oversize assembly with a gradual 90° twist was implemented. Microwave power measurements show that the twisted oversize waveguide assembly reduces the power loss in the observe and pump arms of a W-band bridge by an average of 2.35 dB and 2.41 dB, respectively, over a measured 1.25 GHz bandwidth relative to a straight length of WR10 waveguide. Network analyzer measurements confirm a decrease in insertion loss of 2.37 dB over a 4 GHz bandwidth and show minimal amplitude distortion of approximately 0.15 dB. Continuous wave EPR experiments confirm these results. The measured phase variations of the twisted oversize waveguide assembly, relative to an ideal distortionless transmission line, are reduced by a factor of two compared to a straight length of WR10 waveguide. Oversize waveguide with proper transitions is demonstrated as an effective way to increase incident power and the return signal for broadband EPR experiments. Detailed performance characteristics, including continuous wave experiment using 1 μM 2,2,6,6-tetramethylpiperidine-1-oxyl in aqueous solution, provided here serve as a benchmark for other broadband low-loss probes in

  14. Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS): A rapid test for enteric coating thickness and integrity of controlled release pellet formulations.

    Science.gov (United States)

    Alfarsi, Anas; Dillon, Amy; McSweeney, Seán; Krüse, Jacob; Griffin, Brendan; Devine, Ken; Sherry, Patricia; Henken, Stephan; Fitzpatrick, Stephen; Fitzpatrick, Dara

    2018-04-12

    There are no rapid dissolution based tests for determining coating thickness, integrity and drug concentration in controlled release pellets either during production or post-production. The manufacture of pellets requires several coating steps depending on the formulation. The sub-coating and enteric coating steps typically take up to six hours each followed by additional drying steps. Post production regulatory dissolution testing also takes up to six hours to determine if the batch can be released for commercial sale. The thickness of the enteric coating is a key factor that determines the release rate of the drug in the gastro-intestinal tract. Also, the amount of drug per unit mass decreases with increasing thickness of the enteric coating. In this study, the coating process is tracked from start to finish on an hourly basis by taking samples of pellets during production and testing those using BARDS (Broadband Acoustic Resonance Dissolution Spectroscopy). BARDS offers a rapid approach to characterising enteric coatings with measurements based on reproducible changes in the compressibility of a solvent due to the evolution of air during dissolution. This is monitored acoustically via associated changes in the frequency of induced acoustic resonances. A steady state acoustic lag time is associated with the disintegration of the enteric coatings in basic solution. This lag time is pH dependent and is indicative of the rate at which the coating layer dissolves. BARDS represents a possible future surrogate test for conventional USP dissolution testing as its data correlates directly with the thickness of the enteric coating, its integrity and also with the drug loading as validated by HPLC. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Contactless, probeless and non-titrimetric determination of acid-base reactions using broadband acoustic resonance dissolution spectroscopy (BARDS).

    Science.gov (United States)

    Ahmed, M Rizwan; McSweeney, Sean; Krüse, Jacob; Vos, Bastiaan; Fitzpatrick, Dara

    2018-02-12

    pH determination is a routine measurement in scientific laboratories worldwide. Most major advances in pH measurement were made in the 19th and early 20th century. pH measurements are critical for the determination of acid base reactions. This study demonstrates how an acid-base reaction can be monitored without the use of a pH probe, indicator and titres of reagent. The stoichiometric reaction between carbonate and HCl acid yields specific quantities of CO 2 , which causes reproducible changes to the compressibility of the solvent. This in turn slows down the speed of sound in solution which is induced by a magnetic follower gently tapping the inner wall of the vessel. As a consequence the frequencies of the acoustic resonances in the vessel are reduced. This approach is called Broadband Acoustic Resonance Dissolution Spectroscopy (BARDS) which harnesses this phenomenon for many applications. The acid-carbonate experiments have also been validated using H 2 SO 4 acid and using both potassium and sodium counterions for the carbonate. This method can be used to interrogate strong acid-base reactions in a rapid and non-invasive manner using carbonate as the base. The data demonstrate the first example of a reactant also acting as an indicator. The applicability of the method to weak acids has yet to be determined. A novel conclusion from the study is that a person with a well-trained ear is capable of determining the concentration and pH of a strong acid just by listening. This brings pH measurement into the realm of human perception.

  16. A novel multiplex absorption spectrometer for time-resolved studies

    Science.gov (United States)

    Lewis, Thomas; Heard, Dwayne E.; Blitz, Mark A.

    2018-02-01

    A Time-Resolved Ultraviolet/Visible (UV/Vis) Absorption Spectrometer (TRUVAS) has been developed that can simultaneously monitor absorption at all wavelengths between 200 and 800 nm with millisecond time resolution. A pulsed photolysis laser (KrF 248 nm) is used to initiate chemical reactions that create the target species. The absorption signals from these species evolve as the composition of the gas in the photolysis region changes over time. The instrument can operate at pressures over the range ˜10-800 Torr and can measure time-resolved absorbances systems (in particular the Herriott cell), there are fundamental differences, most notably the ability to adjust each mirror to maximise the overlap between the probe beam and the photolysis laser. Another feature which aids the sensitivity and versatility of the system is the use of 2 high-throughput spectrographs coupled with sensitive line-array CCDs, which can measure absorbance from ˜200 to 800 nm simultaneously. The capability of the instrument is demonstrated via measurements of the absorption spectrum of the peroxy radical, HOCH2CH2O2, and its self-reaction kinetics.

  17. Time-resolved Laue diffraction from protein crystals: Instrumental considerations

    International Nuclear Information System (INIS)

    Bilderback, D.H.; Cornell Univ., Ithaca, NY; Moffat, K.; Szebenyi, D.M.E.

    1984-01-01

    A serious limitation of macromolecular crystallography has been its inability to determine changes in structure on a biochemical time scale of milliseconds or less. Recently, we have shown that X-ray exposures on single crystals of macromolecules may be obtained in the millisecond time range through the use of intense, polychromatic radiation with Δlambda/lambda approx.= 0.2 derived from the Cornell High Energy Synchrotron Source, CHESS. Such radiation falling on a stationary crystal yields a Laue diffraction pattern, in which almost all Laue reflections arise from a unique set of Miller indices and where their intensities are automatically integrated over wavelength. This Laue technique requires wide band pass optics, which may be obtained by a combination of reflection and transmission mirrors, filters or layered synthetic microstructures. Time-resolved macromolecular crystallography may be achieved by several data collection schemes: 'one-shot' recording coupled to a simple streak camera, repetitive sample perturbation coupled to a detector with temporal resolution and repetitive perturbation which uses the synchrotron pulses for stroboscopic triggering and detection. These schemes are appropriate for different time scales, roughly the milli-, micro- and nanosecond regimes. It appears that time-resolved crystallography is entirely feasible, with an ultimate time resolution limited only by the length of a synchrotron light pulse, some 150 ps at CHESS. (orig.)

  18. Time resolved fluorescence of cow and goat milk powder

    Science.gov (United States)

    Brandao, Mariana P.; de Carvalho dos Anjos, Virgílio; Bell., Maria José V.

    2017-01-01

    Milk powder is an international dairy commodity. Goat and cow milk powders are significant sources of nutrients and the investigation of the authenticity and classification of milk powder is particularly important. The use of time-resolved fluorescence techniques to distinguish chemical composition and structure modifications could assist develop a portable and non-destructive methodology to perform milk powder classification and determine composition. This study goal is to differentiate milk powder samples from cows and goats using fluorescence lifetimes. The samples were excited at 315 nm and the fluorescence intensity decay registered at 468 nm. We observed fluorescence lifetimes of 1.5 ± 0.3, 6.4 ± 0.4 and 18.7 ± 2.5 ns for goat milk powder; and 1.7 ± 0.3, 6.9 ± 0.2 and 29.9 ± 1.6 ns for cow's milk powder. We discriminate goat and cow powder milk by analysis of variance using Fisher's method. In addition, we employed quadratic discriminant analysis to differentiate the milk samples with accuracy of 100%. Our results suggest that time-resolved fluorescence can provide a new method to the analysis of powder milk and its composition.

  19. Time resolved plasma characterization in a long conduction time planar plasma opening switch

    International Nuclear Information System (INIS)

    Adler, L.K.; Greenly, J.B.; Qi, N.; Hammer, D.A.

    1989-01-01

    The authors discuss additional experiments in which the plasma dynamics and properties will be monitored in detail before and during opening. Space and time resolved density, temperature and motion information about the plasma and neutrals is given by emission spectroscopy and streak photography and correlated to the current and voltage traces. Specifically, we will look for the effects of neutrals evolving off of surfaces, stagnation of the switch plasma, and rvec J x rvec B motion of the plasma downstream of the switch. Diagnostics include current and voltage monitors, a multi-aperture biased Faraday cup, emission spectroscopy and streak photography. Pairs of B dot loops are positioned in the stripline just upstream and downstream of the POS. Also, two single B loops were placed further downstream to look for bulk plasma motion. An inductive monitor gives the voltage at the upstream side of the POS and the Faraday cup monitors the gun plasma consistency from shot to shot

  20. A time resolved microfocus XEOL facility at the Diamond Light Source

    International Nuclear Information System (INIS)

    Mosselmans, J F W; Taylor, R P; Quinn, P D; Cibin, G; Gianolio, D; Finch, A A; Sapelkin, A V

    2013-01-01

    We have constructed a Time-Resolved X-ray Excited Optical Luminescence (TR-XEOL) detection system at the Microfocus Spectroscopy beamline I18 at the Diamond Light Source. Using the synchrotron in h ybrid bunch mode , the data collection is triggered by the RF clock, and we are able to record XEOL photons with a time resolution of 6.1 ps during the 230 ns gap between the hybrid bunch and the main train of electron bunches. We can detect photons over the range 180-850 nm using a bespoke optical fibre, with X-ray excitation energies between 2 and 20 keV. We have used the system to study a range of feldspars. The detector is portable and has also been used on beamline B18 to collect Optically Determined X-ray Absorption Spectroscopy (OD-XAS) in QEXAFS mode.

  1. A time resolved microfocus XEOL facility at the Diamond Light Source

    Science.gov (United States)

    Mosselmans, J. F. W.; Taylor, R. P.; Quinn, P. D.; Finch, A. A.; Cibin, G.; Gianolio, D.; Sapelkin, A. V.

    2013-03-01

    We have constructed a Time-Resolved X-ray Excited Optical Luminescence (TR-XEOL) detection system at the Microfocus Spectroscopy beamline I18 at the Diamond Light Source. Using the synchrotron in "hybrid bunch mode", the data collection is triggered by the RF clock, and we are able to record XEOL photons with a time resolution of 6.1 ps during the 230 ns gap between the hybrid bunch and the main train of electron bunches. We can detect photons over the range 180-850 nm using a bespoke optical fibre, with X-ray excitation energies between 2 and 20 keV. We have used the system to study a range of feldspars. The detector is portable and has also been used on beamline B18 to collect Optically Determined X-ray Absorption Spectroscopy (OD-XAS) in QEXAFS mode.

  2. Time-resolving electron temperature diagnostic for ALCATOR C

    International Nuclear Information System (INIS)

    Fairfax, S.A.

    1984-05-01

    A diagnostic that provides time-resolved central electron temperatures has been designed, built, and tested on the ALCATOR C Tokamak. The diagnostic uses an array of fixed-wavelength x-ray crystal monochromators to sample the x-ray continuum and determine the absolute electron temperature. The resolution and central energy of each channel were chosen to exclude any contributions from impurity line radiation. This document describes the need for such a diagnostic, the design methodology, and the results with typical ALCATOR C plasmas. Sawtooth (m = 1) temperature oscillations were observed after pellet fueling of the plasma. This is the first time that such oscillations have been observed with an x-ray temperature diagnostic

  3. Fast time-resolved aerosol collector: proof of concept

    Science.gov (United States)

    Yu, X.-Y.; Cowin, J. P.; Iedema, M. J.; Ali, H.

    2010-10-01

    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.

  4. Time-resolved tomographic images of a relativistic electron beam

    International Nuclear Information System (INIS)

    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 0 , 61 0 , and 117 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

  5. Photon-Counting Arrays for Time-Resolved Imaging

    Directory of Open Access Journals (Sweden)

    I. Michel Antolovic

    2016-06-01

    Full Text Available The paper presents a camera comprising 512 × 128 pixels capable of single-photon detection and gating with a maximum frame rate of 156 kfps. The photon capture is performed through a gated single-photon avalanche diode that generates a digital pulse upon photon detection and through a digital one-bit counter. Gray levels are obtained through multiple counting and accumulation, while time-resolved imaging is achieved through a 4-ns gating window controlled with subnanosecond accuracy by a field-programmable gate array. The sensor, which is equipped with microlenses to enhance its effective fill factor, was electro-optically characterized in terms of sensitivity and uniformity. Several examples of capture of fast events are shown to demonstrate the suitability of the approach.

  6. Toward broadband mechanical spectroscopy

    DEFF Research Database (Denmark)

    Hecksher, Tina; Torchinsky, Darius; Klieber, Christoph

    2017-01-01

    Diverse material classes exhibit qualitatively similar behavior when made viscous upon cooling toward the glass transition, suggesting a common theoretical basis. We used seven different measurement methods to determine the mechanical relaxation kinetics of a prototype molecular glass former over...

  7. Systematic errors in the determination of the spectroscopic g-factor in broadband ferromagnetic resonance spectroscopy: A proposed solution

    Science.gov (United States)

    Gonzalez-Fuentes, C.; Dumas, R. K.; García, C.

    2018-01-01

    A theoretical and experimental study of the influence of small offsets of the magnetic field (δH) on the measurement accuracy of the spectroscopic g-factor (g) and saturation magnetization (Ms) obtained by broadband ferromagnetic resonance (FMR) measurements is presented. The random nature of δH generates systematic and opposite sign deviations of the values of g and Ms with respect to their true values. A δH on the order of a few Oe leads to a ˜10% error of g and Ms for a typical range of frequencies employed in broadband FMR experiments. We propose a simple experimental methodology to significantly minimize the effect of δH on the fitted values of g and Ms, eliminating their apparent dependence in the range of frequencies employed. Our method was successfully tested using broadband FMR measurements on a 5 nm thick Ni80Fe20 film for frequencies ranging between 3 and 17 GHz.

  8. Applications of a table-top time-resolved luminescence spectrometer with nanosecond soft X-ray pulse excitation

    Czech Academy of Sciences Publication Activity Database

    Brůža, P.; Pánek, D.; Fidler, V.; Benedikt, P.; Čuba, V.; Gbur, T.; Boháček, Pavel; Nikl, Martin

    2014-01-01

    Roč. 61, č. 1 (2014), s. 448-451 ISSN 0018-9499 R&D Projects: GA ČR GA13-09876S Institutional support: RVO:68378271 Keywords : LiCaAlF 6 * luminescence * scintillators * soft x-ray * SrHfO 3 * time-resolved spectroscopy * ZnO :Ga Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.283, year: 2014

  9. Time-resolved laser-induced fluorescence system

    Science.gov (United States)

    Bautista, F. J.; De la Rosa, J.; Gallegos, F. J.

    2006-02-01

    Fluorescence methods are being used increasingly in the measurement of species concentrations in gases, liquids and solids. Laser induced fluorescence is spontaneous emission from atoms or molecules that have been excited by laser radiation. Here we present a time resolved fluorescence instrument that consists of a 5 μJ Nitrogen laser (337.1 nm), a sample holder, a quartz optical fiber, a spectrometer, a PMT and a PC that allows the measurement of visible fluorescence spectra (350-750 nm). Time response of the system is approximately 5 ns. The instrument has been used in the measurement of colored bond paper, antifreeze, diesel, cochineal pigment and malignant tissues. The data acquisition was achieved through computer control of a digital oscilloscope (using General Purpose Interface Bus GPIB) and the spectrometer via serial (RS232). The instrument software provides a graphic interface that lets make some data acquisition tasks like finding fluorescence spectra, and fluorescence lifetimes. The software was developed using the Lab-View 6i graphic programming package and can be easily managed in order to add more functions to it.

  10. In-pile Thermal Conductivity Characterization with Time Resolved Raman

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xinwei [Iowa State Univ., Ames, IA (United States). Dept. of Mechanical Engineering; Hurley, David H. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

    2018-03-19

    The project is designed to achieve three objectives: (1) Develop a novel time resolved Raman technology for direct measurement of fuel and cladding thermal conductivity. (2) Validate and improve the technology development by measuring ceramic materials germane to the nuclear industry. (3) Conduct instrumentation development to integrate optical fiber into our sensing system for eventual in-pile measurement. We have developed three new techniques: time-domain differential Raman (TD-Raman), frequency-resolved Raman (FR-Raman), and energy transport state-resolved Raman (ET-Raman). The TD-Raman varies the laser heating time and does simultaneous Raman thermal probing, the FR-Raman probes the material’s thermal response under periodical laser heating of different frequencies, and the ET-Raman probes the thermal response under steady and pulsed laser heating. The measurement capacity of these techniques have been fully assessed and verified by measuring micro/nanoscale materials. All these techniques do not need the data of laser absorption and absolute material temperature rise, yet still be able to measure the thermal conductivity and thermal diffusivity with unprecedented accuracy. It is expected they will have broad applications for in-pile thermal characterization of nuclear materials based on pure optical heating and sensing.

