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Sample records for resolving reonance-ionization spectroscopy

  1. TIME-RESOLVED VIBRATIONAL SPECTROSCOPY

    SciTech Connect

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

    2009-05-14

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

  2. Time-resolved photoelectron spectroscopy of liquids

    NASA Astrophysics Data System (ADS)

    Buchner, Franziska; Lübcke, Andrea; Heine, Nadja; Schultz, Thomas

    2010-11-01

    We present a novel setup for the investigation of ultrafast dynamic processes in a liquid jet using time-resolved photoelectron spectroscopy. A magnetic-bottle type spectrometer with a high collection efficiency allows the very sensitive detection of photoelectrons emitted from a 10 μm thick liquid jet. This translates into good signal/noise ratio and rapid data acquisition making femtosecond time-resolved experiments feasible. We describe the experimental setup, a detailed spectrometer characterization based on the spectroscopy of nitric oxide in the gas phase, and results from femtosecond time-resolved experiments on sodium iodide solutions. The latter experiments reveal the formation and evolution of the solvated electron and we characterize two distinct spectral components corresponding to initially thermalized and unthermalized solvated electrons. The absence of dark states in photoionization, the direct measurement of electron binding energies, and the ability to resolve dynamic processes on the femtosecond time scale make time-resolved photoelectron spectroscopy from the liquid jet a very promising method for the characterization of photochemical processes in liquids.

  3. Time-resolved photoelectron spectroscopy of liquids.

    PubMed

    Buchner, Franziska; Lübcke, Andrea; Heine, Nadja; Schultz, Thomas

    2010-11-01

    We present a novel setup for the investigation of ultrafast dynamic processes in a liquid jet using time-resolved photoelectron spectroscopy. A magnetic-bottle type spectrometer with a high collection efficiency allows the very sensitive detection of photoelectrons emitted from a 10 μm thick liquid jet. This translates into good signal/noise ratio and rapid data acquisition making femtosecond time-resolved experiments feasible. We describe the experimental setup, a detailed spectrometer characterization based on the spectroscopy of nitric oxide in the gas phase, and results from femtosecond time-resolved experiments on sodium iodide solutions. The latter experiments reveal the formation and evolution of the solvated electron and we characterize two distinct spectral components corresponding to initially thermalized and unthermalized solvated electrons. The absence of dark states in photoionization, the direct measurement of electron binding energies, and the ability to resolve dynamic processes on the femtosecond time scale make time-resolved photoelectron spectroscopy from the liquid jet a very promising method for the characterization of photochemical processes in liquids. PMID:21133461

  4. Time-resolved multiple probe spectroscopy

    SciTech Connect

    Greetham, G. M.; Sole, D.; Clark, I. P.; Parker, A. W.; Pollard, M. R.; Towrie, M.

    2012-10-15

    Time-resolved multiple probe spectroscopy combines optical, electronic, and data acquisition capabilities to enable measurement of picosecond to millisecond time-resolved spectra within a single experiment, using a single activation pulse. This technology enables a wide range of dynamic processes to be studied on a single laser and sample system. The technique includes a 1 kHz pump, 10 kHz probe flash photolysis-like mode of acquisition (pump-probe-probe-probe, etc.), increasing the amount of information from each experiment. We demonstrate the capability of the instrument by measuring the photolysis of tungsten hexacarbonyl (W(CO){sub 6}) monitored by IR absorption spectroscopy, following picosecond vibrational cooling of product formation through to slower bimolecular diffusion reactions on the microsecond time scale.

  5. Spatially Resolved Infrared Spectroscopy of Seyfert Galaxies

    NASA Astrophysics Data System (ADS)

    Knop, Robert Andrew, Jr.

    This thesis presents infrared spectroscopy of the circumnuclear regions of 23 Seyfert galaxies. Observations are spectrally resolved with a resolution of λΔλ~1000 and spatially resolved to ~1'', corresponding to ~102 pc for the objects in the sample. The instrument used for the observations, the Palomar Near-Infrared Spectrometer, is described, and problems peculiar to reduction of data from it are discussed. The lines observed include Paβ, Brγ, (FeII) (λ=1.2567μm), and H2 (λ=2.1213μm). In nine objects, the coronal line (SIX) (λ=1.2524μm) is also detected. Spatially resolved line emission is clearly visible in approximately half of the objects observed. The data for five of the objects showing the best spatially resolved infrared line emission are analyzed in detail. These objects include Seyfert 1.5 galaxy NGC 4151 and Seyfert 2 galaxies Mk 1066, NGC 2110, NGC 4388, and Mk 3. The data for the remaining objects is presented in tabular form, and each object is discussed briefly. The data argue that processes associated with the Seyfert nucleus are responsible for the bulk of the observed (FeII) emission. Kinematic and spatial associations can be drawn between features in the (FeII) line profiles and other processes associated with the active nucleus, such as outflows seen in ionized optical emission and radio lobes. Most of the (FeII) appears to emerge from partially ionized regions excited by nuclear x-rays, with an additional contribution from fast shocks. Some of the H2 emission also appears to be associated with the nuclear activity. However, in some cases the H2 emission is observed to have a different spatial distribution from (FeII) and the H+ emission. The H2 emission is probably thermally excited. No significant differences are found between the infrared line emission of Seyfert and Seyfert 1.x galaxies.

  6. Phase-resolved cyclotron spectroscopy of polars

    NASA Astrophysics Data System (ADS)

    Campbell, Ryan

    In this thesis we use phase-resolved cyclotron spectroscopy to study polars. Polars are a subset of cataclysmic variables where the primary WD is highly magnetic. In this case, the accretion flow is constrained along the magnetic field lines and eventually deposited on the WD, where the accreting material interacts with the atmosphere, forming a standing hydrodynamic shock at a location termed the accretion region, and emitting cyclotron radiation. Due to its field strength, cyclotron radiation from polars falls at either UV, optical or NIR wavelengths. While a substantial amount of optical cyclotron spectra have been published on polars, the NIR remains relatively unstudied. In this thesis, we present NIR spectroscopy for fifteen polars. Additionally, while a single cyclotron spectrum is needed to constrain the shock parameters, phase- resolved spectroscopy allows for a more in-depth analysis of the shock structure and the geometry of the accretion region. Of the fifteen polars observed, eight yielded spectra of adequate quality to be modeled in this manner: EF Eri, EQ Cet, AN UMa, VV Pup, AM Her, ST LMi, MR Ser, and MQ Dra. Initially, we used the industry standard "Constant Lambda (CL)" code to model each object. The code is fast, but produces only globally averaged values of the salient shock parameters: B - the magnetic field strength, kT - the plasma temperature, logL - the "size parameter" of the accretion column, and TH- the viewing angle between the observer and the magnetic field. For each object we present CL models for our NIR phase-resolved cyclotron spectra. Subsequently, we use a more advanced "Structured-Shock" code built by Fischer & Beuermann (2001)("F&B") to remodel three objects: EQ Cet, MQ Dra, and EF Eri. The F&B code allows for input of more physical parameters and most importantly does ray tracing through a simulated one-dimensional accretion column. To determine the outgoing spectrum, temperature and velocity profiles are needed to

  7. Rotationally resolved infrared spectroscopy of adamantane

    NASA Astrophysics Data System (ADS)

    Pirali, O.; Boudon, V.; Oomens, J.; Vervloet, M.

    2012-01-01

    We present the first rotationally resolved spectra of adamantane (C10H16) applying gas-phase Fourier transform infrared (IR) absorption spectroscopy. High-resolution IR spectra are recorded in the 33-4500 cm-1range using as source of IR radiation both synchrotron radiation (at the AILES beamline of the SOLEIL synchrotron) as well as a classical globar. Adamantane is a spherical top molecule with tetrahedral symmetry (Td point group) and has no permanent dipole moment in its vibronic ground state. Of the 72 fundamental vibrational modes in adamantane, only 11 are IR active. Here we present rotationally resolved spectra for seven of them: ν30, ν28, ν27, ν26, ν25, ν24, and ν23. The typical rotational structure of spherical tops is observed and analyzed using the STDS software developed in the Dijon group, which provides the first accurate energy levels and rotational constants for seven fundamental modes. Rotational levels with quantum numbers as high as J = 107 have been identified and included in the fit leading to a typical standard deviation of about 10-3 cm-1.

  8. Spatially resolved photoluminescence spectroscopy of quantum dots

    NASA Astrophysics Data System (ADS)

    Dybiec, Maciej

    applications was in the scope of this research. Bio-conjugation and functionalization are the fundamental issues for bio-marker tagging application of semiconductor quantum dots. It was discovered that spatially resolved photoluminescence spectroscopy and PL photo-degradation kinetics can confirm the bio-conjugation. Development of a methodology that will allow the spectroscopic confirmation of bio-conjugation of quantum dot fluorescent tags and optimization of their performance was the final goal for this research project.

  9. Position-resolved Positron Annihilation Lifetime Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wagner, A.; Butterling, M.; Fiedler, F.; Fritz, F.; Kempe, M.; Cowan, T. E.

    2013-06-01

    A new method which allows for position-resolved positron lifetime spectroscopy studies in extended volume samples is presented. In addition to the existing technique of in-situ production of positrons inside large (cm3) bulk samples using high-energy photons up to 16 MeV from bremsstrahlung production, granular position-sensitive photon detectors have been employed. A beam of intense bremsstrahlung is provided by the superconducting electron linear accelerator ELBE (Electron Linear Accelerator with high Brilliance and low Emittance) which delivers electron bunches of less than 10 ps temporal width and an adjustable bunch separation of multiples of 38 ns, average beam currents of 1 mA, and energies up to 40 MeV. Since the generation of bremsstrahlung and the transport to the sample preserves the sharp timing of the electron beam, positrons generated inside the entire sample volume by pair production feature a sharp start time stamp for positron annihilation lifetime studies with high timing resolutions and high signal to background ratios due to the coincident detection of two annihilation photons. Two commercially available detectors from a high-resolution medial positron-emission tomography system are being employed with 169 individual Lu2SiO5:Ce scintillation crystals, each. In first experiments, a positron-lifetime gated image of a planar Si/SiO2 (pieces of 12.5 mm × 25 mm size) sample and a 3-D structured metal in Teflon target could be obtained proving the feasibility of a three dimensional lifetime-gated tomographic system.

  10. Thymine Dimer Formation probed by Time-Resolved Vibrational Spectroscopy

    NASA Astrophysics Data System (ADS)

    Schreier, Wolfgang J.; Schrader, Tobias E.; Roller, Florian O.; Gilch, Peter; Zinth, Wolfgang; Kohler, Bern

    Cyclobutane pyrimidine dimers are the major photoproducts formed when DNA is exposed to UV light. Femtosecond time-resolved vibrational spectroscopy reveals that thymine dimers are formed in thymidine oligonucleotides in an ultrafast photoreaction.

  11. Time-resolved orbital angular momentum spectroscopy

    SciTech Connect

    Noyan, Mehmet A.; Kikkawa, James M.

    2015-07-20

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

  12. Spatially resolved spectroscopy using tapered stripline NMR

    NASA Astrophysics Data System (ADS)

    Tijssen, Koen C. H.; Bart, Jacob; Tiggelaar, Roald M.; Janssen, J. W. G. (Hans); Kentgens, Arno P. M.; van Bentum, P. Jan M.

    2016-02-01

    Magnetic field B0 gradients are essential in modern Nuclear Magnetic Resonance spectroscopy and imaging. Although RF/B1 gradients can be used to fulfill a similar role, this is not used in common practice because of practical limitations in the design of B1 gradient coils. Here we present a new method to create B1 gradients using stripline RF coils. The conductor-width of a stripline NMR chip and the strength of its radiofrequency field are correlated, so a stripline chip can be tapered to produce any arbitrary shaped B1 field gradient. Here we show the characterization of this tapered stripline configuration and demonstrate three applications: magnetic resonance imaging on samples with nL-μL volumes, reaction monitoring of fast chemical reactions (10-2-101 s) and the compensation of B0 field gradients to obtain high-resolution spectra in inhomogeneous magnetic fields.

  13. Seventh international conference on time-resolved vibrational spectroscopy

    SciTech Connect

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

    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.

  14. Time Resolved Spectroscopy of Eclipsing Polars

    NASA Astrophysics Data System (ADS)

    Barrett, Paul

    2005-09-01

    No changes have been made since the last annual progress report was submitted in conjunction with a unilateral NCX. Dr. Barrett was affected by an STScI Reduction in Force (RIF). He is now employed by the Johns Hopkins University and plans to continue his research there. No expenses have been charged to this grant, however the FUSE data for the eclipsing polar V1432 Aql has been received and processed using CALFWSE v3.0.6. The resulting summed spectrum has been used for a preliminary analysis of the interstellar absorption towards V1432 Aql. We find a hydrogen column density of less than 1.5e21 cm^-2. We have used this result in the paper "X-Ray Emission and Optical Polarization of V1432 Aquilae: An Asynchronous Polar" to fix the hydrogen column density in the soft (<0.5 keV) X-ray band when analyzing the XMM-Newton spectra of this polar. This has enabled us to find an accurate temperature for the blackbody component of 88+/-2 eV, which is significantly higher than that of other polars (20 - 40 eV). We hope to complete our analysis of the phase-resolved emission line spectra of V1432 Aql and to prepare the results for publication in a refereed journal. We hope to begin work on this star within the next few months.

  15. Time Resolved Spectroscopy of Eclipsing Polars

    NASA Technical Reports Server (NTRS)

    Barrett, Paul

    2005-01-01

    No changes have been made since the last annual progress report was submitted in conjunction with a unilateral NCX. Dr. Barrett was affected by an STScI Reduction in Force (RIF). He is now employed by the Johns Hopkins University and plans to continue his research there. No expenses have been charged to this grant, however the FUSE data for the eclipsing polar V1432 Aql has been received and processed using CALFWSE v3.0.6. The resulting summed spectrum has been used for a preliminary analysis of the interstellar absorption towards V1432 Aql. We find a hydrogen column density of less than 1.5e21 cm^-2. We have used this result in the paper "X-Ray Emission and Optical Polarization of V1432 Aquilae: An Asynchronous Polar" to fix the hydrogen column density in the soft (<0.5 keV) X-ray band when analyzing the XMM-Newton spectra of this polar. This has enabled us to find an accurate temperature for the blackbody component of 88+/-2 eV, which is significantly higher than that of other polars (20 - 40 eV). We hope to complete our analysis of the phase-resolved emission line spectra of V1432 Aql and to prepare the results for publication in a refereed journal. We hope to begin work on this star within the next few months.

  16. [System of ns time-resolved spectroscopy diagnosis and radioprotection].