  11. Time-Resolved Hard X-Ray Spectrometer

    International Nuclear Information System (INIS)

    Kenneth Moya; Ian McKennaa; Thomas Keenana; Michael Cuneob

    2007-01-01

    Wired array studies are being conducted at the SNL Z accelerator to maximize the x-ray generation for inertial confinement fusion targets and high energy density physics experiments. An integral component of these studies is the characterization of the time-resolved spectral content of the x-rays. Due to potential spatial anisotropy in the emitted radiation, it is also critical to diagnose the time-evolved spectral content in a space-resolved manner. To accomplish these two measurement goals, we developed an x-ray spectrometer using a set of high-speed detectors (silicon PIN diodes) with a collimated field-of-view that converged on a 1-cm-diameter spot at the pinch axis. Spectral discrimination is achieved by placing high Z absorbers in front of these detectors. We built two spectrometers to permit simultaneous different angular views of the emitted radiation. Spectral data have been acquired from recent Z shots for the radial and polar views. UNSPEC1 has been adapted to analyze and unfold the measured data to reconstruct the x-ray spectrum. The unfold operator code, UFO2, is being adapted for a more comprehensive spectral unfolding treatment

  12. Spectral and time-resolved studies on ocular structures

    Science.gov (United States)

    Schweitzer, D.; Jentsch, S.; Schenke, S.; Hammer, M.; Biskup, C.; Gaillard, E.

    2007-07-01

    Measurements of endogeous fluorophores open the possibility for evaluation of metabolic state at the eye. For interpretation of 2-dimensional measurements of time-resolved auto fluorescence in 2 separate spectral ranges at the human eye, comparing measurements were performed on porcine eyes. Determining excitation and emission spectra, attention was drawn of proof of coenzymes NADH and FAD in isolated anatomical structures cornea, aqueous humor, lens, vitreous, neuronal retina, retinal pigment epithelium (RPE), choroid, and sclera. All these structures exhibit auto fluorescence, highest in lens. Excitation at 350 nm results in local fluorescence maxima at 460 nm, corresponding to NADH, in all structures. This short-wave excitation allows metabolic studies only at the anterior eye, because of the limited transmission of the ocular media. During excitation at 446 nm the existence of FAD is expressed by local fluorescence maxima at 530 nm. The composition fluorescence spectra allow no discrimination between single ocular structures. Approximating the dynamic fluorescence by a double exponential function, the shortest lifetimes were detected in RPE and neuronal retina. The histograms of mean lifetime t M cover each other on lens with cornea and also on sclera with choroid. Despite the lifetimes are close between RPE and neuronal retina, the relative contributions Q I are wide different. The gradient of trend lines in cluster diagrams of amplitudes α II vs. α I allows a discrimination of ocular structures.

  13. Time-resolved photoluminescence of SiOx encapsulated Si

    Science.gov (United States)

    Kalem, Seref; Hannas, Amal; Österman, Tomas; Sundström, Villy

    Silicon and its oxide SiOx offer a number of exciting electrical and optical properties originating from defects and size reduction enabling engineering new electronic devices including resistive switching memories. Here we present the results of photoluminescence dynamics relevant to defects and quantum confinement effects. Time-resolved luminescence at room temperature exhibits an ultrafast decay component of less than 10 ps at around 480 nm and a slower component of around 60 ps as measured by streak camera. Red shift at the initial stages of the blue luminescence decay confirms the presence of a charge transfer to long lived states. Time-correlated single photon counting measurements revealed a life-time of about 5 ns for these states. The same quantum structures emit in near infrared close to optical communication wavelengths. Nature of the emission is described and modeling is provided for the luminescence dynamics. The electrical characteristics of metal-oxide-semiconductor devices were correlated with the optical and vibrational measurement results in order to have better insight into the switching mechanisms in such resistive devices as possible next generation RAM memory elements. ``This work was supported by ENIAC Joint Undertaking and Laser-Lab Europe''.

  14. Time resolved EUV spectra from Zpinching capillary discharge plasma

    Science.gov (United States)

    Jancarek, Alexandr; Nevrkla, Michal; Nawaz, Fahad

    2015-09-01

    We developed symmetrically charged driver to obtain high voltage, high current Z-pinching capillary discharge. Plasma is created by up to 70 kA, 29 ns risetime current pulse passing through a 5 mm inner diameter, 224 mm long capillary filled with gas to initial pressure in the range of 1 kPa. Due to the low inductance design of the driver, the pinch is observable directly from the measured current curve. Time-integrated and time-resolved spectra of discharge plasma radiation are recorded together with the capillary current and analyzed. The most encouraging spectra were captured in the wavelength range 8.3 ÷ 14 nm. This spectral region contains nitrogen Balmer series lines including potentially lasing NVII 2 - 3 transition. Spectral lines are identified in the NIST database using the FLY kinetic code. The line of 13.38 nm wavelength, transition NVII 2 - 3, was observed in gated, and also in time-integrated spectra for currents >60 kA. This work has been supported by the Ministry of Education, Youth and Sports of the Czech Republic grants LG13029.

  15. Time-resolved pump-probe experiments at the LCLS

    Energy Technology Data Exchange (ETDEWEB)

    Glownia, James; /SLAC /Stanford U., Appl. Phys. Dept.; Cryan, J.; /SLAC /Stanford U., Phys. Dept.; Andreasson, J.; /Uppsala U.; Belkacem, A.; /LBNL, Berkeley; Berrah, N.; /Western Michigan U.; Blaga, C.L.; /Ohio State U.; Bostedt, C.; Bozek, J.; /SLAC; DiMauro, L.F.; /Ohio State U.; Fang, L.; /Western Michigan U.; Frisch, J.; /SLAC; Gessner, O.; /LBNL; Guhr, M.; /SLAC; Hajdu, J.; /Uppsala U.; Hertlein, M.P.; /LBNL; Hoener, M.; /Western Michigan U. /LBNL; Huang, G.; Kornilov, O.; /LBNL; Marangos, J.P.; /Imperial Coll., London; March, A.M.; /Argonne; McFarland, B.K.; /SLAC /Stanford U., Phys. Dept. /SLAC /IRAMIS, Saclay /Stanford U., Phys. Dept. /Georgia Tech /Argonne /Kansas State U. /SLAC /Stanford U., Phys. Dept. /SLAC /Stanford U., Appl. Phys. Dept. /Stanford U., Appl. Phys. Dept. /SLAC /LBNL /Argonne /SLAC /SLAC /Stanford U., Appl. Phys. Dept. /Stanford U., Phys. Dept.

    2011-08-12

    The first time-resolved x-ray/optical pump-probe experiments at the SLAC Linac Coherent Light Source (LCLS) used a combination of feedback methods and post-analysis binning techniques to synchronize an ultrafast optical laser to the linac-based x-ray laser. Transient molecular nitrogen alignment revival features were resolved in time-dependent x-ray-induced fragmentation spectra. These alignment features were used to find the temporal overlap of the pump and probe pulses. The strong-field dissociation of x-ray generated quasi-bound molecular dications was used to establish the residual timing jitter. This analysis shows that the relative arrival time of the Ti:Sapphire laser and the x-ray pulses had a distribution with a standard deviation of approximately 120 fs. The largest contribution to the jitter noise spectrum was the locking of the laser oscillator to the reference RF of the accelerator, which suggests that simple technical improvements could reduce the jitter to better than 50 fs.

  16. Time-resolved soft x-ray spectra from laser-produced Cu plasma

    International Nuclear Information System (INIS)

    Cone, K.V.; Dunn, J.; Baldis, H.A.; May, M.J.; Purvis, M.A.; Scott, H.A.; Schneider, M.B.

    2012-01-01

    The volumetric heating of a thin copper target has been studied with time resolved x-ray spectroscopy. The copper target was heated from a plasma produced using the Lawrence Livermore National Laboratory's Compact Multipulse Terrawatt (COMET) laser. A variable spaced grating spectrometer coupled to an x-ray streak camera measured soft x-ray emission (800-1550 eV) from the back of the copper target to characterize the bulk heating of the target. Radiation hydrodynamic simulations were modeled in 2-dimensions using the HYDRA code. The target conditions calculated by HYDRA were post-processed with the atomic kinetics code CRETIN to generate synthetic emission spectra. A comparison between the experimental and simulated spectra indicates the presence of specific ionization states of copper and the corresponding electron temperatures and ion densities throughout the laser-heated copper target.

  17. Time-resolved x-ray spectra from laser-generated high-density plasmas

    Science.gov (United States)

    Andiel, U.; Eidmann, Klaus; Witte, Klaus-Juergen

    2001-04-01

    We focused frequency doubled ultra short laser pulses on solid C, F, Na and Al targets, K-shell emission was systematically investigated by time resolved spectroscopy using a sub-ps streak camera. A large number of laser shots can be accumulated when triggering the camera with an Auston switch system at very high temporal precision. The system provides an outstanding time resolution of 1.7ps accumulating thousands of laser shots. The time duration of the He-(alpha) K-shell resonance lines was observed in the range of (2-4)ps and shows a decrease with the atomic number. The experimental results are well reproduced by hydro code simulations post processed with an atomic kinetics code.

  18. Time-resolved studies at PETRA III with a highly repetitive synchronized laser system

    Energy Technology Data Exchange (ETDEWEB)

    Schlie, Mortiz

    2013-09-15

    Atomic and molecular processes can nowadays be directly followed in the time domain. This is a core technique for a better understanding of the involved fundamental physics, thus auguring new applications in the future as well. Usually the so-called pump-probe technique making use of two synchronized ultrashort light pulses is utilized to obtain this time-resolved data. In this work, the development and characterization of a synchronization system enabling such pump-probe studies at the storage ring PETRA III in combination with an external, then synchronized fs-laser system is described. The synchronization is based on an extended PLL approach with three interconnected feedback loops allowing to monitor short-time losses of the lock and thus prevent them. This way, the jitter between the laser PHAROS and the PETRA III reference signal is reduced to {sigma} <5 ps. Thus the system allows to conduct experiments at a repetition rate of 130 kHz with a temporal resolution limited only by the X-ray pulse length. A major emphasis in the fundamental introductory chapters is an intuitive explanation of the basic principles of phase locked loops and the different aspects of phase noise to allow a deeper understanding of the synchronization. Furthermore, first pump-probe experiments conducted at different beamlines at PETRA III are presented, demonstrating the usability of the laser system in a scientific environment as well. In first characterizing experiments the pulse duration of PETRA III X-ray pulses has been measured to be 90 ps FWHM. In particular, there have been time resolved X-ray absorption spectroscopy experiments on Gaq3 and Znq2 conducted at beamline P11. First results show dynamics of the electronic excitation on the timescale of a few hundred pico seconds up to a few nano seconds and provide a basic understanding for further research on those molecules. For Gaq3 this data is analyzed in detail and compared with visible fluorescence measurements suggesting at

  19. Time-resolved studies at PETRA III with a highly repetitive synchronized laser system

    International Nuclear Information System (INIS)

    Schlie, Mortiz

    2013-09-01

    Atomic and molecular processes can nowadays be directly followed in the time domain. This is a core technique for a better understanding of the involved fundamental physics, thus auguring new applications in the future as well. Usually the so-called pump-probe technique making use of two synchronized ultrashort light pulses is utilized to obtain this time-resolved data. In this work, the development and characterization of a synchronization system enabling such pump-probe studies at the storage ring PETRA III in combination with an external, then synchronized fs-laser system is described. The synchronization is based on an extended PLL approach with three interconnected feedback loops allowing to monitor short-time losses of the lock and thus prevent them. This way, the jitter between the laser PHAROS and the PETRA III reference signal is reduced to σ <5 ps. Thus the system allows to conduct experiments at a repetition rate of 130 kHz with a temporal resolution limited only by the X-ray pulse length. A major emphasis in the fundamental introductory chapters is an intuitive explanation of the basic principles of phase locked loops and the different aspects of phase noise to allow a deeper understanding of the synchronization. Furthermore, first pump-probe experiments conducted at different beamlines at PETRA III are presented, demonstrating the usability of the laser system in a scientific environment as well. In first characterizing experiments the pulse duration of PETRA III X-ray pulses has been measured to be 90 ps FWHM. In particular, there have been time resolved X-ray absorption spectroscopy experiments on Gaq3 and Znq2 conducted at beamline P11. First results show dynamics of the electronic excitation on the timescale of a few hundred pico seconds up to a few nano seconds and provide a basic understanding for further research on those molecules. For Gaq3 this data is analyzed in detail and compared with visible fluorescence measurements suggesting at least

  20. Ultrasensitive time-resolved immunofluorometric assay of pepsinogen I

    International Nuclear Information System (INIS)

    Huang Biao; Xiao Hualong; Zhang Xiangrui; Zhu Lan; Jiang Menjun

    2004-01-01

    Purpose: To construct a two-site sandwich-type assay for pepsinogen I with time-resolved fluoroimmunoassay (TRFIA) as a detection technique. Methods: On the noncompetitive assay, one monoclonal antibody (McAb) coating on wells directed against a specific antigenic site on the pepsinogen I, the europium-labelled McAb which was prepared by with helpful of the europium-chelate of N-(p-isothiocyanatobenzyl)- diethylenetriamine-N, N, N, N-tetraacetic acid directed against a different antigenic site on the pepsinogen I molecule we called labelling McAb. The luminescent enhancement system was enhancement solution which contained mainly 2-naphthoyltrifluoroacetone. 25μl of Calibrators or samples and 200 μl of the assay buffer were pipetted into coated microtiter wells. The plates were incubated with mechanical shaking for 1 h at 25 degree C, washed two times, then added 100 μl Eu3+- McAb solution diluted 50-fold in assay buffer. The plates were incubated again with mechanical shaking for 1 h at 25 degree C,After six washings, 200 μl of enhancement solution were dispense into each well. The plates were shaken for 5 min and fluorescence readings. All the proceeding were done by auto DELFIA1235, software was designed by our lab. The calibration curve and calculation of the concentrations in the unknown samples were performed automatically by using Multicalc software program, where a spline algorithm on logarithmically transformed data was employed. Results: The average labelling yield is 8.6 Eu3+/McAb giving high sensitivity with low background(<1000 cps). The measurement range was 3.5-328 μ g /L with ED25, ED50, ED80 of 11.34 ±0.2 μ g/L, 38.73±0.8 μ g /L and 132,3±2.9 μ g/L. The detection limit, defined as the concentration of PGI corresponding to the fluorescence of the zero calibrators plus two SDs, is 0..05μg/L. Within-run and between-run precision was l.9% and 4.7% which assessed at various PGI concentrations between 5 and 300 μg/L. We checked for cross

  1. Time-resolved diffraction studies of muscle using synchrotron radiation

    International Nuclear Information System (INIS)

    Harford, Jeffrey; Squire, John

    1997-01-01

    details the practical methods involved in recording time-resolved x-ray diffraction patterns from active muscles and the theoretical approaches that are being used to interpret the diffraction patterns that are obtained. The ultimate aim is to produce a series of time-sliced images of the changing molecular arrangements and shapes in the muscle as force is produced; together these images will form 'Muscle - The Movie'. (author)

  2. Time-resolved soft x-ray absorption setup using multi-bunch operation modes at synchrotrons

    International Nuclear Information System (INIS)

    Stebel, L.; Sigalotti, P.; Ressel, B.; Cautero, G.; Malvestuto, M.; Capogrosso, V.; Bondino, F.; Magnano, E.; Parmigiani, F.

    2011-01-01

    Here, we report on a novel experimental apparatus for performing time-resolved soft x-ray absorption spectroscopy in the sub-ns time scale using non-hybrid multi-bunch mode synchrotron radiation. The present setup is based on a variable repetition rate Ti:sapphire laser (pump pulse) synchronized with the ∼500 MHz x-ray synchrotron radiation bunches and on a detection system that discriminates and singles out the significant x-ray photon pulses by means of a custom made photon counting unit. The whole setup has been validated by measuring the time evolution of the L 3 absorption edge during the melting and the solidification of a Ge single crystal irradiated by an intense ultrafast laser pulse. These results pave the way for performing synchrotron time-resolved experiments in the sub-ns time domain with variable repetition rate exploiting the full flux of the synchrotron radiation.

  3. Time resolved FTIR study of the catalytic CO oxidation under periodic variation of the reactant concentration

    Energy Technology Data Exchange (ETDEWEB)

    Kritzenberger, J; Wokaun, A [Paul Scherrer Inst. (PSI), Villigen (Switzerland)

    1997-06-01

    Oxidation of CO over palladium/zirconia catalyst obtained from an amorphous Pd{sub 25}Zr{sub 75} precursor was investigated by time resolved FTIR spectroscopy. Sine wave shaped modulation of the reactant concentration, i.e. variation of CO or O{sub 2} partial pressure, was used to induce variations of the IR signals of product (CO{sub 2}) and unconverted reactant (CO), which were detected in a multi-pass absorption cell. The phase shift {phi} between external perturbation and variation of the CO{sub 2} signal was examined in dependence on temperature (100{sup o}C{<=}T{<=}350{sup o}C) and modulation frequency (1.39x10{sup -4}Hz{<=}{omega}{<=}6.67x10{sup -2}Hz). From the phase shift values, a simple Eley-Rideal mechanism is excluded, and the rate limiting step of the Langmuir-Hinshelwood mechanism for the CO oxidation may be identified. Adsorption and possible surface movement of CO to the actual reaction site determine the rate of the CO oxidation on the palladium/zirconia catalyst used in our study. The introduction of an external perturbation is a first step towards the application of two-dimensional infrared spectroscopy to heterogeneous catalyzed reactions. (author) 3 figs., 4 refs.