    PubMed

    Yao, Wei-Bo; Guo, Jian-Ming; Zhang, Yong-min; Tang, Jun-Ping; Cheng, Liang; Xu, Qi-fuo

    2014-06-01

    Cathode plasma of high current electron beam diode is an important research on high power microwave and strong pulsed radio accelerator. It is a reliable method to study cathode plasma by diagnosing the cathode plasma parameters with non-contact spectroscopy measurement system. The present paper introduced the work principle, system composition and performance of the nanosecond (ns) time-resolved spectroscopy diagnosis system. Furthermore, it introduced the implementing method and the temporal relation of lower jitter synchronous trigger system. Simultaneously, the authors designed electromagnetic and radio shield room to protect the diagnosis system due to the high electromagnetic and high X-ray and γ-ray radiation, which seriously interferes with the system. Time-resolved spectroscopy experiment on brass (H62) cathode shows that, the element and matter composition of cathode plasma is clearly increase with the increase in the diode pulsed voltage and current magnitude. The spectroscopy diagnosis system could be of up to 10 ns time resolve capability. It's least is 2 ns. Synchronous trigger system's jitter is less than 4 ns. The spectroscopy diagnosis system will open a new way to study the cathode emission mechanism in depth. PMID:25358142

  17. Spatially resolved tunneling spectroscopy on TTF-TCNQ

    NASA Astrophysics Data System (ADS)

    Wang, Z. Z.; Girard, J. C.; Pasquier, C.; Jérome, D.

    2004-04-01

    Local tunneling spectroscopy has been measured with low temperature UHV-STM on in-situ cleaved ab surface of organic TTF-TCNQ crystal. Due to ultra low image drift and clear molecular resolution, the spectroscopy is performed at specific molecular site either on TCNQ or TTF chains. In normal state (T= 63 K), a large pseudo-gap exists both in TTF and TCNQ chains. Above pseudo-gap local density of states differs for TTF and TCNQ chains that is in good agreement with double band model. By the signature of an anomalous in local spectroscopy measurement, a single impurity has been detected on a TTF chain. Charge density wave fluctuation is pinned by impurity above critical temperature (T=54K). Results obtained show that, Scanning Tunneling Spectroscopy can provide spatially resolved spectroscopic information at nanometer scale. Key words. TTF-TCNQ, local tunneling spectroscopy, pseudogap.

  18. Depth-resolved measurements with elliptically polarized reflectance spectroscopy

    PubMed Central

    Bailey, Maria J.; Sokolov, Konstantin

    2016-01-01

    The ability of elliptical polarized reflectance spectroscopy (EPRS) to detect spectroscopic alterations in tissue mimicking phantoms and in biological tissue in situ is demonstrated. It is shown that there is a linear relationship between light penetration depth and ellipticity. This dependence is used to demonstrate the feasibility of a depth-resolved spectroscopic imaging using EPRS. The advantages and drawbacks of EPRS in evaluation of biological tissue are analyzed and discussed. PMID:27446712

  19. Momentum Resolved Radio Frequency Spectroscopy in Trapped Fermi Gases

    SciTech Connect

    Chen Qijin; Levin, K.

    2009-05-15

    We address recent momentum-resolved radio frequency (rf) spectroscopy experiments, showing how they yield more stringent tests than other comparisons with theory, associated with the ultracold Fermi gases. We demonstrate that, by providing a clear dispersion signature of pairing, they remove the ambiguity plaguing the interpretation of previous rf experiments. Our calculated spectral intensities are in semiquantitative agreement with the data. Even in the presence of a trap, the spectra are predicted to exhibit two BCS-like branches.

  20. Quantitatively Resolving Multivalent Interactions on Macroscopic Scale Using Force Spectroscopy

    PubMed Central

    Hu, Qiongzheng; Yang, Haopeng; Wang, Yuhong; Xu, Shoujun

    2016-01-01

    Multivalent interactions remain difficult to be characterized and consequently controlled, particularly on a macroscopic scale. Using force-induced remnant magnetization spectroscopy (FIRMS), we have resolved the single-, double-, and triple- biotin—streptavidin interactions, multivalent DNA interactions and CXCL12-CXCR4 interactions, on millimetre-scale surfaces. Our results establish FIRMS as a viable method for systematic resolution and controlled formation of multivalent interactions. PMID:26864087

  1. TIMESCALE-RESOLVED SPECTROSCOPY OF Cyg X-1

    SciTech Connect

    Wu, Y. X.; Li, T. P.; Belloni, T. M.; Wang, T. S.; Liu, H.

    2009-04-20

    We propose the timescale-resolved spectroscopy (TRS) as a new method to combine the timing and spectral study. The TRS is based on the time domain power spectrum and reflects the variable amplitudes of spectral components on different timescales. We produce the TRS with the RXTE PCA data for Cyg X-1 and study the spectral parameters (the power-law photon index and the equivalent width of the iron fluorescent line) as a function of timescale. The results of TRS and frequency-resolved spectra have been compared, and similarities have been found for the two methods with the identical motivations. We also discover the correspondences between the evolution of photon index with timescale and the evolution of the equivalent width with timescale. The observations can be divided into three types according to the correspondences and different type is connected with different spectral state.

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  3. Spectrally resolved photon-echo spectroscopy of Rhodamine-6G

    PubMed Central

    Kumar, Ajitesh; Karthick, S. K.; Goswami, D.

    2013-01-01

    Wavelength dependent study of a laser dye: Rhodamine-6G (Rh6G) by using spectrally resolved photon-echo spectroscopy is presented. The coherence and population dynamics of Rh6G solution in methanol changes as the excitation wavelength is tuned near its absorption maxima of 528 nm. Specifically, the central wavelength of the femtosecond laser pulse was set to 535 nm and to 560 nm while the respective spectra of the photon-echo signals were collected. This gives information on how the ultrafast dynamics of the Rh6G molecule changes with a change in the excitation wavelength. PMID:24098869

  4. Resolving multi-exciton generation by attosecond spectroscopy.

    PubMed

    Neukirch, A J; Neumark, D M; Kling, M F; Prezhdo, O V

    2014-10-20

    We propose an experimentally viable attosecond transient absorption spectroscopy scheme to resolve controversies regarding multiexciton (ME) generation in nanoscale systems. Absence of oscillations indicates that light excites single excitons, and MEs are created by incoherent impact ionization. An oscillation indicates the coherent mechanism, involving excitation of superpositions of single and MEs. The oscillation decay, ranging from 5 fs at ambient temperature to 20 fs at 100 K, gives the elastic exciton-phonon scattering time. The signal is best observed with multiple-cycle pump pulses. PMID:25401661

  5. Spatially resolved concentration measurements based on backscatter absorption spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

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

  6. An instrument for the investigation of actinides with spin resolved photoelectron spectroscopy and bremsstrahlung isochromat spectroscopy

    SciTech Connect

    Yu, S.-W.; Tobin, J. G.; Chung, B. W.

    2011-01-01

    A new system for spin resolved photoelectron spectroscopy and bremsstrahlung isochromat spectroscopy has been built and commissioned at Lawrence Livermore National Laboratory for the investigation of the electronic structure of the actinides.Actinide materials are very toxic and radioactive and therefore cannot be brought to most general user facilities for spectroscopic studies. The technical details of the new system and preliminary data obtained therein will be presented and discussed.

  7. Momentum-resolved spectroscopy of a Fermi liquid.

    PubMed

    Doggen, Elmer V H; Kinnunen, Jami J

    2015-01-01

    We consider a recent momentum-resolved radio-frequency spectroscopy experiment, in which Fermi liquid properties of a strongly interacting atomic Fermi gas were studied. Here we show that by extending the Brueckner-Goldstone model, we can formulate a theory that goes beyond basic mean-field theories and that can be used for studying spectroscopies of dilute atomic gases in the strongly interacting regime. The model hosts well-defined quasiparticles and works across a wide range of temperatures and interaction strengths. The theory provides excellent qualitative agreement with the experiment. Comparing the predictions of the present theory with the mean-field Bardeen-Cooper-Schrieffer theory yields insights into the role of pair correlations, Tan's contact, and the Hartree mean-field energy shift. PMID:25941948

  8. Multidimensional Time-Resolved Spectroscopy of Vibrational Coherence in Biopolyenes

    NASA Astrophysics Data System (ADS)

    Buckup, Tiago; Motzkus, Marcus

    2014-04-01

    Multidimensional femtosecond time-resolved vibrational coherence spectroscopy allows one to investigate the evolution of vibrational coherence in electronic excited states. Methods such as pump-degenerate four-wave mixing and pump-impulsive vibrational spectroscopy combine an initial ultrashort laser pulse with a nonlinear probing sequence to reinduce vibrational coherence exclusively in the excited states. By carefully exploiting specific electronic resonances, one can detect vibrational coherence from 0 cm-1 to over 2,000 cm-1 and map its evolution. This review focuses on the observation and mapping of high-frequency vibrational coherence for all-trans biological polyenes such as β-carotene, lycopene, retinal, and retinal Schiff base. We discuss the role of molecular symmetry in vibrational coherence activity in the S1 electronic state and the interplay of coupling between electronic states and vibrational coherence.

  9. Visible/Infrared Imaging Spectroscopy and Energy-Resolving Detectors

    NASA Astrophysics Data System (ADS)

    Eisenhauer, Frank; Raab, Walfried

    2015-08-01

    Imaging spectroscopy has seen rapid progress over the past 25 years, leading to breakthroughs in many fields of astronomy that would not have been otherwise possible. This review overviews the visible/infrared imaging spectroscopy techniques as well as energy-resolving detectors. We introduce the working principle of scanning Fabry-Perot and Fourier transform spectrometers and explain the most common integral field concepts based on mirror slicers, lenslet arrays, and fibers. The main advantage of integral field spectrographs is the simultaneous measurement of spatial and spectral information. Although Fabry-Perot and Fourier transform spectrometers can provide a larger field of view, it is ultimately the higher sensitivity of integral field units that make them the technique of choice. This is arguably the case for image slicers, which make the most efficient use of the available detector pixels and have equal or higher transmission than lenslet arrays and fiber integral field units, respectively. We also address the more specific issues of large étendue operation, focal ratio degradation, anamorphic magnification, and diffraction-limited operation. This review also covers the emerging technology of energy-resolving detectors, which promise very simple and efficient instrument designs. These energy-resolving detectors are based on superconducting thin film technology and exploit either the very small superconducting energy to count the number of quasi-particles excited in the absorption of the photon or the extremely steep phase transition between the normal- and superconducting phase to measure a temperature increase. We have put special emphasis on an overview of the underlying physical phenomena as well as on the recent technological progress and astronomical path finder experiments.

  10. Temperature Resolved 3-D Submillimeter Spectroscopy of Astronomical `WEEDs'.

    NASA Astrophysics Data System (ADS)

    Fortman, Sarah M.; Medvedev, Ivan R.; Neese, Christopher F.; De Lucia, Frank C.

    2009-06-01

    We have previously reported on the experimental spectroscopic approach that makes possible the calculation of lower state energy levels and transition strengths without the need for spectral assignment. Analysis of the temperature dependent measurements significantly improves the estimate of the lower state energy, recovered by division of temperature dependent spectral intensities. Also, this approach provides results both in the standard astronomical catalog form (frequency, line strength, lower state energy) and as experimental temperature dependent spectra. We are reporting on temperature resolved 3-D spectroscopy of ethyl cyanide -- a well known astronomical `weed'. "An experimental approach to the prediction of complete millimeter and submillimeter spectra at astrophysical temperatures: Applications to confusion-limited astrophysical observations," I. R. Medvedev and F. C. De Lucia, Ap. J. 656, 621-628 (2007).

  11. Angle resolved electron energy loss spectroscopy on graphite

    NASA Astrophysics Data System (ADS)

    Diebold, U.; Preisinger, A.; Schattschneider, P.; Varga, P.

    We report on angle resolved electron energy loss spectroscopy (EELS) in reflection mode with low primary energy on a graphite single crystal. Measurements with primary electron energy of 175 eV have been performed in off-Bragg-reflex geometry in two different directions within the (0001) surface plane of the graphite single crystal. In addition, EELS measurements in specular reflection mode with different primary energies and angles of incidence were done in order to distinguish between surface and bulk plasmon losses. The energy losses and the transferred momenta of the losses have been analyzed. The results are compared with the loss functions for bulk and surface excitations calculated from the dielectric function ɛ(ω, q) obtained from TEELS-data (EELS in transmission mode) [Springer Tracts Mod. Phys. 54 (1970) 77].

  12. Nonselective and polarization effects in time-resolved optogalvanic spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhechev, D.; Steflekova, V.

    2016-02-01

    Three interfering effects in optogalvanic (OG) spectroscopy are identified in a hollow cathode discharge (HCD) - OG detector. The laser beam is found to generate two nonselective processes, namely photoelectron emission (PE) from the cathode surface with a sub-breakdown bias applied, and nonresonant space ionization. The convolution of these galvanic contributions was determined experimentally as an instrumental function and a deconvolution procedure to determine the actual OG signal was developed. Specific plasma conductance is detected dependent on the polarization of the laser beam irradiating. Linearly/circularly polarized light beam is found to induce OG signals differ in amplitude (and their shape parameters in the time-resolved OG signals (TROGS)). The phenomena coherence and specific conductance are found to be in causal relationship. The additional conductance due to coherent states of atoms manifests itself as an intrinsic instrumental property of OG detector.

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

    PubMed

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

    2005-01-01

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

  14. Complete momentum and energy resolved TOF electron spectrometerfor time-resolved photoemission spectroscopy

    SciTech Connect

    Hussain, Zahid; Lebedev, G.; Tremsin, A.; Siegmund, O.; Chen, Y.; Shen, Z.X.; Hussain, Z.

    2007-08-12

    Over the last decade, high-resolution Angle-Resolved Photoemission Spectroscopy (ARPES) has emerged as a tool of choice for studying the electronic structure of solids, in particular, strongly correlated complex materials such as cuprate superconductors. In this paper we present the design of a novel time-of-flight based electron analyzer with capability of 2D in momentum space (kx and ky) and all energies (calculated from time of flight) in the third dimension. This analyzer will utilize an improved version of a 2D delay linedetector capable of imaging with<35 mm (700x700 pixels) spatial resolution and better than 120 ps FWHM timing resolution. Electron optics concepts and optimization procedure are considered for achieving an energy resolution less than 1 meV and an angular resolution better than 0.11.

  15. Broadband Mid-Infrared Comb-Resolved Fourier Transform Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lee, Kevin; Mills, Andrew; Mohr, Christian; Jiang, Jie; Fermann, Martin; Maslowski, Piotr

    2014-06-01

    We report on a comb-resolved, broadband, direct-comb spectroscopy system in the mid-IR and its application to the detection of trace gases and molecular line shape analysis. By coupling an optical parametric oscillator (OPO), a 100 m multipass cell, and a high-resolution Fourier transform spectrometer (FTS), sensitive, comb-resolved broadband spectroscopy of dilute gases is possible. The OPO has radiation output at 3.1-3.7 and 4.5-5.5 μm. The laser repetition rate is scanned to arbitrary values with 1 Hz accuracy around 417 MHz. The comb-resolved spectrum is produced with an absolute frequency axis depending only on the RF reference (in this case a GPS disciplined oscillator), stable to 1 part in 10^9. The minimum detectable absorption is 1.6x10-6 wn Hz-1/2. The operating range of the experimental setup enables access to strong fundamental transitions of numerous molecular species for applications based on trace gas detection such as environmental monitoring, industrial gas calibration or medical application of human breath analysis. In addition to these capabilities, we show the application for careful line shape analysis of argon-broadened CO band spectra around 4.7 μm. Fits of the obtained spectra clearly illustrate the discrepancy between the measured spectra and the Voigt profile (VP), indicating the need to include effects such as Dicke narrowing and the speed-dependence of the collisional width and shift in the line shape model, as was shown in previous cw-laser studies. In contrast to cw-laser based experiments, in this case the entire spectrum (˜ 250 wn) covering the whole P and R branches can be measured in 16 s with 417 MHz resolution, decreasing the acquisition time by orders of magnitude. The parallel acquisition allows collection of multiple lines simultaneously, removing the correlation of possible temperature and pressure drifts. While cw-systems are capable of measuring spectra with higher precision, this demonstration opens the door for fast

  16. Electron-transfer acceleration investigated by time resolved infrared spectroscopy.

    PubMed

    Vlček, Antonín; Kvapilová, Hana; Towrie, Michael; Záliš, Stanislav

    2015-03-17

    Ultrafast electron transfer (ET) processes are important primary steps in natural and artificial photosynthesis, as well as in molecular electronic/photonic devices. In biological systems, ET often occurs surprisingly fast over long distances of several tens of angströms. Laser-pulse irradiation is conveniently used to generate strongly oxidizing (or reducing) excited states whose reactions are then studied by time-resolved spectroscopic techniques. While photoluminescence decay and UV-vis absorption supply precise kinetics data, time-resolved infrared absorption (TRIR) and Raman-based spectroscopies have the advantage of providing additional structural information and monitoring vibrational energy flows and dissipation, as well as medium relaxation, that accompany ultrafast ET. We will discuss three cases of photoinduced ET involving the Re(I)(CO)3(N,N) moiety (N,N = polypyridine) that occur much faster than would be expected from ET theories. [Re(4-N-methylpyridinium-pyridine)(CO)3(N,N)](2+) represents a case of excited-state picosecond ET between two different ligands that remains ultrafast even in slow-relaxing solvents, beating the adiabatic limit. This is caused by vibrational/solvational excitation of the precursor state and participation of high-frequency quantum modes in barrier crossing. The case of Re-tryptophan assemblies demonstrates that excited-state Trp → *Re(II) ET is accelerated from nanoseconds to picoseconds when the Re(I)(CO)3(N,N) chromophore is appended to a protein, close to a tryptophan residue. TRIR in combination with DFT calculations and structural studies reveals an interaction between the N,N ligand and the tryptophan indole. It results in partial electronic delocalization in the precursor excited state and likely contributes to the ultrafast ET rate. Long-lived vibrational/solvational excitation of the protein Re(I)(CO)3(N,N)···Trp moiety, documented by dynamic IR band shifts, could be another accelerating factor. The last

  17. Vibrationally resolved anion photoelectron spectroscopy of metal clusters

    NASA Astrophysics Data System (ADS)

    Miller, Stephen R.

    Vibrationally resolved anion photoelectron spectroscopy of metal clusters Vibrationally resolved anion photoelectron spectroscopy (APES) and density functional theory (DFT) are applied to the study of structure and reactivity in small metal containing molecules. The studies described fall into two general categories: the study of bare metal clusters and the study of metal/organic ligand reactions. The current lack of spectroscopic data for small, bare gas-phase metal compounds makes the experimental study of such compounds important for understanding structure and bonding in open-shell metallic species. The heteronuclear diatomic anions MCu- (M = Cr, Mo) were prepared in a flowing afterglow ion-molecule reactor, and studied experimentally with APES. Anion and neutral vibrational frequencies and MCu electron affinities were obtained for both systems. The experiments were supplemented by DFT calculations. The combined use of experiment and theory allows for the assignment of both photoelectron spectra, including a reassignment of the CrCu ground state reported in the literature. Similarly, DFT was used to assign the anionic/neutral electronic states observed in the photoelectron spectra of Al3- and Al3O-. The study of partially ligated organometallic complexes offers a means of examining the interactions between metal atoms and individual ligand molecules. DFT was used to assign electronic states observed in the photoelectron spectra of NbC2H2-, NbC4H4 -NbC6H6- and VC6H 6-. Comparison of the NbnHn - (n = 2, 4, 6) spectra (obtained through the reaction of C2 H4 and Nb) with DFT results provides the first direct spectroscopic evidence of the conversion of ethylene to benzene by a gas phase metal atom. Experiments were used to probe the reactivity of Y with C2H 4 in an effort to examine the generality of the metal induced C 2H4 dehydrogenation/cyclization reactions. Some of the key products in the Y reactions were YC2H-, YC 2H2-, and YC6H5 -. However, the results

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

    PubMed

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

    2016-01-01

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

  19. Direct chemical characterization of natural wood resins by temperature-resolved and space-resolved Fourier transform infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Jian-bo; Zhou, Qun; Sun, Su-qin

    2016-07-01

    Wood resins are valuable natural products with wide utilizations. Either in the form of resin exudates or in the form of resin-containing woods, natural wood resins are usually complex mixtures consisting of various compounds. Therefore, effective chemical characterization methods are necessary for the research and quality control of natural wood resins. No need for separation or labeling, wood resin samples can be measured directly by Fourier transform infrared (FT-IR) spectroscopy, which reduces the testing costs and avoids the possible distortions caused by the pretreatments. However, the absorption bands of various compositions in the resin sample are assembled in a single spectrum by the separation-free measurement, which makes it difficult to identify the compounds of interest and decreases the limits of detection. In this research, the temperature-resolved and space-resolved FT-IR techniques are proposed to resolve the overlapped signals for the direct, selective, and sensitive characterization of natural wood resins. For resin exudates, the temperature-resolved FT-IR spectroscopy and two-dimensional correlation analysis can resolve the absorption bands of different compounds according to their responses to the thermal perturbations. For resin-containing woods, the FT-IR microspectroscopic imaging and principal component analysis can resolve the absorption bands of different compounds according to their positions. The study of six kinds of wood resins proves the feasibility of temperature-resolved and space-resolved FT-IR techniques for the direct, selective, and sensitive chemical characterization of natural wood resins.

  20. Angle-resolved Photoemission Spectroscopy At Ultra-low Temperatures

    PubMed Central

    Borisenko, Sergey V.; Zabolotnyy, Volodymyr B.; Kordyuk, Alexander A.; Evtushinsky, Danil V.; Kim, Timur K.; Carleschi, Emanuela; Doyle, Bryan P.; Fittipaldi, Rosalba; Cuoco, Mario; Vecchione, Antonio; Berger, Helmut

    2012-01-01

    The physical properties of a material are defined by its electronic structure. Electrons in solids are characterized by energy (ω) and momentum (k) and the probability to find them in a particular state with given ω and k is described by the spectral function A(k, ω). This function can be directly measured in an experiment based on the well-known photoelectric effect, for the explanation of which Albert Einstein received the Nobel Prize back in 1921. In the photoelectric effect the light shone on a surface ejects electrons from the material. According to Einstein, energy conservation allows one to determine the energy of an electron inside the sample, provided the energy of the light photon and kinetic energy of the outgoing photoelectron are known. Momentum conservation makes it also possible to estimate k relating it to the momentum of the photoelectron by measuring the angle at which the photoelectron left the surface. The modern version of this technique is called Angle-Resolved Photoemission Spectroscopy (ARPES) and exploits both conservation laws in order to determine the electronic structure, i.e. energy and momentum of electrons inside the solid. In order to resolve the details crucial for understanding the topical problems of condensed matter physics, three quantities need to be minimized: uncertainty* in photon energy, uncertainty in kinetic energy of photoelectrons and temperature of the sample. In our approach we combine three recent achievements in the field of synchrotron radiation, surface science and cryogenics. We use synchrotron radiation with tunable photon energy contributing an uncertainty of the order of 1 meV, an electron energy analyzer which detects the kinetic energies with a precision of the order of 1 meV and a He3 cryostat which allows us to keep the temperature of the sample below 1 K. We discuss the exemplary results obtained on single crystals of Sr2RuO4 and some other materials. The electronic structure of this material can be

  1. Angle-resolved photoemission spectroscopy at ultra-low temperatures.

    PubMed

    Borisenko, Sergey V; Zabolotnyy, Volodymyr B; Kordyuk, Alexander A; Evtushinsky, Danil V; Kim, Timur K; Carleschi, Emanuela; Doyle, Bryan P; Fittipaldi, Rosalba; Cuoco, Mario; Vecchione, Antonio; Berger, Helmut

    2012-01-01

    The physical properties of a material are defined by its electronic structure. Electrons in solids are characterized by energy (ω) and momentum (k) and the probability to find them in a particular state with given ω and k is described by the spectral function A(k, ω). This function can be directly measured in an experiment based on the well-known photoelectric effect, for the explanation of which Albert Einstein received the Nobel Prize back in 1921. In the photoelectric effect the light shone on a surface ejects electrons from the material. According to Einstein, energy conservation allows one to determine the energy of an electron inside the sample, provided the energy of the light photon and kinetic energy of the outgoing photoelectron are known. Momentum conservation makes it also possible to estimate k relating it to the momentum of the photoelectron by measuring the angle at which the photoelectron left the surface. The modern version of this technique is called Angle-Resolved Photoemission Spectroscopy (ARPES) and exploits both conservation laws in order to determine the electronic structure, i.e. energy and momentum of electrons inside the solid. In order to resolve the details crucial for understanding the topical problems of condensed matter physics, three quantities need to be minimized: uncertainty* in photon energy, uncertainty in kinetic energy of photoelectrons and temperature of the sample. In our approach we combine three recent achievements in the field of synchrotron radiation, surface science and cryogenics. We use synchrotron radiation with tunable photon energy contributing an uncertainty of the order of 1 meV, an electron energy analyzer which detects the kinetic energies with a precision of the order of 1 meV and a He(3) cryostat which allows us to keep the temperature of the sample below 1 K. We discuss the exemplary results obtained on single crystals of Sr2RuO4 and some other materials. The electronic structure of this material can be

  2. Time-Resolved Spectroscopy of Active Binary Stars

    NASA Technical Reports Server (NTRS)

    Brown, Alexander

    2000-01-01

    This NASA grant covered EUVE observing and data analysis programs during EUVE Cycle 5 GO observing. The research involved a single Guest Observer project 97-EUVE-061 "Time-Resolved Spectroscopy of Active Binary Stars". The grant provided funding that covered 1.25 months of the PI's salary. The activities undertaken included observation planning and data analysis (both temporal and spectral). This project was awarded 910 ksec of observing time to study seven active binary stars, all but one of which were actually observed. Lambda-And was observed on 1997 Jul 30 - Aug 3 and Aug 7-14 for a total of 297 ksec; these observations showed two large complex flares that were analyzed by Osten & Brown (1999). AR Psc, observed for 350 ksec on 1997 Aug 27 - Sep 13, showed only relatively small flares that were also discussed by Osten & Brown (1999). EUVE observations of El Eri were obtained on 1994 August 24-28, simultaneous with ASCA X-ray spectra. Four flares were detected by EUVE with one of these also observed simultaneously, by ASCA. The other three EUVE observations were of the stars BY Dra (1997 Sep 22-28), V478 Lyr (1998 May 18-27), and sigma Gem (1998 Dec 10-22). The first two stars showed a few small flares. The sigma Gem data shows a beautiful complete flare with a factor of ten peak brightness compared to quiescence. The flare rise and almost all the decay phase are observed. Unfortunately no observations in other spectral regions were obtained for these stars. Analysis of the lambda-And and AR Psc observations is complete and the results were published in Osten & Brown (1999). Analysis of the BY Dra, V478 Lyr and sigma Gem EUVE data is complete and will be published in Osten (2000, in prep.). The El Eri EUV analysis is also completed and the simultaneous EUV/X-ray study will be published in Osten et al. (2000, in prep.). Both these latter papers will be submitted in summer 2000. All these results will form part of Rachel Osten's PhD thesis.

  3. Angle-resolved photoemission spectroscopy (ARPES) studies of cuprate superconductors

    SciTech Connect

    Palczewski, Ari Deibert

    2010-01-01

    This dissertation is comprised of three different angle-resolved photoemission spectroscopy (ARPES) studies on cuprate superconductors. The first study compares the band structure from two different single layer cuprates Tl2Ba2CuO6+δ (Tl2201) Tc, max ≈ 95 K and (Bi 1.35Pb0.85)(Sr1.47La0.38)CuO6+δ (Bi2201) Tc, max ≈ 35 K. The aim of the study was to provide some insight into the reasons why single layer cuprate's maximum transition temperatures are so different. The study found two major differences in the band structure. First, the Fermi surface segments close to (π,0) are more parallel in Tl2201 than in Bi2201. Second, the shadow band usually related to crystal structure is only present in Bi2201, but absent in higher Tc Tl2201. The second study looks at the different ways of doping Bi2Sr2CaCu2O8+δ (Bi2212) in-situ by only changing the post bake-out vacuum conditions and temperature. The aim of the study is to systematically look into the generally overlooked experimental conditions that change the doping of a cleaved sample in ultra high vacuum (UHV) experiments. The study found two major experimental facts. First, in inadequate UHV conditions the carrier concentration of Bi2212 increases with time, due to the absorption of oxygen from CO2/CO molecules, prime contaminants present in UHV systems. Second, in a very clean UHV system at elevated temperatures (above about 200 K), the carrier concentration decreases due to the loss of oxygen atoms from the Bi-O layer. The final study probed the particle-hole symmetry of the pseudogap phase in high temperature superconducting cuprates by looking at the thermally excited bands above the Fermi level. The data showed a particle-hole symmetric pseudogap which symmetrically closes away from the nested FS before the node. The data is consistent

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

    PubMed

    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

  5. Spatially Resolved Spectroscopy of the SNR IC443

    NASA Technical Reports Server (NTRS)

    Gorenstein, P.