  4. Structure and function of proteins investigated by crystallographic and spectroscopic time-resolved methods

    Science.gov (United States)

    Purwar, Namrta

    crystal. Time-resolved X-ray data collected at pH's of 4, 7 and 9 demonstrate that pH alters the kinetics of the PYP photocycle dramatically. At pH 4 the photocycle lasts almost one order of magnitude longer in time compared to pH 7. The final intermediate that accumulates at both pH 7 and pH 4 is absent at pH 9. Results from the dose- and the pH-dependent time-resolved crystallographic experiments show that it is imperative to carefully control the conditions under which time-resolved data are collected. With these considerations we collected a comprehensive time-series from nanoseconds to seconds at 14 different temperature settings from -40 °C to 70 °C. Results from time-resolved crystallography are corroborated by employing time-resolved absorption spectroscopy. For this, absorption spectra on crystals and solution are collected by a fast micro-spectrophotometer custom-designed in our lab. We identify kinetic phases of the PYP photocycle at all 14 temperature settings. Relaxation times associated with these phases are temperature-dependent and can be fit by the Van't Hoff-Arrhenius equation. Kinetic modeling yields entropy and enthalpy values at the barriers of the activation solely from the time-resolved crystallographic data. With this, we advance crystallography to a new frontier: the determination of free energy surfaces. Investigating enzymatic reactions can be challenging, because they are non-cyclic. After one turnover product must be washed away and substrate must be reloaded. A promising approach for routine application can be envisioned at the new 4th generation X-ray sources, such as X-ray free electron lasers (XFELs). With our results we set the scene to comprehensively investigate all kinds of enzymatic reactions with these instruments.

  5. The analysis of time-resolved optically stimulated luminescence: I. Theoretical considerations

    International Nuclear Information System (INIS)

    Chithambo, M L

    2007-01-01

    This is the first of two linked papers on the analysis of time-resolved optically stimulated luminescence. This paper focusses on a theoretical basis of analytical methods and on methods for interpretation of time-resolved luminescence spectra and calculation of luminescence throughput. Using a comparative analysis of the principal features of time-resolved luminescence and relevant analogues from steady state optical stimulation, formulae for configuring a measurement system for optimum performance are presented. We also examine the possible use of stretched-exponential functions for analysis of time-resolved optically stimulated luminescence spectra

  6. Femtosecond time-resolved two-photon photoemission study of organic semiconductor copper phthalocyanine film

    International Nuclear Information System (INIS)

    Tanaka, A.; Tohoku University; University of Rochester, NY; Yan, L.; Watkins, N.J.; Gao, Y.

    2004-01-01

    Full text: Organic semiconductors are recently attracting much interest from the viewpoints of both device and fundamental physics. These organic semiconductors are considered to be important constituents of the future devices, such as organic light-emitting diode, organic field effect transistor, and organic solid-state injection laser. In order to elucidate their detailed physical properties and to develop the future devices, it is indispensable to understand their excited-state dynamics as well as their electronic structures. The femtosecond time-resolved two-photon photoemission (TR-2PPE) spectroscopy is attracting much interest because of its capability to observe the energy-resolved excited electron dynamics. In this work, we have carried out a TR-2PPE study of the organic semiconductor copper phthalocyanine (CuPc) film. Furthermore, we have investigated the detailed electronic structure of CuPc film using the photoemission (PES) and inverse photoemission (IPES) spectroscopies. From the simultaneous PES and IPES measurements for CuPc film with a thickness of 100 nm, the lowest unoccupied molecular orbital (LUMO), highest occupied molecular orbital, and ionization potential of CuPc film have been directly determined. The observed two-photon photoemission (2PPE) spectrum of the present CuPc film, measured with photon energy of about hv=3.3 eV, exhibits a broad feature. From the energy diagram of CuPc film determined by the PES and IPES measurements, the intermediate state observed in the present 2PPE spectrum of CuPc film corresponds to the energy region between about 0.4 and 1.7 eV above the LUMO energy. From the time-resolved pump-probe measurements, it is found that the relaxation lifetimes of excited states in the present CuPc films are very short (all below 50 fs) and monotonously become faster with increasing excitation energy. We attribute this extremely fast relaxation process of photoexcitation to a rapid internal conversion process. From these results

  7. A versatile setup for ultrafast broadband optical spectroscopy of coherent collective modes in strongly correlated quantum systems

    Directory of Open Access Journals (Sweden)

    Edoardo Baldini

    2016-11-01

    Full Text Available A femtosecond pump-probe setup is described that is optimised for broadband transient reflectivity experiments on solid samples over a wide temperature range. By combining high temporal resolution and a broad detection window, this apparatus can investigate the interplay between coherent collective modes and high-energy electronic excitations, which is a distinctive characteristic of correlated electron systems. Using a single-shot readout array detector at frame rates of 10 kHz allows resolving coherent oscillations with amplitudes <10−4. We demonstrate its operation on the charge-transfer insulator La2CuO4, revealing coherent phonons with frequencies up to 13 THz and providing access into their Raman matrix elements.

  8. Time-resolved X-ray absorption spectroscopy for the study of solid state reactions: synthesis of nanocrystalline barium titanate and thermal decomposition of ammonium hexachlorometallate compounds; Zeitaufgeloeste Roentgenabsorptionspektroskopie zur Untersuchung von Festkoerperreaktionen: Synthese von nanokristallinem Bariumtitanat und thermische Zersetzung von Ammoniumhexachlorometallat-Verbindungen

    Energy Technology Data Exchange (ETDEWEB)

    Rumpf, H.

    2001-07-01

    This report presents investigations on the mechanism of two different types of solid-state reactions: At first, barium titanate nanopowders were prepared through a combined polymerization and pyrolysis of a metallo-organic precursor. The mean particle size d{sub m} could be adjusted by choosing appropriate reaction temperatures and tempering atmospheres. In the present in situ study of this particular solid-phase reaction, X-ray absorption near edge structure (XANES) spectroscopy at the Ti K and Ba L{sub 3}-edges was applied in the preparation route of BaTiO{sub 3} nanopowders. A pronounced distortion of the lattice symmetry was found to occur in very fine BaTiO{sub 3} nanopowders (d{sub m} < 20 nm). Secondly, in situ XANES investigations were carried out at the Cl K, Pd L{sub 3}, Rh L{sub 3}, and Pt L{sub 3}-edges to study the mechanism of the thermal decomposition of ammonium hexachlorometallates. The results exceed structural information obtained by in situ X-ray diffraction methods and thermal analysis. Feff8 multiple scattering simulations have been carried out to disclose new intermediate phases of unknown reference compounds. (orig.)

  9. Assembly and application of an instrument for attosecond-time-resolved ionization chronoscopy

    International Nuclear Information System (INIS)

    Uphues, T.

    2006-11-01

    In the framework of this thesis a new setup for attosecond time-resolved measurements has been built and observations of ionization dynamics in rare gas atoms have been made. This new technique is entitled Ionization Chronoscopy and gives further evidence that time-resolved experiments in the attosecond regime will become a powerful tool for investigations in atomic physics. (orig.)

  10. Time-resolved crystallization of deeply cooled liquid hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Kuehnel, Matthias

    2014-02-15

    This thesis serves two main purposes: 1. The introduction of a novel experimental method to investigate phase change dynamics of supercooled liquids 2. First-time measurements for the crystallization behaviour for hydrogen isotopes under various conditions (1) The new method is established by the synergy of a liquid microjet of ∼ 5 μm diameter and a scattering technique with high spatial resolution, here linear Raman spectroscopy. Due to the high directional stability and the known velocity of the liquid filament, its traveling axis corresponds to a time axis static in space. Utilizing evaporative cooling in a vacuum environment, the propagating liquid cools down rapidly and eventually experiences a phase transition to the crystalline state. This temporal evolution is probed along the filament axis, ultimately resulting in a time resolution of 10 ns. The feasibility of this approach is proven successfully within the following experiments. (2) A main object of study are para-hydrogen liquid filaments. Raman spectra reveal a temperature gradient of the liquid across the filament. This behaviour can quantitatively be reconstructed by numerical simulations using a layered model and is rooted in the effectiveness of evaporative cooling on the surface and a finite thermal conductivity. The deepest supercoolings achieved are ∼ 30% below the melting point, at which the filament starts to solidify from the surface towards the core. With a crystal growth velocity extracted from the data the appropriate growth mechanism is identified. The crystal structure that initially forms is metastable and probably the result of Ostwald's rule of stages. Indications for a transition within the solid towards the stable equilibrium phase support this interpretation. The analog isotope ortho-deuterium is evidenced to behave qualitatively similar with quantitative differences being mass related. In further measurements, isotopic mixtures of para-hydrogen and ortho-deuterium are

  11. Time-resolved crystallization of deeply cooled liquid hydrogen isotopes

    International Nuclear Information System (INIS)

    Kuehnel, Matthias

    2014-02-01

    This thesis serves two main purposes: 1. The introduction of a novel experimental method to investigate phase change dynamics of supercooled liquids 2. First-time measurements for the crystallization behaviour for hydrogen isotopes under various conditions (1) The new method is established by the synergy of a liquid microjet of ∼ 5 μm diameter and a scattering technique with high spatial resolution, here linear Raman spectroscopy. Due to the high directional stability and the known velocity of the liquid filament, its traveling axis corresponds to a time axis static in space. Utilizing evaporative cooling in a vacuum environment, the propagating liquid cools down rapidly and eventually experiences a phase transition to the crystalline state. This temporal evolution is probed along the filament axis, ultimately resulting in a time resolution of 10 ns. The feasibility of this approach is proven successfully within the following experiments. (2) A main object of study are para-hydrogen liquid filaments. Raman spectra reveal a temperature gradient of the liquid across the filament. This behaviour can quantitatively be reconstructed by numerical simulations using a layered model and is rooted in the effectiveness of evaporative cooling on the surface and a finite thermal conductivity. The deepest supercoolings achieved are ∼ 30% below the melting point, at which the filament starts to solidify from the surface towards the core. With a crystal growth velocity extracted from the data the appropriate growth mechanism is identified. The crystal structure that initially forms is metastable and probably the result of Ostwald's rule of stages. Indications for a transition within the solid towards the stable equilibrium phase support this interpretation. The analog isotope ortho-deuterium is evidenced to behave qualitatively similar with quantitative differences being mass related. In further measurements, isotopic mixtures of para-hydrogen and ortho-deuterium are

  12. Time-resolved crystallization of deeply cooled liquid hydrogen isotopes

    Energy Technology Data Exchange (ETDEWEB)

    Kuehnel, Matthias

    2014-02-15

    This thesis serves two main purposes: 1. The introduction of a novel experimental method to investigate phase change dynamics of supercooled liquids 2. First-time measurements for the crystallization behaviour for hydrogen isotopes under various conditions (1) The new method is established by the synergy of a liquid microjet of ∼ 5 μm diameter and a scattering technique with high spatial resolution, here linear Raman spectroscopy. Due to the high directional stability and the known velocity of the liquid filament, its traveling axis corresponds to a time axis static in space. Utilizing evaporative cooling in a vacuum environment, the propagating liquid cools down rapidly and eventually experiences a phase transition to the crystalline state. This temporal evolution is probed along the filament axis, ultimately resulting in a time resolution of 10 ns. The feasibility of this approach is proven successfully within the following experiments. (2) A main object of study are para-hydrogen liquid filaments. Raman spectra reveal a temperature gradient of the liquid across the filament. This behaviour can quantitatively be reconstructed by numerical simulations using a layered model and is rooted in the effectiveness of evaporative cooling on the surface and a finite thermal conductivity. The deepest supercoolings achieved are ∼ 30% below the melting point, at which the filament starts to solidify from the surface towards the core. With a crystal growth velocity extracted from the data the appropriate growth mechanism is identified. The crystal structure that initially forms is metastable and probably the result of Ostwald's rule of stages. Indications for a transition within the solid towards the stable equilibrium phase support this interpretation. The analog isotope ortho-deuterium is evidenced to behave qualitatively similar with quantitative differences being mass related. In further measurements, isotopic mixtures of para-hydrogen and ortho-deuterium are

  13. Time resolved diagnostics and kinetic modelling of a modulated hollow cathode discharge of NO2

    International Nuclear Information System (INIS)

    Castillo, M; Herrero, V J; Mendez, I; Tanarro, I

    2004-01-01

    The transients associated with the ignition and the extinction of the cold plasma produced in a low frequency, square-wave modulated, hollow cathode discharge of nitrogen dioxide are characterized by time resolved emission spectroscopy, mass spectrometry and electrical probes. The temporal evolution of the concentrations of neutral species created or destroyed in the NO 2 discharges are compared with the predictions of a simple kinetic model previously developed for discharges of other nitrogen oxides (N 2 O and NO). The physical conditions of pressure, gas flow rate, modulation frequency and electrical current in the NO 2 plasma were selected in order to highlight the time-dependent behaviour of some of the stable species formed in the discharge, especially the nitrogen oxide products, whose concentrations show transient maxima. The usefulness of the analysis of the transient results is emphasized as a means to evaluate the relevance of the different elementary processes and as a key to estimate the values of some of the rate constants critical to the modelling. This work is dedicated to the memory of Professor Jose Campos

  14. Developments in time-resolved x-ray research at APS beamline 7ID

    Energy Technology Data Exchange (ETDEWEB)

    Walko, D. A., E-mail: d-walko@anl.gov; Adams, B. W.; Doumy, G.; Dufresne, E. M.; Li, Yuelin; March, A. M.; Sandy, A. R.; Wang, Jin; Wen, Haidan; Zhu, Yi [Advanced Photon Source, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2016-07-27

    The 7ID beamline of the Advanced Photon Source (APS) is dedicated to time-resolved research using x-ray imaging, scattering, and spectroscopy techniques. Time resolution is achieved via gated detectors and/or mechanical choppers in conjunction with the time structure of the x-ray beam. Three experimental hutches allow for a wide variety of experimental setups. Major areas of research include atomic, molecular, and optical physics; chemistry; condensed matter physics in the bulk, thin film, and surface regimes; and fluid-spray dynamics. Recent developments in facilities at 7ID include a high-power, high-repetition-rate picosecond laser to complement the 1 kHz ultrafast laser. For the ultrafast laser, a newly commissioned optical parametric amplifier provides pump wavelength from 0.2 to 15 µm with energy per pulse up to 200 µJ. A nanodiffraction station has also been commissioned, using Fresnel zone-plate optics to achieve a focused x-ray spot of 300 nm. This nanoprobe is not only used to spatially resolve the evolution of small features in samples after optical excitation, but also has been combined with an intense THz source to study material response under ultrafast electric fields.

  15. Development of an electron momentum spectrometer for time-resolved experiments employing nanosecond pulsed electron beam

    Science.gov (United States)

    Tang, Yaguo; Shan, Xu; Liu, Zhaohui; Niu, Shanshan; Wang, Enliang; Chen, Xiangjun

    2018-03-01

    The low count rate of (e, 2e) electron momentum spectroscopy (EMS) has long been a major limitation of its application to the investigation of molecular dynamics. Here we report a new EMS apparatus developed for time-resolved experiments in the nanosecond time scale, in which a double toroidal energy analyzer is utilized to improve the sensitivity of the spectrometer and a nanosecond pulsed electron gun with a repetition rate of 10 kHz is used to obtain an average beam current up to nA. Meanwhile, a picosecond ultraviolet laser with a repetition rate of 5 kHz is introduced to pump the sample target. The time zero is determined by photoionizing the target using a pump laser and monitoring the change of the electron beam current with time delay between the laser pulse and electron pulse, which is influenced by the plasma induced by the photoionization. The performance of the spectrometer is demonstrated by the EMS measurement on argon using a pulsed electron beam, illustrating the potential abilities of the apparatus for investigating the molecular dynamics in excited states when employing the pump-probe scheme.

  16. Sequestration of Antimony on Calcite Observed by Time-Resolved Nanoscale Imaging.

    Science.gov (United States)

    Renard, François; Putnis, Christine V; Montes-Hernandez, German; King, Helen E; Breedveld, Gijs D; Okkenhaug, Gudny

    2018-01-02

    Antimony, which has damaging effects on the human body and the ecosystem, can be released into soils, ground-, and surface waters either from ore minerals that weather in near surface environments, or due to anthropogenic releases from waste rich in antimony, a component used in batteries, electronics, ammunitions, plastics, and many other industrial applications. Here, we show that dissolved Sb can interact with calcite, a widespread carbonate mineral, through a coupled dissolution-precipitation mechanism. The process is imaged in situ, at room temperature, at the nanometer scale by using an atomic force microscope equipped with a flow-through cell. Time-resolved imaging allowed following the coupled process of calcite dissolution, nucleation of precipitates at the calcite surface and growth of these precipitates. Sb(V) forms a precipitate, whereas Sb(III) needs to be oxidized to Sb(V) before being incorporated in the new phase. Scanning-electron microscopy and Raman spectroscopy allowed identification of the precipitates as two different calcium-antimony phases (Ca 2 Sb 2 O 7 ). This coupled dissolution-precipitation process that occurs in a boundary layer at the calcite surface can sequester Sb as a solid phase on calcite, which has environmental implications as it may reduce the mobility of this hazardous compound in soils and groundwaters.