    1998-01-01

    investigators examined the spatial structure of the thermal component and analyzed the GIS spectra with a non-equilibrium plasma model, and found no systematic variation of the interstellar absorption across the remnant. Evidence for shock acceleration of cosmic rays to high energies (10 TeV) was found by Keohane. X-ray imaging spectroscopy with ASCA reveals two regions of particularly hard emission: an unresolved source embedded in an extended emission region, and a ridge of emission coincident with the southeastern rim. Both features are located on part of the radio shell where the shock wave is interacting with molecular gas, and together they account for a majority of the emission at 7 keV. Though we would not have noticed it a priori, the unresolved feature is coincident with one resolved by the ROSAT HRI. The ASCA measurements were combined with higher energy data from the XTE and GRO missions and with radio and TeV gamma-ray data to produce a nonthermal multiwavelength spectrum for IC 443 which was fit with a cosmic ray interaction model. This model calculates the cynchrotron, bremsstrahlung, invers Compton, and neutral pion decay emission produced by locally accelerated cosmic ray interacting with ambient matter, soft photon fields, and magnetic fields.

  6. Frequency- and time-resolved coherence transfer spectroscopy.

    PubMed

    Rickard, Mark A; Pakoulev, Andrei V; Mathew, Nathan A; Kornau, Kathryn M; Wright, John C

    2007-02-22

    Frequency-domain two-color triply vibrational enhanced four-wave mixing using a new phase-matching geometry discriminates against coherent multidimensional spectral features created solely by radiative transitions, spectrally resolves pathways with different numbers of coherence transfer steps, and temporally resolves modulations created by interference between coherence transfer pathways. Coherence transfer is a nonradiative transition where a superposition of quantum states evolves to a different superposition. The asymmetric and symmetric C[triple bond]O stretching modes of rhodium(I) dicarbonyl acetylacetonate are used as a model system for coherence transfer. A simplified theoretical model based on Redfield theory is used to describe the experimental results. PMID:17300169

  7. Spectrally resolved femtosecond photon echo spectroscopy of astaxanthin

    NASA Astrophysics Data System (ADS)

    Kumar, Ajitesh; Karthick Kumar, S. K.; Gupta, Aditya; Goswami, Debabrata

    2010-12-01

    We have studied the coherence and population dynamics of Astaxanthin solution in methanol and acetonitrile by spectrally resolving their photon echo signals. Our experiments indicate that methanol has a much stronger interaction with the ultrafast dynamics of Astaxanthin in comparison to that of acetonitrile.

  8. Spectrally resolved femtosecond photon echo spectroscopy of astaxanthin

    NASA Astrophysics Data System (ADS)

    Kumar, Ajitesh; Karthick Kumar, S. K.; Gupta, Aditya; Goswami, Debabrata

    2011-08-01

    We have studied the coherence and population dynamics of Astaxanthin solution in methanol and acetonitrile by spectrally resolving their photon echo signals. Our experiments indicate that methanol has a much stronger interaction with the ultrafast dynamics of Astaxanthin in comparison to that of acetonitrile.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Time-resolved Hyperspectral Fluorescence Spectroscopy using Frequency Modulated Excitation

    SciTech Connect

    ,; Neill, M

    2012-07-01

    An intensity-modulated excitation light source is used together with a micro channel plate intensified CCD (ICCD) detector gated at a slightly different frequency to generate a beat frequency from a fluorescent sample. The addition of a spectrograph produces a hyperspectral time-resolved data product where the resulting beat frequency is detected with a low frame rate camera. Measuring the beat frequency of the spectrum as a function of time allows separation of the excited fluorescence from ambient constant light sources. The excitation and detector repetition rates are varied over a range of discrete frequencies, and the phase shift of the beat wave maps out the emission decay rate(s).

  11. Resolved spectroscopy of adolescent and infant galaxies (1 < z < 10)

    NASA Astrophysics Data System (ADS)

    Wright, Shelley; IRIS Science Team

    2014-07-01

    The combination of integral field spectroscopy (IFS) and adaptive optics (AO) on TMT will be revolutionary in studying the distant universe. The high angular resolution exploited by an AO system with this large aperture will be essential for studying high-redshift (1 < z < 5) galaxies' kinematics and chemical abundance histories. At even greater distances, TMT will be essential for conducting follow-up spectroscopy of Ly-alpha emission from first lights galaxies (6 < z < 10) and determining their kinematics and morphologies. I will present simulations and sensitivity calculations for high-z and first light galaxies using the diffraction-limited instrument IRIS coupled with NFIRAOS. I will put these simulations in context with current IFS+AO high-z observations and future capabilities with JWST.

  12. Angular-resolved photoelectron spectroscopy of corrugated surfaces

    NASA Astrophysics Data System (ADS)

    Olejnik, K.; Zemek, J.; Werner, W. S. M.

    2005-12-01

    The influence of surface roughness on angle-resolved photoelectron intensities has been studied by means of a semiempirical method and experimentally. The full three-dimensional information about the surface roughness of real samples measured by atomic force microscopy (AFM) was used as an input for the calculations of the so-called tilt-angle histograms. Both effects of surface roughness, shadowing of photoelectrons and differences between microscopic and macroscopic signal electron emission geometry (true emission angles), are taken into account. Photoelectron current is then calculated using a common formalism XPS/AES valid for ideally flat surfaces, i.e. analytically by the straight-line approximation (SLA) or by Monte Carlo calculations. The approach which can be applied for an arbitrary type of surface roughness is verified on angular-resolved Si 2p photoelectron spectra recorded from model silicon samples with different artificially modified surface roughness, covered by a thin silicon oxide film and a surface contamination. The effect of surface roughness on the Si 2p photoelectron intensities was found to be quite prevalent over electron elastic scattering or surface contamination effects. The so-called magic angle depended on a character of surface roughness.

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

    NASA Astrophysics Data System (ADS)

    Murphy, Joseph R.

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

  14. Time-resolved air monitoring using Fourier absorption spectroscopy

    SciTech Connect

    Biermann, H.W.

    1995-12-31

    Two categories where spectroscopic techniques excel are the capabilities to perform air analyses in situ and to obtain data at very high time resolutions. Because of these features, the Department of Pesticide Regulation augmented its extensive air monitoring capabilities with a Fourier transform infrared (FTIR) spectrometer using open-path optical systems for time resolved ambient air monitoring. A description of the instrumentation and the data analysis procedures will be presented based on two data sets obtained with this FTIR system. In one case, a 100 m folded optical path was used to measure methyl bromide concentrations after fumigation in a warehouse with a time resolution of 15 min and a detection limit of 0.2 ppm. And trying to assess the capability of this FTIR spectrometer to determine flux, water vapor concentrations were measured with a four-meter path length at a time resolution of 0.6 seconds.

  15. Time-resolved phase-sensitive second harmonic generation spectroscopy

    NASA Astrophysics Data System (ADS)

    Nowakowski, Paweł J.; Woods, David A.; Bain, Colin D.; Verlet, Jan R. R.

    2015-02-01

    A methodology based on time-resolved, phase-sensitive second harmonic generation (SHG) for probing the excited state dynamics of species at interfaces is presented. It is based on an interference measurement between the SHG from the sample and a local oscillator generated at a reference together with a lock-in measurement to remove the large constant offset from the interference. The technique is characterized by measuring the phase and excited state dynamics of the dye malachite green at the water/air interface. The key attributes of the technique are that the observed signal is directly proportional to sample concentration, in contrast to the quadratic dependence from non-phase sensitive SHG, and that the real and imaginary parts of the 2nd order non-linear susceptibility can be determined independently. We show that the method is highly sensitive and can provide high quality excited state dynamics in short data acquisition times.

  16. Fingerprints of Majorana fermions in spin-resolved subgap spectroscopy

    NASA Astrophysics Data System (ADS)

    Chirla, Razvan; Moca, Cǎtǎlin Paşcu

    2016-07-01

    When a strongly correlated quantum dot is tunnel coupled to a superconductor, it leads to the formation of Shiba bound states inside the superconducting gap. They have been measured experimentally in a superconductor-quantum dot-normal lead setup. Side coupling the quantum dot to a topological superconducting wire that supports Majorana bound states at its ends, drastically affects the structure of the Shiba states and induces supplementary in-gap states. The anomalous coupling between the Majorana bound states and the quantum dot gives rise to a characteristic imbalance in the spin-resolved spectral functions for the dot operators. These are clear fingerprints for the existence of Majorana fermions and they can be detected experimentally in transport measurements. In terms of methods employed, we have used analytical approaches combined with the numerical renormalization group approach.

  17. Spin- and angle-resolved spectroscopy of S 2p photoionization in the hydrogen sulfide molecule

    SciTech Connect

    Turri, G.; Snell, G.; Canton, S.E.; Bilodeau, R.C.; Langer, B.; Martins, M.; Kukk, E.; Cherepkov, N.; Bozek, J.D.; Kilcoyne, A.L.; Berrah, N.

    2004-08-01

    Angle- and spin-resolved photoelectron spectroscopy with circularly and linearly polarized synchrotron radiation were used to study the electronic structure of the hydrogen sulfide molecule. A strong effect of the molecular environment appears in the spin-resolved measurements and, although less clearly, in the angular distribution of the sulfur 2p photoelectrons. The anisotropy and spin parameters of the three main spectral components have been obtained. The validity of simple atomic models in explaining the results is discussed.

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

    PubMed

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

    2011-03-01

    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 photoemitted 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. PMID:21335912

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

    PubMed

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

    2000-06-01

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

  20. Multispectral scanning time-resolved fluorescence spectroscopy (TRFS) technique for intravascular diagnosis

    PubMed Central

    Xie, Hongtao; Bec, Julien; Liu, Jing; Sun, Yang; Lam, Matthew; Yankelevich, Diego R.; Marcu, Laura

    2012-01-01

    This study describes a scanning time-resolved fluorescence spectroscopy (TRFS) system designed to continuously acquire fluorescence emission and to reconstruct fluorescence lifetime images (FLIM) from a luminal surface by using a catheter-based optical probe with rotary joint and pull-back device. The ability of the system to temporally and spectrally resolve the fluorescence emission from tissue was validated using standard dyes and tissue phantoms (e.g., ex vivo pig aorta phantom). Current results demonstrate that this system is capable to reliably resolve the fluorescence emission of multiple fluorophores located in the lumen; and suggest its potential for intravascular detection of distinct biochemical features of atherosclerotic plaques. PMID:22808425

  1. Time-resolved diffuse spectroscopy measurements using a hybrid Green's function for the radiative transfer equation

    NASA Astrophysics Data System (ADS)

    Simon, Emanuel; Foschum, Florian; Kienle, Alwin

    2013-06-01

    Time-resolved diffuse optical spectroscopy measurements of phantoms at small source-detector separations yield good results for the retrieved coefficients of reduced scattering and absorption when a hybrid Green's function of the radiative transfer equation for semi-infinite media is used.

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

    NASA Astrophysics Data System (ADS)

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

    2013-06-01

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

  3. Resolving stellar populations with crowded field 3D spectroscopy

    NASA Astrophysics Data System (ADS)

    Kamann, S.; Wisotzki, L.; Roth, M. M.

    2013-01-01

    We describe a new method of extracting the spectra of stars from observations of crowded stellar fields with integral field spectroscopy (IFS). Our approach extends the well-established concept of crowded field photometry in images into the domain of 3-dimensional spectroscopic datacubes. The main features of our algorithm follow. (1) We assume that a high-fidelity input source catalogue already exists, e.g. from HST data, and that it is not needed to perform sophisticated source detection in the IFS data. (2) Source positions and properties of the point spread function (PSF) vary smoothly between spectral layers of the datacube, and these variations can be described by simple fitting functions. (3) The shape of the PSF can be adequately described by an analytical function. Even without isolated PSF calibrator stars we can therefore estimate the PSF by a model fit to the full ensemble of stars visible within the field of view. (4) By using sparse matrices to describe the sources, the problem of extracting the spectra of many stars simultaneously becomes computationally tractable. We present extensive performance and validation tests of our algorithm using realistic simulated datacubes that closely reproduce actual IFS observations of the central regions of Galactic globular clusters. We investigate the quality of the extracted spectra under the effects of crowding with respect to the resulting signal-to-noise ratios (S/N) and any possible changes in the continuum level, as well as with respect to absorption line spectral parameters, radial velocities, and equivalent widths. The main effect of blending between two nearby stars is a decrease in the S/N in their spectra. The effect increases with the crowding in the field in a way that the maximum number of stars with useful spectra is always ~0.2 per spatial resolution element. This balance breaks down when exceeding a total source density of one significantly detected star per resolution element. We also explore the

  4. An inexpensive technique for the time resolved laser induced plasma spectroscopy

    NASA Astrophysics Data System (ADS)

    Ahmed, Rizwan; Ahmed, Nasar; Iqbal, J.; Aslam Baig, M.

    2016-08-01

    We present an efficient and inexpensive method for calculating the time resolved emission spectrum from the time integrated spectrum by monitoring the time evolution of neutral and singly ionized species in the laser produced plasma. To validate our assertion of extracting time resolved information from the time integrated spectrum, the time evolution data of the Cu II line at 481.29 nm and the molecular bands of AlO in the wavelength region (450-550 nm) have been studied. The plasma parameters were also estimated from the time resolved and time integrated spectra. A comparison of the results clearly reveals that the time resolved information about the plasma parameters can be extracted from the spectra registered with a time integrated spectrograph. Our proposed method will make the laser induced plasma spectroscopy robust and a low cost technique which is attractive for industry and environmental monitoring.

  5. Combined time- and depth-resolved autofluorescence spectroscopy for tissue diagnosis

    NASA Astrophysics Data System (ADS)

    Wu, Yicong; Qu, Jianan Y.

    2006-02-01

    A fluorescence spectroscopy system combining depth- and time-resolved measurements is developed to investigate the layered fluorescence temporal characteristics of epithelial tissue. It is found that esophageal tissue structure can be resolved well by means of the autofluorescence time-resolved decay process with 375-, 405- and 435- nm excitation. The decay of the autofluorescence signals can be accurately fitted with a dual-exponential function consisting of a short lifetime (0.4 ~ 0.6 ns) and a long lifetime (3 ~ 4 ns) components. The short lifetime component dominates the decay of normal epithelial fluorescence while the decay of the signals from keratinized epithelium and stroma are mainly determined by the long lifetime component. The ratio of the amplitudes of two components provides the information of fine structure of epithelial tissue. This study demonstrates that the combined depth- and time-resolved measurements can potentially provide accurate information for the diagnosis of tissue pathology.

  6. Rapid and economical data acquisition in ultrafast frequency-resolved spectroscopy using choppers and a microcontroller.

    PubMed

    Guo, Liang; Monahan, Daniele M; Fleming, Graham

    2016-08-01

    Spectrometers and cameras are used in ultrafast spectroscopy to achieve high resolution in both time and frequency domains. Frequency-resolved signals from the camera pixels cannot be processed by common lock-in amplifiers, which have only a limited number of input channels. Here we demonstrate a rapid and economical method that achieves the function of a lock-in amplifier using mechanical choppers and a programmable microcontroller. We demonstrate the method's effectiveness by performing a frequency-resolved pump-probe measurement on the dye Nile Blue in solution. PMID:27505778

  7. Remote time-resolved filament-induced breakdown spectroscopy of biological materials

    NASA Astrophysics Data System (ADS)

    Xu, H. L.; Liu, W.; Chin, S. L.