  17. Using Separable Nonnegative Matrix Factorization Techniques for the Analysis of Time-Resolved Raman Spectra

    Science.gov (United States)

    Luce, R.; Hildebrandt, P.; Kuhlmann, U.; Liesen, J.

    2016-09-01

    The key challenge of time-resolved Raman spectroscopy is the identification of the constituent species and the analysis of the kinetics of the underlying reaction network. In this work we present an integral approach that allows for determining both the component spectra and the rate constants simultaneously from a series of vibrational spectra. It is based on an algorithm for non-negative matrix factorization which is applied to the experimental data set following a few pre-processing steps. As a prerequisite for physically unambiguous solutions, each component spectrum must include one vibrational band that does not significantly interfere with vibrational bands of other species. The approach is applied to synthetic "experimental" spectra derived from model systems comprising a set of species with component spectra differing with respect to their degree of spectral interferences and signal-to-noise ratios. In each case, the species involved are connected via monomolecular reaction pathways. The potential and limitations of the approach for recovering the respective rate constants and component spectra are discussed.

  18. Time-resolved X-ray transmission microscopy on magnetic microstructures; Zeitaufloesende Roentgentransmissionsmikroskopie an magnetischen Mikrostrukturen

    Energy Technology Data Exchange (ETDEWEB)

    Puzic, Aleksandar

    2007-10-23

    Three excitation schemes were designed for stroboscopic imaging of magnetization dynamics with time-resolved magnetic transmission X-ray microscopy (TR-MTXM). These techniques were implemented into two types of X-ray microscopes, namely the imaging transmission X-ray microscope (ITXM) and the scanning transmission X-ray microscope (STXM), both installed at the electron storage ring of the Advanced Light Source in Berkeley, USA. Circular diffraction gratings (Fresnel zone plates) used in both microscopes as focusing and imaging elements presently allow for lateral resolution down to 30 nm. Magnetic imaging is performed by using the X-ray magnetic circular dichroism (XMCD) as element specific contrast mechanism. The developed methods have been successfully applied to the experimental investigation of magnetization dynamics in ferromagnetic microstructures. A temporal resolution well below 100 ps was achieved. A conventional pump-probe technique was implemented first. The dynamic response of the magnetization excited by a broadband pulsed magnetic field was imaged spatially resolved using focused X-ray flashes. As a complementary method, the spatially resolved ferromagnetic resonance (SR-FMR) technique was developed for experimental study of magnetization dynamics in the frequency domain. As a third excitation mode, the burst excitation was implemented. The performance and efficiency of the developed methods have been demonstrated by imaging the local magnetization dynamics in laterally patterned ferromagnetic thin-film elements and three-layer stacks. The existence of multiple eigenmodes in the excitation spectra of ferromagnetic microstructures has been verified by using the pump-probe technique. Magnetostatic spin waves were selectively excited and detected with a time resolution of 50 ps using the SR-FMR technique. Thorough analysis of 20 in most cases independently prepared samples has verified that vortices which exhibit a low-amplitude switching of their core

  19. Time-resolved X-ray transmission microscopy on magnetic microstructures

    International Nuclear Information System (INIS)

    Puzic, Aleksandar

    2007-01-01

    Three excitation schemes were designed for stroboscopic imaging of magnetization dynamics with time-resolved magnetic transmission X-ray microscopy (TR-MTXM). These techniques were implemented into two types of X-ray microscopes, namely the imaging transmission X-ray microscope (ITXM) and the scanning transmission X-ray microscope (STXM), both installed at the electron storage ring of the Advanced Light Source in Berkeley, USA. Circular diffraction gratings (Fresnel zone plates) used in both microscopes as focusing and imaging elements presently allow for lateral resolution down to 30 nm. Magnetic imaging is performed by using the X-ray magnetic circular dichroism (XMCD) as element specific contrast mechanism. The developed methods have been successfully applied to the experimental investigation of magnetization dynamics in ferromagnetic microstructures. A temporal resolution well below 100 ps was achieved. A conventional pump-probe technique was implemented first. The dynamic response of the magnetization excited by a broadband pulsed magnetic field was imaged spatially resolved using focused X-ray flashes. As a complementary method, the spatially resolved ferromagnetic resonance (SR-FMR) technique was developed for experimental study of magnetization dynamics in the frequency domain. As a third excitation mode, the burst excitation was implemented. The performance and efficiency of the developed methods have been demonstrated by imaging the local magnetization dynamics in laterally patterned ferromagnetic thin-film elements and three-layer stacks. The existence of multiple eigenmodes in the excitation spectra of ferromagnetic microstructures has been verified by using the pump-probe technique. Magnetostatic spin waves were selectively excited and detected with a time resolution of 50 ps using the SR-FMR technique. Thorough analysis of 20 in most cases independently prepared samples has verified that vortices which exhibit a low-amplitude switching of their core

  20. Time-resolved laser-excited Shpol'skii spectrometry with a fiber-optic probe and ICCD camera

    International Nuclear Information System (INIS)

    Bystol, Adam J.; Campiglia, Andres D.; Gillispie, Gregory D.

    2000-01-01

    Improved methodology for chemical analysis via laser-excited Shpol'skii spectrometry is reported. The complications of traditional methodology for measurements at liquid nitrogen temperature are avoided by freezing the distal end of a bifurcated fiber-optic probe directly into the sample matrix. Emission wavelength-time matrices were rapidly collected by automatically incrementing the gate delay of an intensified charge-coupled device (ICCD) camera relative to the laser excitation pulse. The excitation source is a compact frequency-doubled tunable dye laser whose bandwidth (<0.03 nm) is well matched for Shpol'skii spectroscopy. Data reproducibility for quantitative analysis purposes and analytical figures of merit are demonstrated for several polycyclic aromatic hydrocarbons at 77 K. Although not attempted in this study, time-resolved excitation-emission matrices could easily be collected with this instrumental system. (c) 2000 Society for Applied Spectroscopy

  1. Ultra-broadband 2D electronic spectroscopy of carotenoid-bacteriochlorophyll interactions in the LH1 complex of a purple bacterium

    Energy Technology Data Exchange (ETDEWEB)

    Maiuri, Margherita [CNR-IFN, Dipartimento di Fisica, Politecnico di Milano, P.zza L. da Vinci 32, Milano 20133 (Italy); Department of Chemistry, Princeton University, Washington Road, Princeton, New Jersey 08544 (United States); Réhault, Julien; Polli, Dario; Cerullo, Giulio, E-mail: giulio.cerullo@polimi.it [CNR-IFN, Dipartimento di Fisica, Politecnico di Milano, P.zza L. da Vinci 32, Milano 20133 (Italy); Carey, Anne-Marie; Hacking, Kirsty; Cogdell, Richard J. [Glasgow Biomedical Research Centre, IBLS, University of Glasgow, 126 Place, Glasgow G12 8TA, Scotland (United Kingdom); Garavelli, Marco [Dipartimento di Chimica “G. Ciamician,” Università di Bologna, Via Selmi 2, IT-40126 Bologna (Italy); CNRS, Institut de Chimie de Lyon, École Normale Supérieure de Lyon, Université de Lyon, 46 Allée d’Italie, F-69364 Lyon Cedex 07 (France); Lüer, Larry [Madrid Institute for Advanced Studies, IMDEA Nanociencia, Madrid (Spain)

    2015-06-07

    We investigate the excitation energy transfer (EET) pathways in the photosynthetic light harvesting 1 (LH1) complex of purple bacterium Rhodospirillum rubrum with ultra-broadband two-dimensional electronic spectroscopy (2DES). We employ a 2DES apparatus in the partially collinear geometry, using a passive birefringent interferometer to generate the phase-locked pump pulse pair. This scheme easily lends itself to two-color operation, by coupling a sub-10 fs visible pulse with a sub-15-fs near-infrared pulse. This unique pulse combination allows us to simultaneously track with extremely high temporal resolution both the dynamics of the photoexcited carotenoid spirilloxanthin (Spx) in the visible range and the EET between the Spx and the B890 bacterio-chlorophyll (BChl), whose Q{sub x} and Q{sub y} transitions peak at 585 and 881 nm, respectively, in the near-infrared. Global analysis of the one-color and two-color 2DES maps unravels different relaxation mechanisms in the LH1 complex: (i) the initial events of the internal conversion process within the Spx, (ii) the parallel EET from the first bright state S{sub 2} of the Spx towards the Q{sub x} state of the B890, and (iii) the internal conversion from Q{sub x} to Q{sub y} within the B890.

  2. Broad-band conductivity and dielectric spectroscopy of composites of multiwalled carbon nanotubes and poly(ethylene terephthalate) around their low percolation threshold

    Science.gov (United States)

    Nuzhnyy, D.; Savinov, M.; Bovtun, V.; Kempa, M.; Petzelt, J.; Mayoral, B.; McNally, T.

    2013-02-01

    Composites of multiwalled carbon nanotubes with poly(ethylene terephthalate) (PET-MWCNT) with up to 3 vol% MWCNTs were prepared and characterized by broad-band AC conductivity and dielectric spectroscopy up to the infrared range using several techniques. A very low electrical percolation threshold of 0.07 vol% MWCNTs was revealed from the low-frequency conductivity plateau as well as from DC conductivity, whose values show the same critical power dependence on MWCNT concentration with the exponent t = 4.3. Above the plateau, the AC conductivity increases with frequency up to the THz range, where it becomes overlapped with the absorption of vibrational modes. The temperature dependence down to ˜5 K has shown semiconductor behaviour with a concentration-independent but weakly temperature-dependent small activation energy of ˜3 meV. The behaviour is compatible with the previously suggested fluctuation-induced tunnelling conductivity model through a thin (˜1 nm) polymer contact layer among the adjacent MWCNTs within percolated clusters. At higher frequencies, deviations from the simple universal conductivity behaviour are observed, indicating some distribution of energy barriers for an electron hopping mechanism.

  3. Up-regulation of cerebral cytochrome-c-oxidase and hemodynamics by transcranial infrared laser stimulation: A broadband near-infrared spectroscopy study.

    Science.gov (United States)

    Wang, Xinlong; Tian, Fenghua; Reddy, Divya D; Nalawade, Sahil S; Barrett, Douglas W; Gonzalez-Lima, Francisco; Liu, Hanli

    2017-12-01

    Transcranial infrared laser stimulation (TILS) is a noninvasive form of brain photobiomulation. Cytochrome-c-oxidase (CCO), the terminal enzyme in the mitochondrial electron transport chain, is hypothesized to be the primary intracellular photoacceptor. We hypothesized that TILS up-regulates cerebral CCO and causes hemodynamic changes. We delivered 1064-nm laser stimulation to the forehead of healthy participants ( n = 11), while broadband near-infrared spectroscopy was utilized to acquire light reflectance from the TILS-treated cortical region before, during, and after TILS. Placebo experiments were also performed for accurate comparison. Time course of spectroscopic readings were analyzed and fitted to the modified Beer-Lambert law. With respect to the placebo readings, we observed (1) significant increases in cerebral concentrations of oxidized CCO (Δ[CCO]; >0.08 µM; p 0.8 µM; p 0.5 µM; p < 0.01) during and after TILS, and (2) linear interplays between Δ[CCO] versus Δ[HbO] and between Δ[CCO] versus Δ[HbT]. Ratios of Δ[CCO]/Δ[HbO] and Δ[CCO]/Δ[HbT] were introduced as TILS-induced metabolic-hemodynamic coupling indices to quantify the coupling strength between TILS-enhanced cerebral metabolism and blood oxygen supply. This study provides the first demonstration that TILS causes up-regulation of oxidized CCO in the human brain, and contributes important insight into the physiological mechanisms.

  4. Advances in high repetition rate, ultra-short, gigawatt laser systems for time-resolved spectroscopy

    International Nuclear Information System (INIS)

    DiMauro, L.F.

    1991-01-01

    The objective of this article is to emphasize the current advances in the development of high-repetition rate amplifier pumps. Although this review highlights amplifier pump development, any recent data from achieved outputs via the tunable amplifier section is also discussed. The first section describes desirable parameters attributable to the pump amplifier while the rest of the article deals with specific examples for various options. The pump amplifiers can be characterized into two distinct classes; those achieving operation in the hundred hertz regime and those performing at repetition rates ≥1kHz. 23 refs., 4 figs

  5. Infrared absorption of gaseous ClCS detected with time-resolved Fourier-transform spectroscopy

    International Nuclear Information System (INIS)

    Chu, Li-Kang; Han, Hui-Ling; Lee, Yuan-Pern

    2007-01-01

    A transient infrared absorption spectrum of gaseous ClCS was detected with a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. ClCS was produced upon irradiating a flowing mixture of Cl 2 CS and N 2 or CO 2 with a KrF excimer laser at 248 nm. A transient band in the region of 1160-1220 cm -1 , which diminished on prolonged reaction, is assigned to the C-S stretching (ν 1 ) mode of ClCS. Calculations with density-functional theory (B3P86 and B3LYP/aug-cc-pVTZ) predict the geometry, vibrational wave numbers, and rotational parameters of ClCS. The rotational contour of the spectrum of ClCS simulated based on predicted rotational parameters agrees satisfactorily with experimental observation; from spectral simulation, the band origin is determined to be at 1194.4 cm -1 . Reaction kinetics involving ClCS, CS, and CS 2 are discussed

  6. Time-resolved luminescence spectroscopy of trace uranyl in wet sand

    International Nuclear Information System (INIS)

    Freed, D.

    1993-01-01

    The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ''fingered'' flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs

  7. Time-resolved luminescence spectroscopy of trace uranyl in wet sand

    Energy Technology Data Exchange (ETDEWEB)

    Freed, D [Massachusetts Inst. of Tech., Cambridge, MA (United States)

    1994-12-31

    The objective of the project was to develop a technique to observe and characterize the behaviour of uranium in unsaturated groundwater flow systems, particularly with regard to unstable ``fingered`` flow, which could drastically reduce time of travel. The actual experimental work described was a study of the feasibility of detecting uranyl at the parts-per-billion level in aqueous solution by means of its luminescence spectrum. A high-power UV laser was used to excite aqueous uranyl in a wet sand mixture; the characteristic green phosphorescence emitted in the decay transition was detected by a photomultiplier tube; and the amplified signal was sent to an oscilloscope in communication with Macintosh data acquisition software. At the time of the conference, a more sophisticated sample configuration for imaging the flow of uranyl was already under development. 5 refs., 3 figs.

  8. Picosecond Time-Resolved Temperature and Density Measurements with K-Shell Spectroscopy

    Science.gov (United States)

    Stillman, C. R.; Nilson, P. M.; Ivancic, S. T.; Mileham, C.; Froula, D. H.; Golovkin, I. E.

    2017-10-01

    The thermal x-ray emission from rapidly heated solid targets containing a buried-aluminum layer was measured to track the evolution of the bulk plasma conditions. The targets were driven by high-contrast 1 ω laser pulses at focused intensities up to 1 × 1019 W/cm2. A streaked x-ray spectrometer recorded the AlHeα and lithium-like satellite lines with 2-ps temporal resolution and moderate resolving power (E E ΔE 1000 ΔE 1000) . Time-integrated measurements over the same spectral range were used to correct the streaked data for variations in photocathode sensitivity. Linewidths and intensity ratios from the streaked data were interpreted using a collisional radiative atomic kinetics model to provide the average plasma conditions in the buried layer as a function of time. Experimental uncertainties in the measured plasma conditions are quantified within a consistent model-dependent framework. The data demonstrate the production of a 330 +/-56 eV, 0.9 +/-0.3 g/cm3 plasma that evolves slowly during peak Heα emission. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  9. Photoionization of atmospheric gases studied by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Mics, Zoltan; Kužel, Petr; Jungwirth, Pavel; Bradforth, S. E.

    2008-01-01

    Roč. 465, 1-3 (2008), s. 20-24 ISSN 0009-2614 R&D Projects: GA MŠk LC512; GA ČR(CZ) GA202/06/0286 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z40550506 Keywords : terahertz * pump -probe * atmospheric gases * photoionization * plasma Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.169, year: 2008

  10. Ultrafast carrier dynamics in microcrystalline silicon probed by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Fekete, Ladislav; Kužel, Petr; Němec, Hynek; Kadlec, Filip; Deyneka, Alexander; Stuchlík, Jiří; Fejfar, Antonín

    2009-01-01

    Roč. 79, č. 11 (2009), 115306/1-115306/13 ISSN 1098-0121 R&D Projects: GA MŠk(CZ) LC06040; GA AV ČR(CZ) IAA100100902 Institutional research plan: CEZ:AV0Z10100520; CEZ:AV0Z10100521 Keywords : microcrystalline silicon * amorphous silicon * terahertz * ultrafast * photoconductivity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.475, year: 2009

  11. Conformational Analysis of DNA Repair Intermediates by Time-Resolved Fluorescence Spectroscopy

    OpenAIRE

    Lin, Su; Horning, David P.; Szostak, Jack W.; Chaput, John C.