    2006-05-01

    We report, for what we believe to be the first time, on the feasibility of remote time-resolved filament-induced breakdown spectroscopy (FIBS) of biological materials. The fluorescence from egg white and yeast powder, induced by femtosecond laser pulse filamentation in air, was detected in the backward direction with targets located 3.5 m away from the detection system. The remarkably distinct spectra of egg white and yeast allow us to propose that this technique, time-resolved FIBS, could be potentially useful for remote detection and identification of harmful biological agents.

  8. Angle-Resolved Auger Spectroscopy as a Sensitive Access to Vibronic Coupling

    NASA Astrophysics Data System (ADS)

    Knie, A.; Patanen, M.; Hans, A.; Petrov, I. D.; Bozek, J. D.; Ehresmann, A.; Demekhin, Ph. V.

    2016-05-01

    In the angle-averaged excitation and decay spectra of molecules, vibronic coupling may induce the usually weak dipole-forbidden transitions by the excitation intensity borrowing mechanism. The present complementary theoretical and experimental study of the resonant Auger decay of core-to-Rydberg excited CH4 and Ne demonstrates that vibronic coupling plays a decisive role in the formation of the angle-resolved spectra by additionally involving the decay rate borrowing mechanism. Thereby, we propose that the angle-resolved Auger spectroscopy can in general provide very insightful information on the strength of the vibronic coupling.

  9. Resolving molecular vibronic structure using high-sensitivity two-dimensional electronic spectroscopy

    SciTech Connect

    Bizimana, Laurie A.; Brazard, Johanna; Carbery, William P.; Gellen, Tobias; Turner, Daniel B.

    2015-10-28

    Coherent multidimensional optical spectroscopy is an emerging technique for resolving structure and ultrafast dynamics of molecules, proteins, semiconductors, and other materials. A current challenge is the quality of kinetics that are examined as a function of waiting time. Inspired by noise-suppression methods of transient absorption, here we incorporate shot-by-shot acquisitions and balanced detection into coherent multidimensional optical spectroscopy. We demonstrate that implementing noise-suppression methods in two-dimensional electronic spectroscopy not only improves the quality of features in individual spectra but also increases the sensitivity to ultrafast time-dependent changes in the spectral features. Measurements on cresyl violet perchlorate are consistent with the vibronic pattern predicted by theoretical models of a highly displaced harmonic oscillator. The noise-suppression methods should benefit research into coherent electronic dynamics, and they can be adapted to multidimensional spectroscopies across the infrared and ultraviolet frequency ranges.

  10. Resolving molecular vibronic structure using high-sensitivity two-dimensional electronic spectroscopy

    NASA Astrophysics Data System (ADS)

    Bizimana, Laurie A.; Brazard, Johanna; Carbery, William P.; Gellen, Tobias; Turner, Daniel B.

    2015-10-01

    Coherent multidimensional optical spectroscopy is an emerging technique for resolving structure and ultrafast dynamics of molecules, proteins, semiconductors, and other materials. A current challenge is the quality of kinetics that are examined as a function of waiting time. Inspired by noise-suppression methods of transient absorption, here we incorporate shot-by-shot acquisitions and balanced detection into coherent multidimensional optical spectroscopy. We demonstrate that implementing noise-suppression methods in two-dimensional electronic spectroscopy not only improves the quality of features in individual spectra but also increases the sensitivity to ultrafast time-dependent changes in the spectral features. Measurements on cresyl violet perchlorate are consistent with the vibronic pattern predicted by theoretical models of a highly displaced harmonic oscillator. The noise-suppression methods should benefit research into coherent electronic dynamics, and they can be adapted to multidimensional spectroscopies across the infrared and ultraviolet frequency ranges.

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

    PubMed

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

    2016-08-18

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

  12. Phase-resolved emission spectroscopy of a neutraliser-free gridded ion thruster

    NASA Astrophysics Data System (ADS)

    Dedrick, James; Gibson, Andrew; Rafalskyi, Dmytro; Aanesland, Ane

    2015-09-01

    Power-efficient electric propulsion systems that operate without an external neutraliser have the potential to increase the longevity of traditional concepts. The Neptune gridded-ion thruster prototype, which uses a single radio-requency (rf) power source for plasma generation, ion acceleration and beam neutralisation, is under development. Previous research has suggested that the time-resolved electron dynamics in the plume are important for maintaining charge neutrality and overall performance. In this study, the electron dynamics in the exhaust beam are investigated within the rf cycle using phase-resolved emission spectroscopy. The results are compared with time-resolved and time-integrated electrical diagnostics to investigate the mechanisms behind beam neutralisation. This work received financial support from the York-Paris CIRC and state aid managed by the laboratory of excellence Plas@Par (ANR-11-IDEX-0004-02).

  13. Depth-resolved fluorescence spectroscopy of normal and dysplastic cervical tissue

    NASA Astrophysics Data System (ADS)

    Wu, Yicong; Xi, Peng; Qu, Jianan Y.; Cheung, Tak-Hong; Yu, Mei-Yung

    2005-01-01

    A portable confocal system with the excitations at 355nm and 457nm was instrumented to investigate the depth-resolved fluorescence of cervical tissue. The study focused on extracting biochemical and morphological information carried in the depth-resolved signals measured from the normal squamous epithelial tissue and squamous intraepithelial lesions. Strong keratin fluorescence with the spectral characteristics similar to collagen were observed from the topmost keratinizing layer of all tissue samples. It was found that NADH and FAD fluorescence measured from the underlying non-keratinizing epithelial layer were strongly correlated to the tissue pathology. This study demonstrates that the depth-resolved fluorescence spectroscopy can potentially provide more accurate diagnostic information for determining tissue pathology.

  14. Anisotropy resolved multidimensional emission spectroscopy (ARMES): A new tool for protein analysis.

    PubMed

    Groza, Radu Constantin; Li, Boyan; Ryder, Alan G

    2015-07-30

    Structural analysis of proteins using the emission of intrinsic fluorophores is complicated by spectral overlap. Anisotropy resolved multidimensional emission spectroscopy (ARMES) overcame the overlap problem by the use of anisotropy, with chemometric analysis, to better resolve emission from different fluorophores. Total synchronous fluorescence scan (TSFS) provided information about all the fluorophores that contributed to emission while anisotropy provided information about the environment of each fluorophore. Here the utility of ARMES was demonstrated via study of the chemical and thermal denaturation of human serum albumin (HSA). Multivariate curve resolution (MCR) analysis of the constituent polarized emission ARMES data resolved contributions from four emitters: fluorescence from tryptophan (Trp), solvent exposed tyrosine (Tyr), Tyr in a hydrophobic environment, and room temperature phosphorescence (RTP) from Trp. The MCR scores, anisotropy, and literature validated these assignments and showed all the expected transitions during HSA unfolding. This new methodology for comprehensive intrinsic fluorescence analysis of proteins is applicable to any protein containing multiple fluorophores. PMID:26320645

  15. Communication: Broadband and ultrasensitive femtosecond time-resolved circular dichroism spectroscopy.

    PubMed

    Hiramatsu, Kotaro; Nagata, Takashi

    2015-09-28

    We report the development of broadband and sensitive time-resolved circular dichroism (TRCD) spectroscopy by exploiting optical heterodyne detection. Using this method, transient CD signals of submillidegree level can be detected over the spectral range of 415-730 nm. We also demonstrate that the broadband measurement with the aid of singular value decomposition enables the discrimination of genuine TRCD signals from artificial optical-anisotropy, such as linear birefringence and linear dichroism, induced by photoexcitation. PMID:26428989

  16. High-harmonic XUV source for time- and angle-resolved photoemission spectroscopy

    SciTech Connect

    Dakovski, Georgi L; Li, Yinwan; Durakiewicz, Tomasz; Rodriguez, George

    2009-01-01

    We present a laser-based apparatus for visible pump/XUV probe time- and angle-resolved photoemission spectroscopy (TRARPES) utilizing high-harmonic generation from a noble gas. Femtosecond temporal resolution for each selected harmonic is achieved by using a time-delay-compensated monochromator (TCM). The source has been used to obtain photoemission spectra from insulators (UO{sub 2}) and ultrafast pump/probe processes in semiconductors (GaAs).

  17. Time-resolved emission spectroscopy of gadolinium vanadate ceramics (GdVO4:Bi3+)

    NASA Astrophysics Data System (ADS)

    Leppert, J.; Peudenier, S.; Bayer, E.; Grabmaier, B. C.; Blasse, G.

    1994-07-01

    The preparation of GdVO4:Bi3+ ceramics is indicated. Bismuth shows a strong tendency to evaporate during the sintering process. Time-resolved emission spectroscopy shows for sufficiently low Bi3+ concentrations subsequently: blue VO{4/3-}emission with a decay time corresponding to the transfer rate (106 s-1), yellow VO{4/3-}-Bi3+ emission, rare-earth impurity emission and VO{4/3-}-Bi3+ afterglow.

  18. Development of the Experimental System for Time- and Angle-resolved Photoemission Spectroscopy

    SciTech Connect

    Takahashi, Kazutoshi; Azuma, Junpei; Tokudomi, Shinji; Kamada, Masao

    2007-01-19

    Experimental system for the time- and angle-resolved photoemission spectroscopy have been constructed at BL13 in SAGA Light Source, in order to study the electronic non-equilibrium in the surface layer of laser-excited materials The experimental system is very useful for photoemission spectroscopy in the wide temporal and angular ranges. The time- and angle-resolved photoemission spectra can be obtained with using the gate electronics for the MCP detector of the photoemission spectrometer. The gated MCP detector is synchronized with the laser pulse from Ti:sapphire regenerative amplifier with the repetition frequency of 10 to 300 kHz. The time-window of the gated MCP detector can be changed between 10 nano- and 160 micro-second. The time-resolved measurement in pico-second region can be performed with using the pump-probe technique which uses fundamental, second and third harmonics from the Ti:sapphire laser as the excitation source. Using these systems, we can perform the time- and angle-resolved photoemission study for various photo-excited phenomena and surface dynamics.

  19. Probing interfacial electron dynamics with time-resolved X-ray spectroscopy

    NASA Astrophysics Data System (ADS)

    Neppl, Stefan

    2015-05-01

    Time-resolved core-level spectroscopy techniques using laser pulses to initiate and short X-ray pulses to probe photo-induced processes have the potential to provide electronic state- and atomic site-specific insight into fundamental electron dynamics at complex interfaces. We describe the implementation of femto- and picosecond time-resolved photoelectron spectroscopy at the Linac Coherent Light Source (LCLS) and at the Advanced Light Source (ALS) in order to follow light-driven electron dynamics at dye-semiconductor interfaces on femto- to nanosecond timescales, and from the perspective of individual atomic sites. A distinct transient binding-energy shift of the Ru3d photoemission lines originating from the metal centers of N3 dye-molecules adsorbed on nanoporous ZnO is observed 500 fs after resonant HOMO-LUMO excitation with a visible laser pulse. This dynamical chemical shift is accompanied by a characteristic surface photo-voltage response of the semiconductor substrate. The two phenomena and their correlation will be discussed in the context of electronic bottlenecks for efficient interfacial charge-transfer and possible charge recombination and relaxation pathways leading to the neutralization of the transiently oxidized dye following ultrafast electron injection. First steps towards in operando time-resolved X-ray absorption spectroscopy techniques to monitor interfacial chemical dynamics will be presented.

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

    NASA Astrophysics Data System (ADS)

    Elezzabi, A. Y.; Maraghechi, P.

    2012-05-01

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

  1. Photodissociation of thioglycolic acid studied by femtosecond time-resolved transient absorption spectroscopy

    SciTech Connect

    Attar, Andrew R.; Blumling, Daniel E.; Knappenberger, Kenneth L. Jr.

    2011-01-14

    Steady-state and time-resolved spectroscopies were employed to study the photodissociation of both the neutral (HS-CH{sub 2}-COOH) and doubly deprotonated ({sup -}S-CH{sub 2}-COO{sup -}) forms of thioglycolic acid (TGA), a common surface-passivating ligand used in the aqueous synthesis and organization of semiconducting nanostructures. Room temperature UV-Vis absorption spectroscopy indicated strong absorption by the S{sub 1} and S{sub 2} excited states at 250 nm and 185 nm, respectively. The spectrum also contained a weaker absorption band that extended to approximately 550 nm, which was assigned to the {pi}{sub CO}{sup *}(leftarrow)n{sub O} transition. Femtosecond time-resolved transient absorption spectroscopy was performed on TGA using 400 nm excitation and a white-light continuum probe to provide the temporally and spectrally resolved data. Both forms of TGA underwent a photoinduced dissociation from the excited state to form an {alpha}-thiol-substituted acyl radical ({alpha}-TAR, S-CH{sub 2}-CO). For the acidic form of TGA, radical formation occurred with an apparent time constant of 60 {+-} 5 fs; subsequent unimolecular decay took 400 {+-} 60 fs. Similar kinetics were observed for the deprotonated form of TGA (70 {+-} 10 fs radical formation; 420 {+-} 40 fs decay). The production of the {alpha}-TAR was corroborated by the observation of its characteristic optical absorption. Time-resolved data indicated that the photoinduced dissociation of TGA via cleavage of the C-OH bond occurred rapidly ({<=}100 fs). The prevalence of TGA in aqueous semiconducting nanoparticles makes its absorption in the visible spectral region and subsequent dissociation key to understanding the behavior of nanoscale systems.

  2. Time-resolved FRET fluorescence spectroscopy of visible fluorescent protein pairs.

    PubMed

    Visser, A J W G; Laptenok, S P; Visser, N V; van Hoek, A; Birch, D J S; Brochon, J-C; Borst, J W

    2010-01-01

    Förster resonance energy transfer (FRET) is a powerful method for obtaining information about small-scale lengths between biomacromolecules. Visible fluorescent proteins (VFPs) are widely used as spectrally different FRET pairs, where one VFP acts as a donor and another VFP as an acceptor. The VFPs are usually fused to the proteins of interest, and this fusion product is genetically encoded in cells. FRET between VFPs can be determined by analysis of either the fluorescence decay properties of the donor molecule or the rise time of acceptor fluorescence. Time-resolved fluorescence spectroscopy is the technique of choice to perform these measurements. FRET can be measured not only in solution, but also in living cells by the technique of fluorescence lifetime imaging microscopy (FLIM), where fluorescence lifetimes are determined with the spatial resolution of an optical microscope. Here we focus attention on time-resolved fluorescence spectroscopy of purified, selected VFPs (both single VFPs and FRET pairs of VFPs) in cuvette-type experiments. For quantitative interpretation of FRET-FLIM experiments in cellular systems, details of the molecular fluorescence are needed that can be obtained from experiments with isolated VFPs. For analysis of the time-resolved fluorescence experiments of VFPs, we have utilised the maximum entropy method procedure to obtain a distribution of fluorescence lifetimes. Distributed lifetime patterns turn out to have diagnostic value, for instance, in observing populations of VFP pairs that are FRET-inactive. PMID:19693494

  3. Planetary Surface Exploration Using Time-Resolved Laser Spectroscopy on Rovers and Landers

    NASA Astrophysics Data System (ADS)

    Blacksberg, Jordana; Alerstam, Erik; Maruyama, Yuki; Charbon, Edoardo; Rossman, George

    2013-04-01

    Planetary surface exploration using laser spectroscopy has become increasingly relevant as these techniques become a reality on Mars surface missions. The ChemCam instrument onboard the Curiosity rover is currently using laser induced breakdown spectroscopy (LIBS) on a mast-mounted platform to measure elemental composition of target rocks. The RLS Raman Spectrometer is included on the payload for the ExoMars mission to be launched in 2018 and will identify minerals and organics on the Martian surface. We present a next-generation instrument that builds on these widely used techniques to provide a means for performing both Raman spectroscopy and LIBS in conjunction with microscopic imaging. Microscopic Raman spectroscopy with a laser spot size smaller than the grains of interest can provide surface mapping of mineralogy while preserving morphology. A very small laser spot size (~ 1 µm) is often necessary to identify minor phases that are often of greater interest than the matrix phases. In addition to the difficulties that can be posed by fine-grained material, fluorescence interference from the very same material is often problematic. This is particularly true for many of the minerals of interest that form in environments of aqueous alteration and can be highly fluorescent. We use time-resolved laser spectroscopy to eliminate fluorescence interference that can often make it difficult or impossible to obtain Raman spectra. As an added benefit, we have found that with small changes in operating parameters we can include microscopic LIBS using the same hardware. This new technique relies on sub-ns, high rep-rate lasers with relatively low pulse energy and compact solid state detectors with sub-ns time resolution. The detector technology that makes this instrument possible is a newly developed Single-Photon Avalanche Diode (SPAD) sensor array based on Complementary Metal-Oxide Semiconductor (CMOS) technology. The use of this solid state time-resolved detector offers a

  4. Conventional and Time-Resolved Infrared Spectroscopy of La-1111 Thin Films

    NASA Astrophysics Data System (ADS)

    Xi, Xiaoxiang; Dai, Y.; Homes, C.; Kidszun, M.; Haindl, S.; Carr, G.

    2013-03-01

    We have performed both conventional as well as time-resolved far-infrared spectroscopy on LaFeAsO1-xFx pnictide thin films. The conventional spectroscopy results can be fit using a simple gapped superconductor + normal conductor two-component model. Absorption by quasiparticles in a gap system with nodes is a plausible explanation for the normal component [Lobo et al. Phys. Rev. B 82, 100506(R) (2010)]. The time-resolved study is performed by laser-pump, far-IR probe spectroscopy using synchrotron radiation at NSLS beamline U4IR. A laser pulse breaks superconducting pairs and the synchrotron probe is used to sense the recombination process. In contrast to the picosecond response observed for cuprate superconductors, we observe a nanosecond response typical of a fully gapped superconductor where phonon-bottleneck effects slow the effective recombination rate. This result suggests the presence of a full isotropic gap, as might exist at lower energies due to electronic scattering [Carbotte et al. Phys. Rev. B 81, 104510 (2010)]. Supported by the U.S. Dep't. of Energy under contract DE-AC02-98CH10886 at Brookhaven Nat'l Lab.

  5. Time-resolved magnetic circular dichroism spectroscopy of photolyzed carbonmonoxy cytochrome c oxidase (cytochrome aa3).

    PubMed Central

    Goldbeck, R A; Dawes, T D; Einarsdóttir, O; Woodruff, W H; Kliger, D S

    1991-01-01

    Nanosecond time-resolved magnetic circular dichroism (TRMCD) and time-resolved natural circular dichroism (TRCD) measurements of photolysis products of the CO complex of eukaryotic cytochrome c oxidase (CcO-CO) are presented. TRMCD spectra obtained at 100 ns and 10 microseconds after photolysis are diagnostic of pentacoordinate cytochrome a3Fe2+, as would be expected for simple photodissociation. Other time-resolved spectroscopies (UV-visible and resonance Raman), however, show evidence for unusual Fea3(2+) coordination after CO photolysis (Woodruff, W. H., O. Einarsdóttir, R. B. Dyer, K. A. Bagley, G. Palmer, S. J. Atherton, R. A. Goldbeck, T. D. Dawes, and D. S. Kliger. 1991. Proc. Nat. Acad. Sci. U.S.A. 88:2588-2592). Furthermore, time-resolved IR experiments have shown that photodissociated CO binds to CuB+ prior to recombining with Fea3(2+) (Dyer, R. B., O. Einarsdóttir, P. M. Killough, J. J. López-Garriga, and W. H. Woodruff. 1989. J. Am. Chem. Soc. 111:7657-7659). A model of the CcO-CO photolysis cycle which is consistent with all of the spectroscopic results is presented. A novel feature of this model is the coordination of a ligand endogenous to the protein to the Fe axial site vacated by the photolyzed CO and the simultaneous breaking of the Fe-imidazole(histidine) bond. PMID:1653049

  6. Resolved Sideband Spectroscopy and Cooling of Strontium in a 532-nm Optical Lattice

    NASA Astrophysics Data System (ADS)

    Aman, James; Hill, Joshua; Killian, T. C.

    2016-05-01

    Resolved sideband cooling is a powerful and well established technique for driving ultracold atoms in optical lattices to the motional ground state of individual lattice sites. Here we present spectroscopy of the narrow 5s21S0 --> 5 s 5 p3P1 transition for neutral strontium-84 in a 532nm optical lattice. Resolved red- and blue-detuned sidebands are observed corresponding to changes in the motional state in the lattice sites. Driving the red sideband, we demonstrate cooling into the ground state, which increases the initial phase-space density before forced evaporative cooling. This is a promising technique for improving the production of strontium quantum degenerate gases. Research supported by the Robert A, Welch Foundation under Grant No. C-1844.

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

    PubMed

    Sato, Tokushi; Nozawa, Shunsuke; Ichiyanagi, Kohei; Tomita, Ayana; Chollet, Matthieu; Ichikawa, Hirohiko; Fujii, Hiroshi; Adachi, Shin Ichi; Koshihara, Shin Ya

    2009-01-01

    An experimental set-up for time-resolved X-ray absorption spectroscopy with 100 ps time resolution at beamline NW14A at the Photon Factory Advanced Ring is presented. The X-ray positional active feedback to crystals in a monochromator combined with a figure-of-merit scan of the laser beam position has been utilized as an essential tool to stabilize the spatial overlap of the X-ray and laser beams at the sample position. As a typical example, a time-resolved XAFS measurement of a photo-induced spin crossover reaction of the tris(1,10-phenanthrorine)iron(II) complex in water is presented. PMID:19096182

  8. Polarization and time-resolved photoluminescence spectroscopy of excitons in MoSe2 monolayers

    NASA Astrophysics Data System (ADS)

    Wang, G.; Palleau, E.; Amand, T.; Tongay, S.; Marie, X.; Urbaszek, B.

    2015-03-01

    We investigate valley exciton dynamics in MoSe2 monolayers in polarization- and time-resolved photoluminescence (PL) spectroscopy at 4 K. Following circularly polarized laser excitation, we record a low circular polarization degree of the PL of typically ≤5%. This is about 10 times lower than the polarization induced under comparable conditions in MoS2 and WSe2 monolayers. The evolution of the exciton polarization as a function of excitation laser energy and power is monitored in PL excitation experiments. Fast PL emission times are recorded for both the neutral exciton of ≤3 ps and for the charged exciton (trion) of 12 ps.

  9. A CAMAC system controlled by an IBM AT computer for time-resolved spectroscopy

    SciTech Connect

    Lindquist, L.O.; Moss, C.E.

    1987-01-01

    An IBM AT computer interfaced to a small CAMAC system offers considerable power without the complexity and expense of a large general-purpose system. Our system for time-resolved spectroscopy features menu-driven FORTRAN-based software; high-resolution and high-speed (8K channels, 5-..mu..s fixed dead time) ADCs; segmentable histogram memories (24-bit counts) with large memory space for many histogram segments; independently variable separate histogram dwell times; remote control via a CAMAC serial highway; and ground isolation between the data acquisition equipment and control computer by means of fiber optics.

  10. Application of time-resolved resonance Raman spectroscopy to intramolecular electron transfer

    SciTech Connect

    Schoonover, J.R.; Strouse, G.F.; Chen, P.; Bates, D.; Meyer, T.J. )

    1993-06-09

    Time-resolved resonance Raman spectroscopy has been applied for the first time to the study of intramolecular electron transfer in a chromophore-quencher complex, based on a metal-to-ligand charge-transfer (MLCT) excited state. These measurements allow for (1) the identification of redox sites that are reached following excitation and (2) the inferring of structural information in short-lived intermediates. This technique is a more sensitive probe than transient absorption as shown by its application to the redox-separated complex shown below involving a pyridinium acceptor and a phenothiazine donor.

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

    PubMed

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

    2012-11-10

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

  12. Time- and angle-resolved photoemission spectroscopy of hydrated electrons near a liquid water surface.

    PubMed

    Yamamoto, Yo-ichi; Suzuki, Yoshi-Ichi; Tomasello, Gaia; Horio, Takuya; Karashima, Shutaro; Mitríc, Roland; Suzuki, Toshinori

    2014-05-01

    We present time- and angle-resolved photoemission spectroscopy of trapped electrons near liquid surfaces. Photoemission from the ground state of a hydrated electron at 260 nm is found to be isotropic, while anisotropic photoemission is observed for the excited states of 1,4-diazabicyclo[2,2,2]octane and I- in aqueous solutions. Our results indicate that surface and subsurface species create hydrated electrons in the bulk side. No signature of a surface-bound electron has been observed. PMID:24856723

  13. Phase-resolved optical emission spectroscopy for an electron cyclotron resonance etcher

    SciTech Connect

    Milosavljevic, Vladimir; MacGearailt, Niall; Daniels, Stephen; Turner, Miles M.; Cullen, P. J.

    2013-04-28

    Phase-resolved optical emission spectroscopy (PROES) is used for the measurement of plasma products in a typical industrial electron cyclotron resonance (ECR) plasma etcher. In this paper, the PROES of oxygen and argon atoms spectral lines are investigated over a wide range of process parameters. The PROES shows a discrimination between the plasma species from gas phase and those which come from the solid phase due to surface etching. The relationship between the micro-wave and radio-frequency generators for plasma creation in the ECR can be better understood by the use of PROES.

  14. Size Effects in Angle-Resolved Photoelectron Spectroscopy of Free Rare-Gas Clusters

    SciTech Connect

    Rolles, D.; Zhang, H.; Pesic, Z.D.; Bilodeau, R.C.; Wills, A.; Kukk, E.; Rude, B.S.; Ackerman, G.D.; Bozek, J.D.; Muino, R.D.; de Abajo, F.J.G.; Berrah, N.; /Western Michigan U. /LBNL, ALS /Turku U. /SLAC /Basque U., San Sebastian /Madrid, Inst. Optica

    2007-05-23

    The photoionization of free Xe clusters is investigated by angle-resolved time-of-flight photoelectron spectroscopy. The measurements probe the evolution of the photoelectron angular distribution parameter as a function of photon energy and cluster size. While the overall photon-energy-dependent behavior of the photoelectrons from the clusters is very similar to that of the free atoms, distinct differences in the angular distribution point at cluster-size-dependent effects. Multiple scattering calculations trace their origin to elastic photoelectron scattering.

  15. Comparison of organic phantom recipes and characterization by time-resolved diffuse optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Quarto, G.; Pifferi, A.; Bargigia, I.; Farina, A.; Cubeddu, R.; Taroni, P.

    2013-06-01

    Three recipes for tissue constituent-equivalent phantoms of water and lipids are presented. Nature phantoms are made using no emulsifying agent, but just a professional disperser, instead Agar and Triton phantoms are made using agar or Triton X-100, respectively, as agents to emulsify water and lipids. Different water-to-lipid ratios ranging from 30 to 70 percent by mass are proposed and tested. Optical characterization by time-resolved spectroscopy was performed in terms of optical properties, homogeneity, reproducibility and composition retrieval.

  16. A CAMAC system controlled by an IBM AT computer for time-resolved spectroscopy

    SciTech Connect

    Lindquist, L.O.; Moss, C.E.

    1987-08-01

    An IBM AT computer interfaced to a small CAMAC system offers considerable power without the complexity and expense of a large general-purpose system. The authors' system for time-resolved spectroscopy features menu-driven FORTRAN-based software; high-resolution and high-speed 98K channels, 5-..mu..s fixed dead time) ADCs; segmentable histogram memories (24-bit counts) with large memory space for many histogram segments; independently variable separate histogram dwell times; remote control via a CAMAC serial highway; and ground isolation between the data acquisition equipment and control computer by means of fiber optics.

  17. Band structure parameters of metallic diamond from angle-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Guyot, H.; Achatz, P.; Nicolaou, A.; Le Fèvre, P.; Bertran, F.; Taleb-Ibrahimi, A.; Bustarret, E.

    2015-07-01

    The electronic band structure of heavily boron doped diamond was investigated by angle-resolved photoemission spectroscopy on (100)-oriented epilayers. A unique set of Luttinger parameters was deduced from a comparison of the experimental band structure of metallic diamond along the Δ (Γ X ) and Σ (Γ K ) high-symmetry directions of the reciprocal space, with theoretical band structure calculations performed both within the local density approximation and by an analytical k . p approach. In this way, we were able to describe the experimental band structure over a large three-dimensional region of the reciprocal space and to estimate hole effective masses in agreement with previous theoretical and experimental papers.

  18. Nonlinear Raman Techniques in Femtosecond Time Resolved Spectroscopy for the Analysis and Control of Molecular Dynamics

    SciTech Connect

    Materny, Arnulf; Konradi, Jakow; Namboodiri, Vinu; Namboodiri, Mahesh; Scaria, Abraham

    2008-11-14

    The use of four-wave mixing techniques in femtosecond time-resolved spectroscopy has considerable advantages. Due to the many degrees of freedom offered e.g. by coherent anti-Stokes Raman scattering (CARS), the dynamics even of complex systems can be analyzed in detail. Using pulse shaping techniques in combination with a self-learning loop approach, molecular mode excitation can be controlled very efficiently in a multi-photon excitation process. Results obtained from the optimal control of CARS on {beta}-carotene are discussed.

  19. Bogoliubov Angle, Particle-Hole Mixture and Angular Resolved Photoemission Spectroscopy in Superconductors

    SciTech Connect

    Balatsky, A.