    2009-01-01

    DNA repair enzymes are essential for maintaining the integrity of the DNA sequence. Unfortunately, very little is known about how these enzymes recognize damaged regions along the helix. Structural analysis of cellular repair enzymes bound to DNA reveals that these enzymes are able to recognize DNA in a variety of conformations. However, the prevalence of these deformations in the absence of enzymes remains unclear, as small populations of DNA conformations are often difficult to detect by NM...

  12. Carrier dynamics in microcrystalline silicon studied by time-resolved terahertz spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Fekete, Ladislav; Němec, Hynek; Kadlec, Filip; Kužel, Petr; Stuchlík, Jiří; Fejfar, Antonín; Kočka, Jan

    2006-01-01

    Roč. 352, - (2006), s. 2846-2849 ISSN 0022-3093 R&D Projects: GA AV ČR(CZ) KJB100100512 Institutional research plan: CEZ:AV0Z10100520 Keywords : silicon * solar cells * dielectric properties * relaxation * electric modulus * chemical vapor deposition * microcrystallinity Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.362, year: 2006

  13. Infrared absorption of CH3OSO detected with time-resolved Fourier-transform spectroscopy.

    Science.gov (United States)

    Chen, Jin-Dah; Lee, Yuan-Pern

    2011-03-07

    A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to detect temporally resolved infrared absorption spectra of CH(3)OSO produced upon irradiation of a flowing gaseous mixture of CH(3)OS(O)Cl in N(2) or CO(2) at 248 nm. Two intense transient features with origins near 1152 and 994 cm(-1) are assigned to syn-CH(3)OSO; the former is attributed to overlapping bands at 1154 ± 3 and 1151 ± 3 cm(-1), assigned to the S=O stretching mixed with CH(3) rocking (ν(8)) and the S=O stretching mixed with CH(3) wagging (ν(9)) modes, respectively, and the latter to the C-O stretching (ν(10)) mode at 994 ± 6 cm(-1). Two weak bands at 2991 ± 6 and 2956 ± 3 cm(-1) are assigned as the CH(3) antisymmetric stretching (ν(2)) and symmetric stretching (ν(3)) modes, respectively. Observed vibrational transition wavenumbers agree satisfactorily with those predicted with quantum-chemical calculations at level B3P86∕aug-cc-pVTZ. Based on rotational parameters predicted at that level, the simulated rotational contours of these bands agree satisfactorily with experimental results. The simulation indicates that the S=O stretching mode of anti-CH(3)OSO near 1164 cm(-1) likely makes a small contribution to the observed band near 1152 cm(-1). A simple kinetic model of self-reaction is employed to account for the decay of CH(3)OSO and yields a second-order rate coefficient k=(4 ± 2)×10(-10) cm(3)molecule(-1)s(-1). © 2011 American Institute of Physics.

  14. Temperature-dependent loop formation kinetics in flexible peptides studied by time-resolved fluorescence spectroscopy

    Directory of Open Access Journals (Sweden)

    Harekrushna Sahoo

    2006-01-01

    Full Text Available Looping rates in short polypeptides can be determined by intramolecular fluorescence quenching of a 2,3-diazabicyclo[2.2.2]oct-2-ene-labeled asparagine (Dbo by tryptophan. By this methodology, the looping rates in glycine-serine peptides with the structure Trp-(Gly-Sern-Dbo-NH2 of different lengths (n = 0–10 were determined in dependence on temperature in D2O and the activation parameters were derived. In general, the looping rate increases with decreasing peptide length, but the shortest peptide (n=0 shows exceptional behavior because its looping rate is slower than that for the next longer ones (n=1,2. The activation energies increase from 17.5 kJ mol−1 for the longest peptide (n=10 to 20.5 kJ mol−1 for the shortest one (n=0, while the pre-exponential factors (log⁡(A/s−1 range from 10.20 to 11.38. The data are interpreted in terms of an interplay between internal friction (stiffness of the biopolymer backbone and steric hindrance effects and solvent friction (viscosity-limited diffusion. For the longest peptides, the activation energies resemble more and more the value expected for solvent viscous flow. Internal friction is most important for the shortest peptides, causing a negative curvature and a smaller than ideal slope (ca. –1.1 of the double-logarithmic plots of the looping rates versus the number of peptide chain segments (N. Interestingly, the corresponding plot for the pre-exponential factors (logA versus logN shows the ideal slope (–1.5. While the looping rates can be used to assess the flexibility of peptides in a global way, it is suggested that the activation energies provide a measure of the “thermodynamic” flexibility of a peptide, while the pre-exponential factors reflect the “dynamic” flexibility.

  15. Time-resolved resonance Raman spectroscopy of intermediates of bacteriorhodopsin: The bK(590) intermediate.

    Science.gov (United States)

    Terner, J; Hsieh, C L; Burns, A R; El-Sayed, M A

    1979-07-01

    We have combined microbeam and flow techniques with computer subtraction methods to obtain the resonance Raman spectrum of the short lived batho-intermediate (bK(590)) of bacteriorhodopsin. Comparison of the spectra obtained in (1)H(2)O and (2)H(2)O, as well as the fact that the bK(590) intermediate shows large optical red shifts, suggests that the Schiff base linkage of this intermediate is protonated. The fingerprint region of the spectrum of bK(590), sensitive to the isomeric configuration of the retinal chromophore, does not resemble the corresponding region of the parent bR(570) form. The resonance Raman spectrum of bK(590) as well as the spectra of all of the other main intermediates in the photoreaction cycle of bacteriorhodopsin are discussed and compared with resonance Raman spectra of published model compounds.

  16. Investigation of setting reaction in magnesium potassium phosphate ceramics with time resolved infrared spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Mácová, Petra; Viani, Alberto

    2017-01-01

    Roč. 205, October (2017), s. 62-66 ISSN 0167-577X R&D Projects: GA MŠk(CZ) LO1219 Keywords : amorphous materials * magnesium potassium phosphate cements * FTIR Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass OBOR OECD: Ceramics Impact factor: 2.572, year: 2016 http://www.sciencedirect.com/science/article/pii/S0167577X17309552

  17. Time-resolved in situ spectroscopy during formation of the GaP/Si(100) heterointerface

    Czech Academy of Sciences Publication Activity Database

    Supplie, O.; May, M.M.; Steinbach, G.; Romanyuk, Olexandr; Grosse, F.; Nägelein, A.; Kleinschmidt, P.; Brückner, S.; Hannappel, T.

    2015-01-01

    Roč. 6, č. 3 (2015), 464-469 ISSN 1948-7185 Grant - others:AVČR(CZ) M100101201 Institutional support: RVO:68378271 Keywords : solar cells * GaP/Si * heterointerface structure * MOCVD * XPS * RAS Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 8.539, year: 2015

  18. Luminescence life time and time-resolved spectroscopy of Cr3+ ions in strontium barium niobate

    International Nuclear Information System (INIS)

    Han, T.P.J.; Jaque, F.; Jaque, D.; Garcia-Sole, J.; Ivleva, L.

    2006-01-01

    This paper reports on the photo-luminescence spectroscopic results of congruent strontium-barium-niobate (SBN) crystals doped with Cr 2 O, at cryogenic temperature (20 K). The experimental results reveal the need of re-assignment of the Cr 3+ ions defect centres in this material. For first time, a broad emission band in the near infrared region centred at ca. 950 nm is reported. This emission band has micro-seconds decaytime constant and a band-width full-width at half-maximum (FWHM) larger than 1700 cm -1 and has been ascribed to the vibronically assisted 4 T 2 →4 A 2 transition. A much narrower emission band centred at ca. 764 nm with milli-seconds decaytime constant and a FWHM band-width of ca. 170 cm -1 is correlated to the 2 E →4 A 2 radiative transition (R-line)

  19. Time-resolved spectroscopy of CsI(CO{sub 3}) scintillator

    Energy Technology Data Exchange (ETDEWEB)

    Yakovlev, V. [National Research Tomsk Polytechnic University, 30 Lenin Avenue, Tomsk 634034 (Russian Federation); Trefilova, L., E-mail: laratrefilova@ukr.net [National University of Civil Protection, 94 Chernyshevska Street, Kharkiv 61023 (Ukraine); Lebedinsky, A.; Daulet, Z. [National Research Tomsk Polytechnic University, 30 Lenin Avenue, Tomsk 634034 (Russian Federation); Dubtsov, I. [Institute for Scintillation Materials, NAS of Ukraine, 60 Lenin Avenue, Kharkiv 61001 (Ukraine)

    2016-05-15

    The spectral-kinetics characteristics of short-living absorption and luminescence induced by an electron pulse irradiation (E{sub e}=0.25 MeV, t{sub 1/2}= 7ns, W=2×10{sup 10}÷4×10{sup 12} electron/cm{sup 2}) in CsI(CO{sub 3}) crystal are studied. It is shown that the scintillation pulse of CsI(CO{sub 3}) crystal is caused by the radiative annihilation of perturbed two-halogen excitons of two types, which are located in nearby impurity-vacancy dipole [CO{sub 3}{sup 2–}−υ{sub a}{sup +}] anion sites. The processes responsible for post-radiation rise and decay of both CO{sub 3}{sup 2–}-related luminescence bands with maxima at 2.8 and 3.2 eV are monomolecular with the thermal activation energy E{sub rise}=0.1 eV and E{sub decay}=0.05 eV. The cathodoluminescence pulse kinetics is discussed in the terms of the thermally assistant release of holes captured by CO{sub 3}{sup 2–}-ions and the formation of CO{sub 3}{sup 2–}-perturbed two-halide excitons.

  20. Time-resolved terahertz spectroscopy in a parallel-plate waveguide

    DEFF Research Database (Denmark)

    Cooke, David; Jepsen, Peter Uhd

    2009-01-01

    The parallel plate waveguide (PPWG), formed by two conducting parallel plates separated by a distance on the order of the wavelength of the propagating light, has shown itself to be a near ideal terahertz interconnect exhibiting low loss and dispersionless propagation.[1] It is also a useful tool...

  1. MAPS OF EVOLVING CLOUD STRUCTURES IN LUHMAN 16AB FROM HST TIME-RESOLVED SPECTROSCOPY

    Energy Technology Data Exchange (ETDEWEB)

    Karalidi, Theodora; Apai, Dániel [Steward Observatory, Department of Astronomy, University of Arizona, 933 North Cherry Avenue, Tucson, AZ 85721 (United States); Marley, Mark S. [NASA Ames Research Center, MS-245-3, Moffett Field, CA 94035 (United States); Buenzli, Esther, E-mail: tkaralidi@email.arizona.edu [Institute for Astronomy, ETH Zürich, Wolfgang-Pauli-Str. 27, 8093 Zürich (Switzerland)

    2016-07-10

    WISE J104915.57-531906.1 is the nearest brown dwarf binary to our solar system, consisting of two brown dwarfs in the L / T transition: Luhman 16A and B. In this paper, we present the first map of Luhman 16A, and maps of Luhman 16B for two epochs. Our maps were created by applying Aeolus , a Markov-Chain Monte Carlo code that maps the top-of-the-atmosphere (TOA) structure of brown dwarf and other ultracool atmospheres, to light curves of Luhman 16A and B using the Hubble Space Telescope ’s G141 and G102 grisms. Aeolus retrieved three or four spots in the TOA of Luhman 16A and B, with a surface coverage of 19%–32% (depending on an assumed rotational period of 5 hr or 8 hr) or 21%–38.5% (depending on the observational epoch), respectively. The brightness temperature of the spots of the best-fit models was ∼200 K hotter than the background TOA. We compared our Luhman 16B map with the only previously published map. Interestingly, our map contained a large TOA spot that was cooler (Δ T ∼ 51 K) than the background, which lay at low latitudes, in agreement with the previous Luhman 16B map. Finally, we report the detection of a feature reappearing in Luhman 16B light curves that are separated by tens of hundreds of rotations from each other. We speculate that this feature is related to TOA structures of Luhman 16B.

  2. Time-resolved detection of surface plasmon polaritons with a scanning tunneling microscope

    DEFF Research Database (Denmark)

    Keil, Ulrich Dieter Felix; Ha, T.; Jensen, Jacob Riis

    1998-01-01

    We present the time-resolved detection of surface plasmon polaritons with an STM. The results indicate that the time resolved signal is due to rectification of coherently superimposed plasmon voltages. The comparison with differential reflectivity measurements shows that the tip itself influences...... the decay of the plasmon-field coherence. Generation of the measured signal at the tunneling junction offers the possibility to observe ultrafast effects with a spatial resolution determined by the tunneling junction...

  3. New layout of time resolved beam energy spectrum measurement for dragon-I

    International Nuclear Information System (INIS)

    Liao Shuqing; Zhang Kaizhi; Shi Jinshui

    2010-01-01

    A new layout of time resolved beam energy spectrum measurement is proposed for Dragon-I by a new method named RBS (rotating beams in solenoids). The basic theory of RBS and the new layout are presented and the measuring error is also discussed. The derived time resolved beam energy spectrum is discrete and is determined by measuring the beam's rotating angle and expanding width through a group of solenoids at the export of Dragon-I. (authors)

  4. Improvements in brain activation detection using time-resolved diffuse optical means

    Science.gov (United States)

    Montcel, Bruno; Chabrier, Renee; Poulet, Patrick

    2005-08-01

    An experimental method based on time-resolved absorbance difference is described. The absorbance difference is calculated over each temporal step of the optical signal with the time-resolved Beer-Lambert law. Finite element simulations show that each step corresponds to a different scanned zone and that cerebral contribution increases with the arrival time of photons. Experiments are conducted at 690 and 830 nm with a time-resolved system consisting of picosecond laser diodes, micro-channel plate photo-multiplier tube and photon counting modules. The hemodynamic response to a short finger tapping stimulus is measured over the motor cortex. Time-resolved absorbance difference maps show that variations in the optical signals are not localized in superficial regions of the head, which testify for their cerebral origin. Furthermore improvements in the detection of cerebral activation is achieved through the increase of variations in absorbance by a factor of almost 5 for time-resolved measurements as compared to non-time-resolved measurements.

  5. Application of time-resolved glucose concentration photoacoustic signals based on an improved wavelet denoising

    Science.gov (United States)

    Ren, Zhong; Liu, Guodong; Huang, Zhen

    2014-10-01

    Real-time monitoring of blood glucose concentration (BGC) is a great important procedure in controlling diabetes mellitus and preventing the complication for diabetic patients. Noninvasive measurement of BGC has already become a research hotspot because it can overcome the physical and psychological harm. Photoacoustic spectroscopy is a well-established, hybrid and alternative technique used to determine the BGC. According to the theory of photoacoustic technique, the blood is irradiated by plused laser with nano-second repeation time and micro-joule power, the photoacoustic singals contained the information of BGC are generated due to the thermal-elastic mechanism, then the BGC level can be interpreted from photoacoustic signal via the data analysis. But in practice, the time-resolved photoacoustic signals of BGC are polluted by the varities of noises, e.g., the interference of background sounds and multi-component of blood. The quality of photoacoustic signal of BGC directly impacts the precision of BGC measurement. So, an improved wavelet denoising method was proposed to eliminate the noises contained in BGC photoacoustic signals. To overcome the shortcoming of traditional wavelet threshold denoising, an improved dual-threshold wavelet function was proposed in this paper. Simulation experimental results illustrated that the denoising result of this improved wavelet method was better than that of traditional soft and hard threshold function. To varify the feasibility of this improved function, the actual photoacoustic BGC signals were test, the test reslut demonstrated that the signal-to-noises ratio(SNR) of the improved function increases about 40-80%, and its root-mean-square error (RMSE) decreases about 38.7-52.8%.

  6. Real-time visualization of the vibrational wavepacket dynamics in electronically excited pyrimidine via femtosecond time-resolved photoelectron imaging

    Science.gov (United States)

    Li, Shuai; Long, Jinyou; Ling, Fengzi; Wang, Yanmei; Song, Xinli; Zhang, Song; Zhang, Bing

    2017-07-01

    The vibrational wavepacket dynamics at the very early stages of the S1-T1 intersystem crossing in photoexcited pyrimidine is visualized in real time by femtosecond time-resolved photoelectron imaging and time-resolved mass spectroscopy. A coherent superposition of the vibrational states is prepared by the femtosecond pump pulse at 315.3 nm, resulting in a vibrational wavepacket. The composition of the prepared wavepacket is directly identified by a sustained quantum beat superimposed on the parent-ion transient, possessing a frequency in accord with the energy separation between the 6a1 and 6b2 states. The dephasing time of the vibrational wavepacket is determined to be 82 ps. More importantly, the variable Franck-Condon factors between the wavepacket components and the dispersed cation vibrational levels are experimentally illustrated to identify the dark state and follow the energy-flow dynamics on the femtosecond time scale. The time-dependent intensities of the photoelectron peaks originated from the 6a1 vibrational state exhibit a clear quantum beating pattern with similar periodicity but a phase shift of π rad with respect to those from the 6b2 state, offering an unambiguous picture of the restricted intramolecular vibrational energy redistribution dynamics in the 6a1/6b2 Fermi resonance.

  7. Broadband enhancement of local density of states using silicon-compatible hyperbolic metamaterials

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Yu; Inampudi, Sandeep; Capretti, Antonio [Department of Electrical and Computer Engineering and Photonics Center, Boston University, 8 Saint Mary' s Street Boston, Massachusetts 02215 (United States); Sugimoto, Hiroshi [Department of Electrical and Computer Engineering and Photonics Center, Boston University, 8 Saint Mary' s Street Boston, Massachusetts 02215 (United States); Department of Electrical and Electronic Engineering, Graduate School of Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501 (Japan); Fujii, Minoru [Department of Electrical and Electronic Engineering, Graduate School of Engineering, Kobe University, Rokkodai, Nada, Kobe 657-8501 (Japan); Dal Negro, Luca, E-mail: dalnegro@bu.edu [Department of Electrical and Computer Engineering and Photonics Center, Boston University, 8 Saint Mary' s Street Boston, Massachusetts 02215 (United States); Division of Materials Science and Engineering, Boston University, 15 Saint Mary' s Street, Brookline, Massachusetts 02446 (United States)

    2015-06-15

    Light emitting silicon quantum dots by colloidal synthesis were uniformly spin-coated into a 20 nm-thick film and deposited atop a hyperbolic metamaterial of alternating TiN and SiO{sub 2} sub-wavelength layers. Using steady-state and time-resolved photoluminescence spectroscopy as a function of the emission wavelength in partnership with rigorous electromagnetic modeling of dipolar emission, we demonstrate enhanced Local Density of States and coupling to high-k modes in a broad spectral range. These findings provide an alternative approach for the engineering of novel Si-compatible broadband sources that leverage the control of radiative transitions in hyperbolic metamaterials and the flexibility of the widespread Si platform.

  8. Laser ablation of an indium target: time-resolved Fourier-transform infrared spectra of In I in the 700–7700 cm−1 range

    Czech Academy of Sciences Publication Activity Database

    Civiš, Svatopluk; Kubelík, Petr; Ferus, Martin; Chernov, Vladislav E.; Zanozina, Ekaterina M.; Juha, Libor

    2014-01-01

    Roč. 29, č. 12 (2014), s. 2275-2283 ISSN 0267-9477 R&D Projects: GA MŠk LD14115; GA MŠk(CZ) LG13029 Institutional support: RVO:61388955 ; RVO:68378271 Keywords : time-resolved fluorescence * Fourier transform infra reds * Laser-induced breakdown spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.466, year: 2014

  9. Trans-cranial infrared laser stimulation induces hemodynamic and metabolic response measured by broadband near infrared spectroscopy in vivo on human forehead (Conference Presentation)

    Science.gov (United States)

    Wang, Xinlong; Nalawade, Sahil Sunil; Reddy, Divya Dhandapani; Tian, Fenghua; Gonzalez-Lima, F.; Liu, Hanli

    2017-02-01

    Transcranial infrared laser stimulation (TILS) uses infrared light (lasers or LEDs) for nondestructive and non-thermal photobiomodulation on the human brain. Although TILS has shown its beneficial effects to a variety of neurological and psychological conditions, its physiological mechanism remains unknown. Cytochrome-c-oxidase (CCO), the last enzyme in the electron transportation chain, is proposed to be the primary photoacceptor of this infrared laser. In this study, we wish to validate this proposed mechanism. We applied 8 minutes in vivo TILS on the right forehead of 11 human participants with a 1064-nm laser. Broad-band near infrared spectroscopy (bb-NIRS) from 740-900nm was also employed near the TILS site to monitor hemodynamic and metabolic responses during the stimulation and 5-minute recovery period. For rigorous comparison, we also performed similar 8-min bb-NIR measurements under placebo conditions. A multi-linear regression analysis based on the modified Beer-Lambert law was performed to estimate concentration changes of oxy-hemoglobin (Δ[HbO]), deoxy-hemoglobin (Δ[Hb]), and cytochrome-c-oxidase (Δ[CCO]). We found that TILS induced significant increases of [CCO], [HbO] and a decrease of [Hb] with dose-dependent manner as compared with placebo treatments. Furthermore, strong linear relationships or interplays between [CCO] versus [HbO] and [CCO] versus [Hb] induced by TILS were observed in vivo for the first time. These relationships have clearly revealed close coupling/relationship between the hemodynamic oxygen supply and blood volume versus up-regulation of CCO induced by photobiomodulation. Our results demonstrate the tremendous potential of bb-NIRS as a non-invasive in vivo means to study photobiomodulation mechanisms and perform treatment evaluations of TILS.

  10. Binding and relaxation behavior of Coumarin-153 in lecithin-taurocholate mixed micelles: A time resolved fluorescence spectroscopic study

    Science.gov (United States)

    Chakrabarty, Debdeep; Chakraborty, Anjan; Seth, Debabrata; Hazra, Partha; Sarkar, Nilmoni

    2005-09-01

    The microenvironment of the bile salt-lecithin mixed aggregates has been investigated using steady state and picosecond time resolved fluorescence spectroscopy. The steady state spectra show that the polarity of the bile salt is higher compared to lecithin vesicles or the mixed aggregates. We have observed slow solvent relaxation in bile salt micelles and lecithin vesicles. The solvation time is gradually slowed down due to gradual addition of the bile salt in lecithin vesicles. Addition of bile salt leads to the tighter head group packing in lecithin. Thus, mobility of the water molecules becomes slower and consequently the solvation time is also retarded. We have observed bimodal slow rotational relaxation time in all these systems.

  11. Mapping Charge Carrier Density in Organic Thin-Film Transistors by Time-Resolved Photoluminescence Lifetime Studies

    DEFF Research Database (Denmark)

    Leißner, Till; Jensen, Per Baunegaard With; Liu, Yiming

    2017-01-01

    The device performance of organic transistors is strongly influenced by the charge carrier distribution. A range of factors effect this distribution, including injection barriers at the metal-semiconductor interface, the morphology of the organic film, and charge traps at the dielectric/organic...... interface or at grain boundaries. In our comprehensive experimental and analytical work we demonstrate a method to characterize the charge carrier density in organic thin-film transistors using time-resolved photoluminescence spectroscopy. We developed a numerical model that describes the electrical...... and optical responses consistently. We determined the densities of free and trapped holes at the interface between the organic layer and the SiO2 gate dielectric by comparison to electrical measurements. Furthermore by applying fluorescence lifetime imaging microscopy we determine the local charge carrier...

  12. Portable double-sided pulsed laser heating system for time-resolved geoscience and materials science applications.

    Science.gov (United States)

    Aprilis, G; Strohm, C; Kupenko, I; Linhardt, S; Laskin, A; Vasiukov, D M; Cerantola, V; Koemets, E G; McCammon, C; Kurnosov, A; Chumakov, A I; Rüffer, R; Dubrovinskaia, N; Dubrovinsky, L

    2017-08-01

    A portable double-sided pulsed laser heating system for diamond anvil cells has been developed that is able to stably produce laser pulses as short as a few microseconds with repetition frequencies up to 100 kHz. In situ temperature determination is possible by collecting and fitting the thermal radiation spectrum for a specific wavelength range (particularly, between 650 nm and 850 nm) to the Planck radiation function. Surface temperature information can also be time-resolved by using a gated detector that is synchronized with the laser pulse modulation and space-resolved with the implementation of a multi-point thermal radiation collection technique. The system can be easily coupled with equipment at synchrotron facilities, particularly for nuclear resonance spectroscopy experiments. Examples of applications include investigations of high-pressure high-temperature behavior of iron oxides, both in house and at the European Synchrotron Radiation Facility using the synchrotron Mössbauer source and nuclear inelastic scattering.

  13. Time-resolved SFG study of formate on a Ni( 1 1 1 ) surface under irradiation of picosecond laser pulses

    Science.gov (United States)

    Noguchi, H.; Okada, T.; Onda, K.; Kano, S. S.; Wada, A.; Domen, K.

    2003-03-01

    Time-resolved sum-frequency generation spectroscopy was carried out on a deuterated formate (DCOO) adsorbed on Ni(1 1 1) surface to investigate the surface reaction dynamics under instantaneous surface temperature jump induced by the irradiation by picosecond laser pulses. The irradiation of pump pulse (800 nm) caused the rapid intensity decrease of both CD and OCO stretching modes of bridged formate on Ni(1 1 1). Different temporal behaviors of intensity recovery between these two vibrational modes were observed, i.e., CD stretching mode recovered faster than OCO. This is the first result to show that the dynamics of adsorbates on metals strongly depends on the observed vibrational mode. From the results of temperature and pump fluence dependence, we concluded that the observed intensity change was not due to the decomposition or desorption, but was induced by a non-thermal process.

  14. The time resolved SBS and SRS research in heavy water and its application in CARS

    Science.gov (United States)

    Liu, Jinbo; Gai, Baodong; Yuan, Hong; Sun, Jianfeng; Zhou, Xin; Liu, Di; Xia, Xusheng; Wang, Pengyuan; Hu, Shu; Chen, Ying; Guo, Jingwei; Jin, Yuqi; Sang, Fengting

    2018-05-01

    We present the time-resolved character of stimulated Brillouin scattering (SBS) and backward stimulated Raman scattering (BSRS) in heavy water and its application in Coherent Anti-Stokes Raman Scattering (CARS) technique. A nanosecond laser from a frequency-doubled Nd: YAG laser is introduced into a heavy water cell, to generate SBS and BSRS beams. The SBS and BSRS beams are collinear, and their time resolved characters are studied by a streak camera, experiment show that they are ideal source for an alignment-free CARS system, and the time resolved property of SBS and BSRS beams could affect the CARS efficiency significantly. By inserting a Dye cuvette to the collinear beams, the time-overlapping of SBS and BSRS could be improved, and finally the CARS efficiency is increased, even though the SBS energy is decreased. Possible methods to improve the efficiency of this CARS system are discussed too.

  15. Time-resolved PHERMEX image restorations constrained with an additional multiply-exposed image

    International Nuclear Information System (INIS)

    Kruger, R.P.; Breedlove, J.R. Jr.; Trussell, H.J.

    1978-06-01

    There are a number of possible industrial and scientific applications of nanosecond cineradiographs. Although the technology exists to produce closely spaced pulses of x rays for this application, the quality of the time-resolved radiographs is severely limited. The limitations arise from the necessity of using a fluorescent screen to convert the transmitted x rays to light and then using electro-optical imaging systems to gate and to record the images with conventional high-speed cameras. It has been proposed that, in addition to the time-resolved images, a conventional multiply exposed radiograph be obtained. This report uses both PHERMEX and conventional photographic simulations to demonstrate that the additional information supplied by the multiply exposed radiograph can be used to improve the quality of digital image restorations of the time-resolved pictures over what could be achieved with the degraded images alone

  16. Femtosecond Time-Resolved Resonance-Enhanced CARS of Gaseous Iodine at Room Temperature

    International Nuclear Information System (INIS)

    He Ping; Fan Rong-Wei; Xia Yuan-Qin; Yu Xin; Chen De-Ying; Yao Yong

    2011-01-01

    Time-resolved resonance-enhanced coherent anti-Stokes Raman scattering (CARS) is applied to investigate molecular dynamics in gaseous iodine. 40 fs laser pulses are applied to create and monitor the high vibrational states of iodine at room temperature (corresponding to a vapor pressure as low as about 35 Pa) by femtosecond time-resolved CARS. Depending on the time delay between the probe pulse and the pump/Stokes pulse pairs, the high vibrational states both on the electronically ground states and the excited states can be detected as oscillations in the CARS transient signal. It is proved that the femtosecond time-resolved CARS technique is a promising candidate for investigating the molecular dynamics of a low concentration system and can be applied to environmental and atmospheric monitoring measurements. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  17. Time-resolved electron transport in quantum-dot systems; Zeitaufgeloester Elektronentransport in Quantendotsystemen

    Energy Technology Data Exchange (ETDEWEB)

    Croy, Alexander

    2010-06-30

    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.

  18. Spin and time-resolved magnetic resonance in radiation chemistry. Recent developments and perspectives

    International Nuclear Information System (INIS)

    Shkrob, I.A.; Trifunac, A.D.

    1997-01-01

    Time-resolved pulsed EPR and ODMR in studies on early events in radiation chemistry are examined. It is concluded that these techniques yield valuable and diverse information about chemical reactions in spurs, despite the fact that the spur reactions occur on a time scale that is much shorter than the time resolution of these methods. Several recent examples include EPR of H/D atoms in vitreous silica and cryogenic liquids and ODMR of doped alkane solids and amorphous semiconductors. It is argued that a wider use of time-resolved magnetic resonance methods would benefit the studies on radiation chemistry of disordered solids, simple liquids, and polymers. (author)

  19. Proceedings of the Third Symposium Optical Spectroscopy SOS-84

    International Nuclear Information System (INIS)

    Fassler, D.; Feller, K.H.; Wilhelmi, B.

    1985-01-01

    The main topics of the symposium were: 1) new developments and applications of laser spectroscopy including time resolved UV/VIS spectroscopy, time resolved fluorescence spectroscopy, and laser Raman spectroscopy, 2) dynamics and photokinetics of molecular systems, and 3) spectroscopy and photoprocesses in organized biological systems

  20. Computational time-resolved and resonant x-ray scattering of strongly correlated materials

    Energy Technology Data Exchange (ETDEWEB)

    Bansil, Arun [Northeastern Univ., Boston, MA (United States)

    2016-11-09

    predominantly decays via Auger processes, thereby providing an internal time-scale, which limits intermediate-state processes to timescales of a few femtoseconds. Accordingly, a number of activities directed at modeling K-, L- and M-edge RIXS in correlated materials were also pursused by our CRT. Our research effort supported by this CMCSN grant substantially advanced the understanding of x-ray scattering processes in the time-domain as well as in the more conventional scattering channels, including time-resolved photoemission, and how such processes can be modeled realistically in complex correlated materials more generally. The modeling of relaxation processes involved in time-domain spectroscopies is important also for understanding photoinduced effects such as energy conversion in photosynthesis and solar cell applications, and thus impacts the basic science for energy needs.

  1. Time-resolved optical spectrometer based on a monolithic array of high-precision TDCs and SPADs

    Science.gov (United States)

    Tamborini, Davide; Markovic, Bojan; Di Sieno, Laura; Contini, Davide; Bassi, Andrea; Tisa, Simone; Tosi, Alberto; Zappa, Franco

    2013-12-01

    We present a compact time-resolved spectrometer suitable for optical spectroscopy from 400 nm to 1 μm wavelengths. The detector consists of a monolithic array of 16 high-precision Time-to-Digital Converters (TDC) and Single-Photon Avalanche Diodes (SPAD). The instrument has 10 ps resolution and reaches 70 ps (FWHM) timing precision over a 160 ns full-scale range with a Differential Non-Linearity (DNL) better than 1.5 % LSB. The core of the spectrometer is the application-specific integrated chip composed of 16 pixels with 250 μm pitch, containing a 20 μm diameter SPAD and an independent TDC each, fabricated in a 0.35 μm CMOS technology. In front of this array a monochromator is used to focus different wavelengths into different pixels. The spectrometer has been used for fluorescence lifetime spectroscopy: 5 nm spectral resolution over an 80 nm bandwidth is achieved. Lifetime spectroscopy of Nile blue is demonstrated.

  2. Time resolved Thomson scattering measurements on a high pressure mercury lamp

    NARCIS (Netherlands)

    Vries, de N.; Zhu, Xiao-Yan; Kieft, E.R.; Mullen, van der J.J.A.M.

    2005-01-01

    Time resolved Thomson scattering (TS) measurements have been performed on an ac driven high pressure mercury lamp. For this high intensity discharge (HID) lamp, TS is coherent and a coherent fitting routine, including rotational Raman calibration, was used to determine ne and Te from the measured

  3. Evaluating scintillator performance in time-resolved hard X-ray studies at synchrotron light sources

    International Nuclear Information System (INIS)

    Rutherford, Michael E.; Chapman, David J.; White, Thomas G.; Drakopoulos, Michael; Rack, Alexander; Eakins, Daniel E.