    2010-05-04

    Superconducting excitations - Bogoliubov quasiparticles - are the quantum mechanical mixture of negatively charged electron (-e) and positively charged hole (+e). We propose a new observable for Angular Resolved Photoemission Spectroscopy (ARPES) studies that is the manifestation of the particle-hole entanglement of the superconducting quasiparticles. We call this observable a Bogoliubov angle. This angle measures the relative weight of particle and hole amplitude in the superconducting (Bogoliubov) quasiparticle. We show how this quantity can be measured by comparing the ratio of spectral intensities at positive and negative energies.

  20. ULTRAFAST CHEMISTRY: Using Time-Resolved Vibrational Spectroscopy for Interrogation of Structural Dynamics

    NASA Astrophysics Data System (ADS)

    Nibbering, Erik T. J.; Fidder, Henk; Pines, Ehud

    2005-05-01

    Time-resolved infrared (IR) and Raman spectroscopy elucidates molecular structure evolution during ultrafast chemical reactions. Following vibrational marker modes in real time provides direct insight into the structural dynamics, as is evidenced in studies on intramolecular hydrogen transfer, bimolecular proton transfer, electron transfer, hydrogen bonding during solvation dynamics, bond fission in organometallic compounds and heme proteins, cis-trans isomerization in retinal proteins, and transformations in photochromic switch pairs. Femtosecond IR spectroscopy monitors the site-specific interactions in hydrogen bonds. Conversion between excited electronic states can be followed for intramolecular electron transfer by inspection of the fingerprint IR- or Raman-active vibrations in conjunction with quantum chemical calculations. Excess internal vibrational energy, generated either by optical excitation or by internal conversion from the electronic excited state to the ground state, is observable through transient frequency shifts of IR-active vibrations and through nonequilibrium populations as deduced by Raman resonances.

  1. A tunable low-energy photon source for high-resolution angle-resolved photoemission spectroscopy

    SciTech Connect

    Harter, John W.; Monkman, Eric J.; Shai, Daniel E.; Nie Yuefeng; Uchida, Masaki; Burganov, Bulat; Chatterjee, Shouvik; King, Philip D. C.; Shen, Kyle M.

    2012-11-15

    We describe a tunable low-energy photon source consisting of a laser-driven xenon plasma lamp coupled to a Czerny-Turner monochromator. The combined tunability, brightness, and narrow spectral bandwidth make this light source useful in laboratory-based high-resolution photoemission spectroscopy experiments. The source supplies photons with energies up to {approx}7 eV, delivering under typical conditions >10{sup 12} ph/s within a 10 meV spectral bandwidth, which is comparable to helium plasma lamps and many synchrotron beamlines. We first describe the lamp and monochromator system and then characterize its output, with attention to those parameters which are of interest for photoemission experiments. Finally, we present angle-resolved photoemission spectroscopy data using the light source and compare its performance to a conventional helium plasma lamp.

  2. Time-Resolved Vibrational and Electronic Spectroscopy in Shocked Ammonium Perchlorate Single Crystals

    NASA Astrophysics Data System (ADS)

    Gruzdkov, Yuri; Winey, Michael; Feng, Ruqiang

    1997-07-01

    Experimental methods to obtain time-resolved Raman and absorption spectroscopy data on shocked ammonium perchlorate (AP) single crystals were developed. These included: (a) target designs for thin sample shock wave reverberation experiments; (b) techniques to perform Raman measurements with non-transparent flyers; and (c) adaptation of a high-velocity, 20 mm powder gun for optical spectroscopy. Good quality Raman and absorption spectra, with 50 ns resolution, have been obtained for shock compression along the [210] and [001] directions. Results for peak pressures up to 18 GPa and calculated temperatures up to 600 K are presented. Pressure/temperature-induced frequency hardening and broadening of the different AP Raman modes is observed. Evidence for shock-induced chemical decomposition is discussed.

  3. Multiple spatially resolved reflection spectroscopy for in vivo determination of carotenoids in human skin and blood

    NASA Astrophysics Data System (ADS)

    Darvin, Maxim E.; Magnussen, Björn; Lademann, Juergen; Köcher, Wolfgang

    2016-09-01

    Non-invasive measurement of carotenoid antioxidants in human skin is one of the important tasks to investigate the skin physiology in vivo. Resonance Raman spectroscopy and reflection spectroscopy are the most frequently used non-invasive techniques in dermatology and skin physiology. In the present study, an improved method based on multiple spatially resolved reflection spectroscopy (MSRRS) was introduced. The results obtained were compared with those obtained using the ‘gold standard’ resonance Raman spectroscopy method and showed strong correlations for the total carotenoid concentration (R  =  0.83) as well as for lycopene (R  =  0.80). The measurement stability was confirmed to be better than 10% within the total temperature range from 5 °C to  +  30 °C and pressure contact between the skin and the MSRRS sensor from 800 Pa to 18 000 Pa. In addition, blood samples taken from the subjects were analyzed for carotenoid concentrations. The MSRRS sensor was calibrated on the blood carotenoid concentrations resulting in being able to predict with a correlation of R  =  0.79. On the basis of blood carotenoids it could be demonstrated that the MSRRS cutaneous measurements are not influenced by Fitzpatrick skin types I–VI. The MSRRS sensor is commercially available under the brand name biozoom.

  4. The study of many body physics in high temperature superconductors using angle resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Kaminski, Adam

    Angle Resolved Photoemission Spectroscopy (ARPES) is an experimental technique that has greatly contributed to our understanding of the electronic structure of the High Temperature Superconductors (HTSC). Over the last few years, it has provided vital information about the electronic structure, the Fermi Surface, gap anisotropy and it's temperature dependence, and a new phenomena known as the pseudogap. In this thesis we apply Angle Resolved Photoemission Spectroscopy to the study of electronic interactions in High Temperature Superconductors. The experimental portion of this thesis comprises three main areas, (i) participation in the construction of a new undulator beamline at the Synchrotron Radiation Center-Madison, Wisconsin, (ii) construction of a new ARPES system and (iii) collection and analysis of the data. The experimental results include precise determination of the Fermi Surface in BISCO 2212 and 2201, first observation of intrinsic ARPES lineshape at the nodal point of the Fermi Surface in BISCO 2212, detailed quantitative study of many body interactions along the nodal direction in normal and superconductive state, precise doping dependence analysis of the lineshape at the antinode.

  5. Differentiation of microstructures of sugar foams by means of spatially resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Nguyen Do Trong, Nghia; Watte, Rodrigo; Aernouts, Ben; Verhoelst, Eva; Tsuta, Mizuki; Jakubczyk, Ewa; Gondek, Ewa; Verboven, Pieter; Nicolaï, Bart M.; Saeys, Wouter

    2012-04-01

    Food quality is critically determined by its microstructure and composition. These properties could be quantified noninvasively by means of optical properties (absorption and reduced scattering coefficients) of the food samples. In this research, a spatially-resolved spectroscopy setup based on a fiber-optic probe was developed for acquiring spatiallyresolved diffuse reflectance of three sugar foams with different designed microstructures in the range 500 - 1000 nm. A model for light propagation in turbid media based on diffusion approximation for solving the radiative transport equation was employed to derive optical properties (absorption and reduced scattering coefficients) of these foams. The accuracy of this light propagation model was validated on four liquid phantoms with known optical properties. The obtained results indicated that the optical properties estimation was successfully validated on these liquid phantoms. The estimated reduced scattering coefficients μs' of the foams clearly showed the effect of foaming time on their microstructures. The acquired absorption coefficients μa were also in good agreement with the designed ingredients of these sugar foams. The research results clearly support the potential of spatially-resolved spectroscopy for nondestructive food quality inspection and process monitoring in the food industry.

  6. Fluorescence imaging and time-resolved spectroscopy of steroid using confocal synchrotron radiation microscopy

    NASA Astrophysics Data System (ADS)

    Gerritsen, Hans C.; van der Oord, C. J. R.; Levine, Yehudi K.; Munro, Ian H.; Jones, Gareth R.; Shaw, D. A.; Rommerts, Fokko F.

    1994-08-01

    The Confocal Synchrotron Radiation Microscope at Daresbury was used in a study of the transport and distribution of the steroid Coumestrol in single Leydig cells. The broad spectrum of synchrotron radiation in combination with UV compatible microscope optics affords the extension of confocal microscopy from the visible to the UV region down to about 200 nm. Consequently fluorescent molecules with absorption bands in the UV can be imaged. In addition the pulsed nature of the light source allows us to perform time-resolved fluorescence spectroscopy experiments on microscopic volumes. Coumestrol is a naturally fluorescing plant steroid exhibiting estrogenic activity. In physiological environments it has an absorption peak in the UV at 340 nm and it emits around 440 nm. First results indicate that the Coumestrol transport through the cell membrane is diffusion limited. The weak fluorescence observed in the nuclei of the Leydig cells may be due to fluorescence quenching arising from the interaction of the Coumesterol with nuclear components. However, micro-volume time-resolved fluorescence spectroscopy experiments on cell nuclei have revealed the same decay behavior for Coumesterol in both the cytoplasm and nucleus of the cells.

  7. Disentangling Multichannel Photodissociation Dynamics in Acetone by Time-Resolved Photoelectron-Photoion Coincidence Spectroscopy.

    PubMed

    Maierhofer, Paul; Bainschab, Markus; Thaler, Bernhard; Heim, Pascal; Ernst, Wolfgang E; Koch, Markus

    2016-08-18

    For the investigation of photoinduced dynamics in molecules with time-resolved pump-probe photoionization spectroscopy, it is essential to obtain unequivocal information about the fragmentation behavior induced by the laser pulses. We present time-resolved photoelectron-photoion coincidence (PEPICO) experiments to investigate the excited-state dynamics of isolated acetone molecules triggered by two-photon (269 nm) excitation. In the complex situation of different relaxation pathways, we unambiguously identify three distinct pump-probe ionization channels. The high selectivity of PEPICO detection allows us to observe the fragmentation behavior and to follow the time evolution of each channel separately. For channels leading to fragment ions, we quantitatively obtain the fragment-to-parent branching ratio and are able to determine experimentally whether dissociation occurs in the neutral molecule or in the parent ion. These results highlight the importance of coincidence detection for the interpretation of time-resolved photochemical relaxation and dissociation studies if multiple pathways are present. PMID:27459051

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

    NASA Astrophysics Data System (ADS)

    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.

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

    SciTech Connect

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

    2015-01-15

    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.

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

    NASA Technical Reports Server (NTRS)

    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

  11. Quantifying the cerebral metabolic rate of oxygen by combining diffuse correlation spectroscopy and time-resolved near-infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Verdecchia, Kyle; Diop, Mamadou; Lee, Ting-Yim; St. Lawrence, Keith

    2013-02-01

    Preterm infants are highly susceptible to ischemic brain injury; consequently, continuous bedside monitoring to detect ischemia before irreversible damage occurs would improve patient outcome. In addition to monitoring cerebral blood flow (CBF), assessing the cerebral metabolic rate of oxygen (CMRO2) would be beneficial considering that metabolic thresholds can be used to evaluate tissue viability. The purpose of this study was to demonstrate that changes in absolute CMRO2 could be measured by combining diffuse correlation spectroscopy (DCS) with time-resolved near-infrared spectroscopy (TR-NIRS). Absolute CBF was determined using bolus-tracking TR-NIRS to calibrate the DCS measurements. Cerebral venous blood oxygenation (SvO2) was determined by multiwavelength TR-NIRS measurements, the accuracy of which was assessed by directly measuring the oxygenation of sagittal sinus blood. In eight newborn piglets, CMRO2 was manipulated by varying the anesthetics and by injecting sodium cyanide. No significant differences were found between the two sets of SvO2 measurements obtained by TR-NIRS or sagittal sinus blood samples and the corresponding CMRO2 measurements. Bland-Altman analysis showed a mean CMRO2 difference of 0.0268±0.8340 mL O2/100 g/min between the two techniques over a range from 0.3 to 4 mL O2/100 g/min.

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

    PubMed

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

    2014-01-01

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

  13. Rotationally-Resolved Spectroscopy of the Bending Modes of Deuterated Water Dimer

    NASA Astrophysics Data System (ADS)

    Stewart, Jacob T.; McCall, Benjamin J.

    2013-06-01

    High-resolution spectroscopy of small gas-phase water clusters has provided a wealth of information regarding the intermolecular interactions between water molecules. Water dimer is of particular interest because high-resolution spectroscopy can yield detailed information about the water pair potential. While there have been extensive studies of water dimer throughout the microwave and infrared regions of the spectrum, to date there has been no reported high-resolution spectrum of the intramolecular bending modes of water dimer. We have obtained rotationally-resolved spectra of the bending modes of deuterated water dimer (D_2O)_2, which are, to our knowledge, the first reported spectra of the bending modes of water dimer with rotational resolution. Dimers were produced in a supersonic expansion by bubbling Ar or He through D_2O and expanding the mixture through a 150 μm × 12 mm slit. The expansion was then probed using continuous wave cavity ringdown spectroscopy with light generated by a quantum cascade laser (QCL) operating near 8.5 μm. We have assigned the K_a = 1 ← 0 and K_a = 2 ← 1 sub-bands of the bending mode belonging to the hydrogen bond donor and have observed additional transitions which we attribute to the bending mode associated with the hydrogen bond acceptor.

  14. Time-resolved EUV spectroscopy in the early stage of laser ablation of carbon

    NASA Astrophysics Data System (ADS)

    Loiseleur, Pierre; Hansen, Tue N.; Larour, Jean; Lunney, James G.

    2002-09-01

    In the early stages of laser ablation the combination of high density and optical opacity makes it difficult to use visible spectroscopy for plasma diagnosis. However, these problems can be overcome by working at shorter wavelengths in the EUV. We have used time-resolved EUV emission spectroscopy to study the early stages (1-30 ns) of plasma development in the laser ablation of carbon at an irradiance of 5 GW cm -2. The ablation was done using a 6 ns Nd:YAG laser at 1.06 μm. The spectra were recorded using a grazing incidence spectrometer with a 5 ns-gated micro-channel plate (MCP) detector. An ion probe operating in the time-of-flight mode was used to measure the ion velocity distribution of the plasma outflow. In the 10-35 nm region the predominant line emission was due to Li-like carbon. The temporal variation of the electron density and temperature was deduced by fitting the observed spectrum to a synthetic spectrum calculated using the FLY numerical model of the plasma ionisation and excitation. The temperature deduced from spectroscopy was in good agreement with the estimation from the measured ion velocity distribution in the plasma outflow.