    2016-01-01

    Scintillator performance in time-resolved, hard, indirect detection X-ray studies on the sub-microsecond timescale at synchrotron light sources is reviewed, modelled and examined experimentally. LYSO:Ce is found to be the only commercially available crystal suitable for these experiments. The short pulse duration, small effective source size and high flux of synchrotron radiation is ideally suited for probing a wide range of transient deformation processes in materials under extreme conditions. In this paper, the challenges of high-resolution time-resolved indirect X-ray detection are reviewed in the context of dynamic synchrotron experiments. In particular, the discussion is targeted at two-dimensional integrating detector methods, such as those focused on dynamic radiography and diffraction experiments. The response of a scintillator to periodic synchrotron X-ray excitation is modelled and validated against experimental data collected at the Diamond Light Source (DLS) and European Synchrotron Radiation Facility (ESRF). An upper bound on the dynamic range accessible in a time-resolved experiment for a given bunch separation is calculated for a range of scintillators. New bunch structures are suggested for DLS and ESRF using the highest-performing commercially available crystal LYSO:Ce, allowing time-resolved experiments with an interframe time of 189 ns and a maximum dynamic range of 98 (6.6 bits)

  4. Evaluating scintillator performance in time-resolved hard X-ray studies at synchrotron light sources

    Energy Technology Data Exchange (ETDEWEB)

    Rutherford, Michael E.; Chapman, David J.; White, Thomas G. [Imperial College London, London (United Kingdom); Drakopoulos, Michael [Diamond Light Source, I12 Joint Engineering, Environmental, Processing (JEEP) Beamline, Didcot, Oxfordshire (United Kingdom); Rack, Alexander [European Synchrotron Radiation Facility, Grenoble (France); Eakins, Daniel E., E-mail: d.eakins@imperial.ac.uk [Imperial College London, London (United Kingdom)

    2016-03-24

    Scintillator performance in time-resolved, hard, indirect detection X-ray studies on the sub-microsecond timescale at synchrotron light sources is reviewed, modelled and examined experimentally. LYSO:Ce is found to be the only commercially available crystal suitable for these experiments. The short pulse duration, small effective source size and high flux of synchrotron radiation is ideally suited for probing a wide range of transient deformation processes in materials under extreme conditions. In this paper, the challenges of high-resolution time-resolved indirect X-ray detection are reviewed in the context of dynamic synchrotron experiments. In particular, the discussion is targeted at two-dimensional integrating detector methods, such as those focused on dynamic radiography and diffraction experiments. The response of a scintillator to periodic synchrotron X-ray excitation is modelled and validated against experimental data collected at the Diamond Light Source (DLS) and European Synchrotron Radiation Facility (ESRF). An upper bound on the dynamic range accessible in a time-resolved experiment for a given bunch separation is calculated for a range of scintillators. New bunch structures are suggested for DLS and ESRF using the highest-performing commercially available crystal LYSO:Ce, allowing time-resolved experiments with an interframe time of 189 ns and a maximum dynamic range of 98 (6.6 bits)

  5. Time Resolved Shadowgraph Images of Silicon during Laser Ablation: Shockwaves and Particle Generation

    International Nuclear Information System (INIS)

    Liu, C Y; Mao, X L; Greif, R; Russo, R E

    2007-01-01

    Time resolved shadowgraph images were recorded of shockwaves and particle ejection from silicon during laser ablation. Particle ejection and expansion were correlated to an internal shockwave resonating between the shockwave front and the target surface. The number of particles ablated increased with laser energy and was related to the crater volume

  6. On the use of time resolved laser-induced spectrofluorometry in the nuclear fuel cycle

    International Nuclear Information System (INIS)

    Moulin, C.; Decambox, P.; Mauchien, P.; Davin, T.; Pradel, B.

    1991-01-01

    Time Resolved Laser-Induced Spectrofluorometry (TRLIS) has been used for actinides trace analysis and complexation analysis in the nuclear fuel cycle. Results obtained in the different fields such as in geology, in the Purex process, in the environment, in the medical and in waste storage assessment are presented. 4 figs., 6 refs

  7. Quantitative analysis of time-resolved infrared stimulated luminescence in feldspars

    DEFF Research Database (Denmark)

    Pagonis, Vasilis; Ankjærgaard, Christina; Jain, Mayank

    2016-01-01

    Time-resolved infrared-stimulated luminescence (TR-IRSL) from feldspar samples is of importance in the field of luminescence dating, since it provides information on the luminescence mechanism in these materials. In this paper we present new analytical equations which can be used to analyze TR-IR...

  8. Reduction of Guanosyl Radical by Cysteine and Cysteine-Glycine Studied by Time-Resolved CIDNP

    NARCIS (Netherlands)

    Morozova, O.B.; Kaptein, R.; Yurkovskaya, A.V.

    2012-01-01

    As a model for chemical DNA repair, reduction of guanosyl radicals in the reaction with cysteine or the dipeptide cysteine-glycine has been studied by time-resolved chemically induced dynamic nuclear polarization (CIDNP). Radicals were generated photochemically by pulsed laser irradiation of a

  9. Time-Resolved WAXD and SAXS Investigations on Butyl Branched Alkane at Elevated Pressures

    NARCIS (Netherlands)

    Rastogi, A.; Hobbs, J.K.; Rastogi, S.

    2002-01-01

    The crystallization behavior and the morphological aspect of the butyl branched alkane C96H193CH(C4H9)C94H189 have been investigated using time-resolved wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) at atmospheric and elevated pressures. The solution crystallized sample

  10. Thermally activated delayed fluorescence of fluorescein derivative for time-resolved and confocal fluorescence imaging.

    Science.gov (United States)

    Xiong, Xiaoqing; Song, Fengling; Wang, Jingyun; Zhang, Yukang; Xue, Yingying; Sun, Liangliang; Jiang, Na; Gao, Pan; Tian, Lu; Peng, Xiaojun

    2014-07-09

    Compared with fluorescence imaging utilizing fluorophores whose lifetimes are in the order of nanoseconds, time-resolved fluorescence microscopy has more advantages in monitoring target fluorescence. In this work, compound DCF-MPYM, which is based on a fluorescein derivative, showed long-lived luminescence (22.11 μs in deaerated ethanol) and was used in time-resolved fluorescence imaging in living cells. Both nanosecond time-resolved transient difference absorption spectra and time-correlated single-photon counting (TCSPC) were employed to explain the long lifetime of the compound, which is rare in pure organic fluorophores without rare earth metals and heavy atoms. A mechanism of thermally activated delayed fluorescence (TADF) that considers the long wavelength fluorescence, large Stokes shift, and long-lived triplet state of DCF-MPYM was proposed. The energy gap (ΔEST) of DCF-MPYM between the singlet and triplet state was determined to be 28.36 meV by the decay rate of DF as a function of temperature. The ΔE(ST) was small enough to allow efficient intersystem crossing (ISC) and reverse ISC, leading to efficient TADF at room temperature. The straightforward synthesis of DCF-MPYM and wide availability of its starting materials contribute to the excellent potential of the compound to replace luminescent lanthanide complexes in future time-resolved imaging technologies.

  11. Time-resolved proton polarisation (TPP) images tyrosyl radical sites in bovine liver catalase.

    Science.gov (United States)

    Zimmer, Oliver; Jouve, Hélène M.; Stuhrmann, Heinrich B.

    2017-05-01

    A differentiation between dynamic polarised protons close to tyrosyl radical sites in catalase and those of the bulk is achieved by time-resolved polarised neutron scattering. Three radical sites, all of them being close to the molecular centre and the heme, appear to be equally possible. Among these is tyr-369 the radial site of which had previously been proven by EPR.

  12. Time-resolved magnetic field effects in exciplex systems under X-irradiation

    International Nuclear Information System (INIS)

    Anishchik, S.V.; Lavrik, N.L.

    1988-01-01

    The presence of exciplex systems after X-irradiation of pyrene and N,N-diethylaniline in methanol as well as the influence of the applied magnetic field on exciplex fluorescence was registered using a time-resolving method. The experimental results confirmed the hypothesis on exciplex emergence in the system under study. (author)

  13. Time-resolved investigation of an asymmetric bipolar pulsed magnetron deposition discharge: Influence of pressure

    NARCIS (Netherlands)

    Dunger, Th.; Welzel, Th.; Welzel, S.; Richter, F.

    2005-01-01

    A bipolar pulsed magnetron deposition discharge has been studied with pulse frequencies of 100 and 150 kHz, respectively. The discharge was operated in an argon/oxygen mixture at different total pressures with a circular magnesium target as cathode. Time-resolved Langmuir double probe measurements

  14. Time Resolved Shadowgraph Images of Silicon during Laser Ablation:Shockwaves and Particle Generation

    Energy Technology Data Exchange (ETDEWEB)

    Liu, C.Y.; Mao, X.L.; Greif, R.; Russo, R.E.

    2006-05-06

    Time resolved shadowgraph images were recorded of shockwaves and particle ejection from silicon during laser ablation. Particle ejection and expansion were correlated to an internal shockwave resonating between the shockwave front and the target surface. The number of particles ablated increased with laser energy and was related to the crater volume.

  15. Compact cryogenic Kerr microscope for time-resolved studies of electron spin transport in microstructures

    NARCIS (Netherlands)

    Rizo, P. J.; Pugzlys, A.; Liu, J.; Reuter, D.; Wieck, A. D.; van der Wal, C. H.; van Loosdrecht, P. H. M.; Pugžlys, A.

    2008-01-01

    A compact cryogenic Kerr microscope for operation in the small volume of high-field magnets is described. It is suited for measurements both in Voigt and Faraday configurations. Coupled with a pulsed laser source, the microscope is used to measure the time-resolved Kerr rotation response of

  16. PLASTIQUE: A synchrotron radiation beamline for time resolved fluorescence in the frequency domain

    International Nuclear Information System (INIS)

    De Stasio, G.; Zema, N.; Antonangeli, F.; Parasassi, T.; Rosato, N.

    1991-01-01

    PLASTIQUE is the only synchrotron radiation beamline in the world that performs time resolved fluorescence experiments in the frequency domain. These experiments are extremely valuable sources of informations on the structure and dynamics of molecules. The beamline and some examples of initial data are described

  17. Plastique: A synchrotron radiation beamline for time resolved fluorescence in the frequency domain

    Science.gov (United States)

    De Stasio, Gelsomina; Zema, N.; Antonangeli, F.; Savoia, A.; Parasassi, T.; Rosato, N.

    1991-06-01

    PLASTIQUE is the only synchrotron radiation beamline in the world that performs time resolved fluorescence experiments in frequency domain. These experiments are extremely valuable sources of information on the structure and dynamics of molecules. We describe the beamline and some initial data.

  18. Microscopic resolution broadband dielectric spectroscopy

    International Nuclear Information System (INIS)

    Mukherjee, S; Watson, P; Prance, R J

    2011-01-01

    Results are presented for a non-contact measurement system capable of micron level spatial resolution. It utilises the novel electric potential sensor (EPS) technology, invented at Sussex, to image the electric field above a simple composite dielectric material. EP sensors may be regarded as analogous to a magnetometer and require no adjustments or offsets during either setup or use. The sample consists of a standard glass/epoxy FR4 circuit board, with linear defects machined into the surface by a PCB milling machine. The sample is excited with an a.c. signal over a range of frequencies from 10 kHz to 10 MHz, from the reverse side, by placing it on a conducting sheet connected to the source. The single sensor is raster scanned over the surface at a constant working distance, consistent with the spatial resolution, in order to build up an image of the electric field, with respect to the reference potential. The results demonstrate that both the surface defects and the internal dielectric variations within the composite may be imaged in this way, with good contrast being observed between the glass mat and the epoxy resin.

  19. Microscopic resolution broadband dielectric spectroscopy

    Science.gov (United States)

    Mukherjee, S.; Watson, P.; Prance, R. J.

    2011-08-01

    Results are presented for a non-contact measurement system capable of micron level spatial resolution. It utilises the novel electric potential sensor (EPS) technology, invented at Sussex, to image the electric field above a simple composite dielectric material. EP sensors may be regarded as analogous to a magnetometer and require no adjustments or offsets during either setup or use. The sample consists of a standard glass/epoxy FR4 circuit board, with linear defects machined into the surface by a PCB milling machine. The sample is excited with an a.c. signal over a range of frequencies from 10 kHz to 10 MHz, from the reverse side, by placing it on a conducting sheet connected to the source. The single sensor is raster scanned over the surface at a constant working distance, consistent with the spatial resolution, in order to build up an image of the electric field, with respect to the reference potential. The results demonstrate that both the surface defects and the internal dielectric variations within the composite may be imaged in this way, with good contrast being observed between the glass mat and the epoxy resin.

  20. Usefulness of time-resolved projection MRA on evaluation of hemodynamics in cerebral occlusive diseases

    International Nuclear Information System (INIS)

    Oka, Yoshihisa; Kusunoki, Katsusuke; Nochide, Ichiro; Igase, Keiji; Harada, Hironobu; Sadamoto, Kazuhiko; Nagasawa, Kiyoshi

    2001-01-01

    The usefulness for evaluation of cerebral hemodynamics using time-resolved projection MRA was studied in normal volunteers and patients of cerebrovascular diseases. Six normal volunteers and ten patients with cerebrovascular occlusive diseases including 6 of IC occlusion and 4 of post EC/IC bypass surgery underwent time-resolved projection MRA on a 1.5 T clinical MRI system. Projection angiograms are acquired with 2D-fast SPGR sequence with a time resolution of approximately one image per second, 40 images being acquired consecutively before and after bolus injection Gd-DTPA. And all images were calculated by complex subtraction from the background mask in a work station. In normal volunteers, the quality of images of time-resolved projection MRA was satisfactory. The arteries from internal carotid artery through M2 segment of middle cerebral artery and all major venous systems were well portrayed. In 4 cases of IC occlusion who were assessed the collateral flow through the anterior communicating artery and posterior communicating artery, there were delayed to demonstrate the ipsilateral MCA. However, in 2 cases of IC occlusion that were assessed the collateral flow through leptomeningeal anastomosis, ipsilateral MCA and collateral circulation were not demonstrated. In all patients of post EC/IC bypass surgery, the patency of EC/IC bypass could be evaluated as properly with time-resolved projection MRA as 3D-TOF MRA. Although the temporal and spatial resolutions are insufficient, time-resolved projection MRA was power-full non-invasive method to evaluate the cerebral hemodynamics vis the basal communicating arteries in IC occlusion and identify the patency of EC/IC bypass. (author)

  1. Exploratory study on a statistical method to analyse time resolved data obtained during nanomaterial exposure measurements

    International Nuclear Information System (INIS)

    Clerc, F; Njiki-Menga, G-H; Witschger, O

    2013-01-01

    Most of the measurement strategies that are suggested at the international level to assess workplace exposure to nanomaterials rely on devices measuring, in real time, airborne particles concentrations (according different metrics). Since none of the instruments to measure aerosols can distinguish a particle of interest to the background aerosol, the statistical analysis of time resolved data requires special attention. So far, very few approaches have been used for statistical analysis in the literature. This ranges from simple qualitative analysis of graphs to the implementation of more complex statistical models. To date, there is still no consensus on a particular approach and the current period is always looking for an appropriate and robust method. In this context, this exploratory study investigates a statistical method to analyse time resolved data based on a Bayesian probabilistic approach. To investigate and illustrate the use of the this statistical method, particle number concentration data from a workplace study that investigated the potential for exposure via inhalation from cleanout operations by sandpapering of a reactor producing nanocomposite thin films have been used. In this workplace study, the background issue has been addressed through the near-field and far-field approaches and several size integrated and time resolved devices have been used. The analysis of the results presented here focuses only on data obtained with two handheld condensation particle counters. While one was measuring at the source of the released particles, the other one was measuring in parallel far-field. The Bayesian probabilistic approach allows a probabilistic modelling of data series, and the observed task is modelled in the form of probability distributions. The probability distributions issuing from time resolved data obtained at the source can be compared with the probability distributions issuing from the time resolved data obtained far-field, leading in a

  2. Adoption of Broadband Services

    DEFF Research Database (Denmark)

    Falch, Morten

    2008-01-01

    Broadband is seen as a key infrastructure for developing the information society. For this reason many Governments are actively engaged in stimulating investments in broadband infrastructures and use of broadband services. This chapter compares a wide range of broadband strategies in the most suc....... Many countries have provided active support for stimulating diffusion of broadband and national variants of this type of policies in different countries are important for an explanation of national differences in adoption of broadband....

  3. Quantum-dot-based homogeneous time-resolved fluoroimmunoassay of alpha-fetoprotein

    Energy Technology Data Exchange (ETDEWEB)

    Chen Meijun; Wu Yingsong; Lin Guanfeng; Hou Jingyuan; Li Ming [Institute of Antibody Engineering, School of Biotechnology, Southern Medical University, Guangzhou, 510515 (China); Liu Tiancai, E-mail: liutc@smu.edu.cn [Institute of Antibody Engineering, School of Biotechnology, Southern Medical University, Guangzhou, 510515 (China)

    2012-09-05

    Highlights: Black-Right-Pointing-Pointer QDs-based homogeneous time-resolved fluoroimmunoassay was developed to detect AFP. Black-Right-Pointing-Pointer The conjugates were prepared with QDs-doped microspheres and anti-AFP McAb. Black-Right-Pointing-Pointer The conjugates were prepared with LTCs and another anti-AFP McAb. Black-Right-Pointing-Pointer Excess amounts of conjugates were used for detecting AFP without rinsing. Black-Right-Pointing-Pointer The wedding of QPs and LTCs was suitable for HTRFIA to detect AFP. - Abstract: Quantum dots (QDs) with novel photoproperties are not widely used in clinic diagnosis, and homogeneous time-resolved fluorescence assays possess many advantages over current methods for alpha-fetoprotein (AFP) detection. A novel QD-based homogeneous time-resolved fluorescence assay was developed and used for detection of AFP, a primary marker for many cancers and diseases. QD-doped carboxyl-modified polystyrene microparticles (QPs) were prepared by doping oil-soluble QDs possessing a 605 nm emission peak. The antibody conjugates (QPs-E014) were prepared from QPs and an anti-AFP monoclonal antibody, and luminescent terbium chelates (LTCs) were prepared and conjugated to a second anti-AFP monoclonal antibody (LTCs-E010). In a double-antibodies sandwich structure, QPs-E014 and LTCs-E010 were used for detection of AFP, serving as energy acceptor and donor, respectively, with an AFP bridge. The results demonstrated that the luminescence lifetime of these QPs was sufficiently long for use in a time-resolved fluoroassay, with the efficiency of time-resolved Foerster resonance transfer (TR-FRET) at 67.3% and the spatial distance of the donor to acceptor calculated to be 66.1 Angstrom-Sign . Signals from TR-FRET were found to be proportional to AFP concentrations. The resulting standard curve was log Y = 3.65786 + 0.43863{center_dot}log X (R = 0.996) with Y the QPs fluorescence intensity and X the AFP concentration; the calculated sensitivity was 0

  4. Timepix3 as X-ray detector for time resolved synchrotron experiments

    Energy Technology Data Exchange (ETDEWEB)

    Yousef, Hazem, E-mail: hazem.yousef@diamond.ac.uk; Crevatin, Giulio; Gimenez, Eva N.; Horswell, Ian; Omar, David; Tartoni, Nicola

    2017-02-11

    The Timepix3 ASIC can be used very effectively for time resolved experiments at synchrotron facilities. We have carried out characterizations with the synchrotron beam in order to determine the time resolution and other characteristics such as the energy resolution, charge sharing and signals overlapping. The best time resolution achieved is 19 ns FWHM for 12 keV photons and 350 V bias voltage. The time resolution shows dependency on the photon energy as well as on the chip and acquisition parameters. - Highlights: • An estimate time resolution of the Timepix3 is produced based on the arrival time. • At high resolution, the time structure of the DLS synchrotron beam is resolved. • The arrival time information improves combining the charge split events. • The results enable performing a wide range of time resolved experiments.

  5. Laser-time resolved fluorimetric determination of trace of boron in U3O8

    International Nuclear Information System (INIS)

    Xu Yongyuan; Wang Yulong; Wang Qin

    1988-01-01

    In this work, a laser-time resolved fluorimetric determinatin of trace of boron in U 3 O 8 had been developed. The boron complex with dibenzoyl methane (DBM) in a suitable medium is excited by a small nitrogen laser and emits the delay fluorescence with lifetime of 2 ms which is much longer than that of the fluorescence of uranium. Since the fluorescence of uranium doesn't interfere with determination of boron in the time resolved fluorimetric method boron need not be separated from uranium in advance. Thus the determination is very rapid and simple. The limit of determination is 0.02 ngB/ml. When 10 mgU is taken, 0.01 ppm of boron in uranium can be determined. Several samples of U 3 O 8 with boron content from 0.04 to 0.5 ppm have been determined by using this method. The results of determination have been accordant with other methods

  6. Time-resolved X-ray studies using third generation synchrotron radiation sources

    International Nuclear Information System (INIS)

    Mills, D.M.

    1991-10-01

    The third generation, high-brilliance, hard x-ray, synchrotron radiation (SR) sources currently under construction (ESRF at Grenoble, France; APS at Argonne, Illinois; and SPring-8 at Harima, Japan) will usher in a new era of x-ray experimentation for both physical and biological sciences. One of the most exciting areas of experimentation will be the extension of x-ray scattering and diffraction techniques to the study of transient or time-evolving systems. The high repetition rate, short-pulse duration, high brilliance, and variable spectral bandwidth of these sources make them ideal for x-ray time-resolved studies. The temporal properties (bunch length, interpulse period, etc.) of these new sources will be summarized. Finally, the scientific potential and the technological challenges of time-resolved x-ray scattering from these new sources will be described. 13 refs., 4 figs

  7. Time-resolved X-ray scattering program at the Advanced Photon Source

    International Nuclear Information System (INIS)

    Rodricks, B.

    1994-01-01

    The Time-Resolved Scattering Program's goal is the development of instruments and techniques for time-resolved studies. This entails the development of wide bandpass and focusing optics, high-speed detectors, mechanical choppers, and components for the measurement and creation of changes in samples. Techniques being developed are pump-probe experiments, single-bunch scattering experiments, high-speed white and pink beam Laue scattering, and nanosecond to microsecond synchronization of instruments. This program will be carried out primarily from a white-beam, bend-magnet source, experimental station, 1-BM-B, that immediately follows the first optics enclosure (1-BM-A). This paper will describe the experimental station and instruments under development to carry out the program

  8. Time-resolved UV-excited microarray reader for fluorescence energy transfer (FRET) measurements

    Science.gov (United States)

    Orellana, Adelina; Hokkanen, Ari P.; Pastinen, Tomi; Takkinen, Kristina; Soderlund, Hans

    2001-05-01

    Analytical systems based on immunochemistry are largely used in medical diagnostics and in biotechnology. There is a significant pressure to develop the present assay formats to become easier to use, faster, and less reagent consuming. Further developments towards high density array--like multianalyte measurement systems would be valuable. To this aim we have studied the applicability of fluorescence resonance energy transfer and time-resolved fluorescence resonance energy transfer in immunoassays on microspots and in microwells. We have used engineered recombinant antibodies detecting the pentameric protein CRP as a model analyte system, and tested different assay formats. We describe also the construction of a time-resolved scanning epifluorometer with which we could measure the FRET interaction between the slow fluorescence decay from europium chelates and its energy transfer to the rapidly decaying fluorophore Cy5.

  9. A review of the analysis of complex time-resolved fluorescence anisotropy data

    International Nuclear Information System (INIS)

    Smith, Trevor A; Ghiggino, Kenneth P

    2015-01-01

    Time-resolved fluorescence anisotropy measurements (TRAMs) are widely used to probe the dynamics of the various processes that can lead to the depolarisation of emission following photoselection by polarised excitation. The most commonly investigated of these emission depolarising phenomena is molecular rotational motion, but TRAMs are very useful for determining the kinetics of a host of other processes. In this paper we review several examples for which we have observed in our laboratories initially unexpectedly complex temporal behaviour of the time-resolved fluorescence anisotropy signal from relatively ‘simple’ chemical systems. In certain circumstances the anisotropy (i) decays on timescales when superficially it might be thought it should remain constant, (ii) shows marked ‘dip and rise’ behaviour in its intensity, or (iii) can change sign as the anisotropy evolves in time. Fundamentally simple processes, including molecular rotational motion, energy migration and excited state photophysics, can cause such behaviour. (topical review)

  10. A system for time-resolved x-ray diffraction and its application to muscle contraction

    International Nuclear Information System (INIS)

    Amemiya, Yoshiyuki; Hashizume, Hiroo.

    1979-01-01

    A data-collection system has been built which permits time-resolved studies of X-ray diffraction diagrams obtained from contracting muscle on millisecond time scale. The system consists of a linear delay-line position sensitive proportional counter (PSPC), a special data transfer unit and an on-line computer. The PSPC used with a mirror-monochromator camera can detect equatorial reflections from stimulated muscle in a total exposure time of a few seconds. Time-resolved data-collection is achieved by stimulating muscle at a regular time interval, dividing a complete cycle of muscle contraction into many successive time slices and accumulating in computer memory X-ray data for each time slice from many repeated cycles of stimulation. The performances of the system have been demonstrated by recording equatorial reflections from frog skeletal muscle during isometric and isotonic twitch with a time resolution of 25 ms. (author)

  11. Mix and Inject: Reaction Initiation by Diffusion for Time-Resolved Macromolecular Crystallography

    Directory of Open Access Journals (Sweden)

    Marius Schmidt

    2013-01-01

    Full Text Available Time-resolved macromolecular crystallography unifies structure determination with chemical kinetics, since the structures of transient states and chemical and kinetic mechanisms can be determined simultaneously from the same data. To start a reaction in an enzyme, typically, an initially inactive substrate present in the crystal is activated. This has particular disadvantages that are circumvented when active substrate is directly provided by diffusion. However, then it is prohibitive to use macroscopic crystals because diffusion times become too long. With small micro- and nanocrystals diffusion times are adequately short for most enzymes and the reaction can be swiftly initiated. We demonstrate here that a time-resolved crystallographic experiment becomes feasible by mixing substrate with enzyme nanocrystals which are subsequently injected into the X-ray beam of a pulsed X-ray source.

  12. A direct electron detector for time-resolved MeV electron microscopy

    Energy Technology Data Exchange (ETDEWEB)

    Vecchione, T.; Denes, P.; Jobe, R. K.; Johnson, I. J.; Joseph, J. M.; Li, R. K.; Perazzo, A.; Shen, X.; Wang, X. J.; Weathersby, S. P.; Yang, J.; Zhang, D.

    2017-03-01

    The introduction of direct electron detectors enabled the structural biology revolution of cryogenic electron microscopy. Direct electron detectors are now expected to have a similarly dramatic impact on time-resolved MeV electron microscopy, particularly by enabling both spatial and temporal jitter correction. Here we report on the commissioning of a direct electron detector for time-resolved MeV electron microscopy. The direct electron detector demonstrated MeV single electron sensitivity and is capable of recording megapixel images at 180 Hz. The detector has a 15-bit dynamic range, better than 30-μmμm spatial resolution and less than 20 analogue-to-digital converter count RMS pixel noise. The unique capabilities of the direct electron detector and the data analysis required to take advantage of these capabilities are presented. The technical challenges associated with generating and processing large amounts of data are also discussed.

  13. Sub-nanosecond time-resolved near-field scanning magneto-optical microscope.

    Science.gov (United States)

    Rudge, J; Xu, H; Kolthammer, J; Hong, Y K; Choi, B C

    2015-02-01

    We report on the development of a new magnetic microscope, time-resolved near-field scanning magneto-optical microscope, which combines a near-field scanning optical microscope and magneto-optical contrast. By taking advantage of the high temporal resolution of time-resolved Kerr microscope and the sub-wavelength spatial resolution of a near-field microscope, we achieved a temporal resolution of ∼50 ps and a spatial resolution of microscope, the magnetic field pulse induced gyrotropic vortex dynamics occurring in 1 μm diameter, 20 nm thick CoFeB circular disks has been investigated. The microscope provides sub-wavelength resolution magnetic images of the gyrotropic motion of the vortex core at a resonance frequency of ∼240 MHz.

  14. MCNP simulations of a new time-resolved Compton scattering imaging technique

    International Nuclear Information System (INIS)

    Ilan, Y.

    2004-01-01

    Medical images of human tissue can be produced using Computed Tomography (CT), Positron Emission Tomography (PET), Ultrasound or Magnetic Resonance Imaging (MRI). In all of the above techniques, in order to get a three-dimensional (3D) image, one has to rotate or move the source, the detectors or the scanned target. This procedure is complicated, time consuming and increases the cost and weight of the scanning equipment. Time resolved optical tomography has been suggested as an alternative to the above conventional methods. This technique implies near infrared light (NIR) and fast time-resolved detectors to obtain a 3D image of the scanned target. However, due to the limited penetration of the NIR light in the tissue, the application of this technique is limited to soft tissue like a female breast or a premature infant brain

  15. Time-resolved protein nano-crystallography using an X-ray free-electron laser

    International Nuclear Information System (INIS)

    Aquila, Andrew; Hunter, Mark S.; Fromme, Petra; Fromme, Raimund; Grotjohann, Ingo; Doak, R. Bruce; Kirian, Richard A.; Schmidt, Kevin E.; Wang, Xiaoyu; Weierstall, Uwe; Spence, John C.H.; White, Thomas A.; Caleman, Carl; DePonte, Daniel P.; Fleckenstein, Holger; Gumprecht, Lars; Liang, Mengning; Martin, Andrew V.; Schulz, Joachim; Stellato, Francesco; Stern, Stephan; Barty, Anton; Andreasson, Jakob; Davidsson, Jan; Hajdu, Janos; Maia, Filipe R.N.C.; Seibert, M. Marvin; Timneanu, Nicusor; Arnlund, David; Johansson, Linda; Malmerberg, Erik; Neutze, Richard; Bajt, Sasa; Barthelmess, Miriam; Graafsma, Heinz; Hirsemann, Helmut; Wunderer, Cornelia; Barends, Thomas R.M.; Foucar, Lutz; Krasniqi, Faton; Lomb, Lukas; Rolles, Daniel; Schlichting, Ilme; Schmidt, Carlo; Bogan, Michael J.; Hampton, Christina Y.; Sierra, Raymond; Starodub, Dmitri; Bostedt, Christoph; Bozek, John D.; Messerschmidt, Marc; Williams, Garth J.; Bottin, Herve

    2012-01-01

    We demonstrate the use of an X-ray free electron laser synchronized with an optical pump laser to obtain X-ray diffraction snapshots from the photo-activated states of large membrane protein complexes in the form of nano-crystals flowing in a liquid jet. Light-induced changes of Photosystem I-Ferredoxin co-crystals were observed at time delays of 5 to 10 μs after excitation. The result correlates with the microsecond kinetics of electron transfer from Photosystem I to ferredoxin. The undocking process that follows the electron transfer leads to large rearrangements in the crystals that will terminally lead to the disintegration of the crystals. We describe the experimental setup and obtain the first time resolved femtosecond serial X-ray crystallography results from an irreversible photo-chemical reaction at the Linac Coherent Light Source. This technique opens the door to time-resolved structural studies of reaction dynamics in biological systems. (authors)

  16. Coherent optical effect on time-resolved vibrational SFG spectrum of adsorbates

    Science.gov (United States)

    Ueba, H.; Sawabu, T.; Mii, T.

    2002-04-01

    We present a theory to study the influence of the coherent mixing between pump-infrared and probe-visible pulse on a time-resolved sum-frequency generation (TR-SFG) spectrum for vibrations at surfaces. The general formula of the time-dependent and its Fourier transform of the SFG polarization and its Fourier transform allows us to calculate the time-resolved vibrational SFG spectrum and the transient characteristics of the SFG intensity as a function of the delay time td between the pump-infrared and probe-visible pulse. It is found the coherent optical effect manifests itself in the broadening and narrowing of the SFG spectrum with the intrinsic width of T2 at negative and positive td, respectively, being in qualitative agreement with recent experimental results. The influence of the coherent mixing on the transient behavior of the SFG intensity is also discussed in conjunction to the T2 determination.

  17. Time-resolved wave profile measurements in copper to Megabar pressures

    Energy Technology Data Exchange (ETDEWEB)

    Chhabildas, L C; Asay, J R

    1981-01-01

    Many time-resolved techniques have been developed which have greatly aided in the understanding of dynamic material behavior such as the high pressure-dynamic strength of materials. In the paper, time-resolved measurements of copper (at shock-induced high pressures and temperatures) are used to illustrate the capability of using such techniques to investigate high pressure strength. Continuous shock loading and release wave profiles have been made in copper to 93 GPa using velocity interferometric techniques. Fine structure in the release wave profiles from the shocked state indicates an increase in shear strength of copper to 1.5 GPa at 93 GPa from its ambient value of 0.08 GPa.

  18. Time resolved Thomson scattering diagnostic of pulsed gas metal arc welding (GMAW) process

    International Nuclear Information System (INIS)

    Kühn-Kauffeldt, M; Schein, J; Marquès, J L

    2014-01-01

    In this work a Thomson scattering diagnostic technique was applied to obtain time resolved electron temperature and density values during a gas metal arc welding (GMAW) process. The investigated GMAW process was run with aluminum wire (AlMg 4,5 Mn) with 1.2 mm diameter as a wire electrode, argon as a shielding gas and peak currents in the range of 400 A. Time resolved measurements could be achieved by triggering the laser pulse at shifted time positions with respect to the current pulse driving the process. Time evaluation of resulting electron temperatures and densities is used to investigate the state of the plasma in different phases of the current pulse and to determine the influence of the metal vapor and droplets on the plasma properties

  19. Developments in time-resolved high pressure x-ray diffraction using rapid compression and decompression

    International Nuclear Information System (INIS)

    Smith, Jesse S.; Sinogeikin, Stanislav V.; Lin, Chuanlong; Rod, Eric; Bai, Ligang; Shen, Guoyin

    2015-01-01

    Complementary advances in high pressure research apparatus and techniques make it possible to carry out time-resolved high pressure research using what would customarily be considered static high pressure apparatus. This work specifically explores time-resolved high pressure x-ray diffraction with rapid compression and/or decompression of a sample in a diamond anvil cell. Key aspects of the synchrotron beamline and ancillary equipment are presented, including source considerations, rapid (de)compression apparatus, high frequency imaging detectors, and software suitable for processing large volumes of data. A number of examples are presented, including fast equation of state measurements, compression rate dependent synthesis of metastable states in silicon and germanium, and ultrahigh compression rates using a piezoelectric driven diamond anvil cell

  20. Timepix3 as X-ray detector for time resolved synchrotron experiments

    International Nuclear Information System (INIS)

    Yousef, Hazem; Crevatin, Giulio; Gimenez, Eva N.; Horswell, Ian; Omar, David; Tartoni, Nicola

    2017-01-01

    The Timepix3 ASIC can be used very effectively for time resolved experiments at synchrotron facilities. We have carried out characterizations with the synchrotron beam in order to determine the time resolution and other characteristics such as the energy resolution, charge sharing and signals overlapping. The best time resolution achieved is 19 ns FWHM for 12 keV photons and 350 V bias voltage. The time resolution shows dependency on the photon energy as well as on the chip and acquisition parameters. - Highlights: • An estimate time resolution of the Timepix3 is produced based on the arrival time. • At high resolution, the time structure of the DLS synchrotron beam is resolved. • The arrival time information improves combining the charge split events. • The results enable performing a wide range of time resolved experiments.