  15. Time-resolved spectroscopy of the intrinsic fluorescence of nucleic acid species

    NASA Astrophysics Data System (ADS)

    Daniels, Malcolm; Hart, Lucas P.; Ho, Paul S.; Ballini, Jean-Pierre; Vigny, Paul

    1990-05-01

    Polarization and lifetime studies have shown that the fluorescence from nucleic acid species is complex, both at the individual chromophore level and because of the effect of stacking interactions on the electronic states. Recent work aimed at elucidating some aspects of this behavior by decay analysis and time-resolved spectroscopy is surveyed. Experimental work has been carried out using the ACO synchrotron at LURE, France) with time-correlated single photon counting, or a frequency-doubled N2-pumped dye laser, pulse width 700 ps, with fast-gated (100 ps width) analog detection and signal averaging. Decay curves are treated by global analysis using the Marquardt non-linear least-squares algorithm (synchrotron data) or the SPLMOD program (EMBO), which carries out a non-linear leastsquares minimization using cubic splines, for the laser data. Resolution of the decay data gives a model-based estimate of the number of components and their lifetimes. This information is then used to deconvolute timewindowed spectra (time-delayed spectra) into the time-resolved spectra. It is a particular feature of the combination of delayed photon counting with the continuous wavelength distribution of pulsed synchrotron radiation that excitation spectra correlating with emissions of different lifetimes can be obtained by uninterrupted repetitive scanning over a wide range of exciting wavelengths, in the present work from 230 nm to 354 urn. Such time-delayed excitation spectra can also be deconvoluted into components corresponding to the various time-resolved emission spectra. Examples of these three types of information viz resolved lifetimes, time-resolved emission spectra and their excitation spectra are presented and discussed for the following systems. I. adenosine; 6N, 6N-dimethyladenosine; protonated adenosine; this work shows the role of rotamers in the excited state behavior of this chromophore and demonstrates the forbidden nature of the lowest excited state. II. d(AT); d

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

    NASA Astrophysics Data System (ADS)

    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.

  17. Spatially resolved spectroscopy analysis of the XMM-Newton large program on SN1006

    NASA Astrophysics Data System (ADS)

    Li, Jiang-Tao; Decourchelle, Anne; Miceli, Marco; Vink, Jacco; Bocchino, Fabrizio

    2016-04-01

    We perform analysis of the XMM-Newton large program on SN1006 based on our newly developed methods of spatially resolved spectroscopy analysis. We extract spectra from low and high resolution meshes. The former (3596 meshes) is used to roughly decompose the thermal and non-thermal components and characterize the spatial distributions of different parameters, such as temperature, abundances of different elements, ionization age, and electron density of the thermal component, as well as photon index and cutoff frequency of the non-thermal component. On the other hand, the low resolution meshes (583 meshes) focus on the interior region dominated by the thermal emission and have enough counts to well characterize the Si lines. We fit the spectra from the low resolution meshes with different models, in order to decompose the multiple plasma components at different thermal and ionization states and compare their spatial distributions. In this poster, we will present the initial results of this project.

  18. Dynamics of Molecular Orientation Observed Using Angle Resolved Photoemission Spectroscopy during Deposition of Pentacene on Graphite.

    PubMed

    Park, Sang Han; Kwon, Soonnam

    2016-04-19

    A real-time method to observe both the structural and the electronic configuration of an organic molecule during deposition is reported for the model system of pentacene on graphite. Structural phase transition of the thin films as a function of coverage is monitored by using in situ angle resolved photoemission spectroscopy (ARPES) results to observe the change of the electronic configuration at the same time. A photoemission theory that uses independent atomic center approximations is introduced to identify the molecular orientation from the ARPES technique. This study provides a practical insight into interpreting ARPES data regarding dynamic changes of molecular orientation during initial growth of molecules on a well-defined surface. PMID:26999332

  19. Accessing Phonon Polaritons in Hyperbolic Crystals by Angle-Resolved Photoemission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Tomadin, Andrea; Principi, Alessandro; Song, Justin C. W.; Levitov, Leonid S.; Polini, Marco

    2015-08-01

    Recently studied hyperbolic materials host unique phonon-polariton (PP) modes. The ultrashort wavelengths of these modes, as well as their low damping, hold promise for extreme subdiffraction nanophotonics schemes. Polar hyperbolic materials such as hexagonal boron nitride can be used to realize long-range coupling between PP modes and extraneous charge degrees of freedom. The latter, in turn, can be used to control and probe PP modes. Here we analyze coupling between PP modes and plasmons in an adjacent graphene sheet, which opens the door to accessing PP modes by angle-resolved photoemission spectroscopy (ARPES). A rich structure in the graphene ARPES spectrum due to PP modes is predicted, providing a new probe of PP modes and their coupling to graphene plasmons.

  20. Accessing Phonon Polaritons in Hyperbolic Crystals by Angle-Resolved Photoemission Spectroscopy.

    PubMed

    Tomadin, Andrea; Principi, Alessandro; Song, Justin C W; Levitov, Leonid S; Polini, Marco

    2015-08-21

    Recently studied hyperbolic materials host unique phonon-polariton (PP) modes. The ultrashort wavelengths of these modes, as well as their low damping, hold promise for extreme subdiffraction nanophotonics schemes. Polar hyperbolic materials such as hexagonal boron nitride can be used to realize long-range coupling between PP modes and extraneous charge degrees of freedom. The latter, in turn, can be used to control and probe PP modes. Here we analyze coupling between PP modes and plasmons in an adjacent graphene sheet, which opens the door to accessing PP modes by angle-resolved photoemission spectroscopy (ARPES). A rich structure in the graphene ARPES spectrum due to PP modes is predicted, providing a new probe of PP modes and their coupling to graphene plasmons. PMID:26340206

  1. A brief update of angle-resolved photoemission spectroscopy on a correlated electron system

    SciTech Connect

    Lee, W.S.

    2010-02-24

    In this paper, we briefly summarize the capabilities of state-of-the-art angle-resolved photoemission spectroscopy (ARPES) in the field of experimental condensed matter physics. Due to the advancement of the detector technology and the high flux light sources, ARPES has become a powerful tool to study the low energy excitations of solids, especially those novel quantum materials in which many-body physics are at play. To benchmark today's state-of-the-art ARPES technique, we demonstrate that the precision of today's ARPES has advanced to a regime comparable to the bulk-sensitive de Haas-van Alphen (dHvA) measurements. Finally, as an example of new discoveries driven by the advancement of the ARPES technique, we summarize some of our recent ARPES measurements on underdoped high-T{sub c} superconducting cuprates, which have provided further insight into the complex pseudogap problem.

  2. Angle-resolved spectroscopy study of Ni-based superconductor SrNi2As2

    NASA Astrophysics Data System (ADS)

    Zeng, L.-K.; Richard, P.; van Roekeghem, A.; Yin, J.-X.; Wu, S.-F.; Chen, Z. G.; Wang, N. L.; Biermann, S.; Qian, T.; Ding, H.

    2016-07-01

    We performed an angle-resolved photoemission spectroscopy study of the Ni-based superconductor SrNi2As2 . Electron and hole Fermi surface pockets are observed, but their different shapes and sizes lead to very poor nesting conditions. The experimental electronic band structure of SrNi2As2 is in good agreement with first-principles calculations after a slight renormalization (by a factor 1.1), confirming the picture of Hund's exchange-dominated electronic correlations decreasing with increasing filling of the 3 d shell in the Fe-, Co-, and Ni-based compounds. These findings emphasize the importance of Hund's coupling and 3 d -orbital filling as key tuning parameters of electronic correlations in transition-metal pnictides.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  4. Quantized Electron Accumulation States in Indium Nitride Studied by Angle-Resolved Photoemission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Colakerol, Leyla; Veal, T. D.; Jeong, Hae-Kyung; Plucinski, Lukasz; Demasi, Alex; Learmonth, Timothy; Glans, Per-Anders; Wang, Shancai; Zhang, Yufeng; Piper, L. F. J.; Jefferson, P. H.; Fedorov, Alexei; Chen, Tai-Chou; Moustakas, T. D.; McConville, C. F.; Smith, Kevin E.

    2006-12-01

    Electron accumulation states in InN have been measured using high resolution angle-resolved photoemission spectroscopy (ARPES). The electrons in the accumulation layer have been discovered to reside in quantum well states. ARPES was also used to measure the Fermi surface of these quantum well states, as well as their constant binding energy contours below the Fermi level EF. The energy of the Fermi level and the size of the Fermi surface for these quantum well states could be controlled by varying the method of surface preparation. This is the first unambiguous observation that electrons in the InN accumulation layer are quantized and the first time the Fermi surface associated with such states has been measured.

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

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

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

    NASA Astrophysics Data System (ADS)

    Kuramochi, Hikaru; Takeuchi, Satoshi; Tahara, Tahei

    2016-04-01

    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-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.

  7. Raman spectroscopy and time-resolved photoluminescence of BN and BxCyNz nanotubes

    SciTech Connect

    Wu, J.; Han, Wei-Qiang; Walukiewicz, W.; Ager III, J.W.; Shan, W.; Haller,E.E.; Zettl, A.

    2004-01-21

    We report Raman and time-resolved photoluminescence spectroscopic studies of multiwalled BN and B{sub x}C{sub y}N{sub z} nanotubes. The Raman spectroscopy shows that the as-grown B{sub x}C{sub y}N{sub z} charge recombination, respectively. Comparison of the photoluminescence of BN nanotubes to that decay process is characterized by two time constants that are attributed to intra- and inter-BN sheet nanotubes as predicted by theory. nanotubes are radially phase separated into BN shells and carbon shells. The photoluminescence of hexagonal BN is consistent with the existence of a spatially indirect band gap in multi-walled BN.

  8. The Fossil Record of Black Hole Seeds, with Spatially Resolved Spectroscopy

    NASA Astrophysics Data System (ADS)

    Trump, Jonathan R.; CANDELS, 3D-HST

    2016-01-01

    I will present the first robust measurement of black hole occupation over a wide range of host galaxy mass (8resolved spectroscopy, which reliably distinguishes a nuclear AGN from extended star formation and largely avoids the star-formation dilution bias plaguing traditional low-mass AGN selection. The observations suggest bimodal seed formation: while many low-mass galaxies host massive black holes, their black hole occupation is ~10% that of massive galaxies. The measured black hole occupation qualitatively agrees with theoretical models of black hole formation, with massive direct-collapse seeds forming only in massive halos and black hole formation confined to lower-mass Pop III remnants in small halos.

  9. Substrate interactions with suspended and supported monolayer MoS2: Angle-resolved photoemission spectroscopy

    DOE PAGESBeta

    Jin, Wencan; Yeh, Po -Chun; Zaki, Nader; Zhang, Datong; Liou, Jonathan T.; Dadap, Jerry I.; Barinov, Alexey; Yablonskikh, Mikhail; Sadowski, Jerzy T.; Sutter, Peter; et al

    2015-03-17

    We report the directly measured electronic structure of exfoliated monolayer molybdenum disulfide (MoS₂) using micrometer-scale angle-resolved photoemission spectroscopy. Measurements of both suspended and supported monolayer MoS₂ elucidate the effects of interaction with a substrate. Thus, a suggested relaxation of the in-plane lattice constant is found for both suspended and supported monolayer MoS₂ crystals. For suspended MoS₂, a careful investigation of the measured uppermost valence band gives an effective mass at Γ¯ and Κ¯ of 2.00m₀ and 0.43m₀, respectively. We also measure an increase in the band linewidth from the midpoint of Γ¯Κ¯ to the vicinity of Κ¯ and briefly discussmore » its possible origin.« less

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

    SciTech Connect

    Sheps, Leonid; Chandler, David W.

    2013-04-01

    Experimental measurements of elementary reaction rate coefficients and product branching ratios are essential to our understanding of many fundamentally important processes in Combustion Chemistry. However, such measurements are often impossible because of a lack of adequate detection techniques. Some of the largest gaps in our knowledge concern some of the most important radical species, because their short lifetimes and low steady-state concentrations make them particularly difficult to detect. To address this challenge, we propose a novel general detection method for gas-phase chemical kinetics: time-resolved broadband cavity-enhanced absorption spectroscopy (TR-BB-CEAS). This all-optical, non-intrusive, multiplexed method enables sensitive direct probing of transient reaction intermediates in a simple, inexpensive, and robust experimental package.

  11. Preparation of layered thin film samples for angle-resolved photoemission spectroscopy

    SciTech Connect

    Harrison, S. E.; Zhou, B.; Huo, Y.; Harris, J. S.; Pushp, A.; Kellock, A. J.; Parkin, S. S. P.; Chen, Y.; Hesjedal, T.

    2014-09-22

    Materials with layered van der Waals crystal structures are exciting research topics in condensed matter physics and materials science due to outstanding physical properties associated with their strong two dimensional nature. Prominent examples include bismuth tritelluride and triselenide topological insulators (TIs), which are characterized by a bulk bandgap and pairwise counter-propagating spin-polarized electronic surface states. Angle-resolved photoemission spectroscopy (ARPES) of ex-situ grown thin film samples has been limited by the lack of suitable surface preparation techniques. We demonstrate the shortcomings of previously successful conventional surface preparation techniques when applied to ternary TI systems which are susceptible to severe oxidation. We show that in-situ cleaving is a simple and effective technique for preparation of clean surfaces on ex-situ grown thin films for high quality ARPES measurements. The method presented here is universally applicable to other layered van der Waals systems as well.

  12. Pulsation-resolved deep tissue dynamics measured with diffusing-wave spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Jun; Jaillon, Franck; Dietsche, Gregor; Maret, Georg; Gisler, Thomas

    2006-08-01

    We present a technique for measuring transient microscopic dynamics within deep tissue with sub-second temporal resolution, using diffusing-wave spectroscopy with gated single-photon avalanche photodiodes (APDs) combined with standard ungated multi-tau correlators. Using the temporal autocorrelation function of a reference signal allows to correct the temporal intensity autocorrelation function of the sample signal for the distortions induced by the non-constant average photon count rate. We apply this technique to pulsation-synchronized measurements of tissue dynamics in humans. Measurements on the forearm show no dependence on the pulsation phase. In contrast, the decay rate of the DWS signal measured on the wrist over the radial artery shows a pulsation-induced modulation of 60-90% consistent with pulsatile variations of arterial erythrocyte flow velocity. This might make time-resolved DWS interesting as a sensitive and fast method for investigating deep tissue perfusion, e.g. in intensive care.

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

    NASA Astrophysics Data System (ADS)

    Kashyap, V.

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

  14. A high-order harmonic generation apparatus for time- and angle-resolved photoelectron spectroscopy

    SciTech Connect

    Frietsch, B.; Gahl, C.; Teichmann, M.; Weinelt, M.; Carley, R.; Döbrich, K.; Schwarzkopf, O.; Wernet, Ph.

    2013-07-15

    We present a table top setup for time- and angle-resolved photoelectron spectroscopy to investigate band structure dynamics of correlated materials driven far from equilibrium by femtosecond laser pulse excitation. With the electron-phonon equilibration time being in the order of 1–2 ps it is necessary to achieve sub-picosecond time resolution. Few techniques provide both the necessary time and energy resolution to map non-equilibrium states of the band structure. Laser-driven high-order harmonic generation is such a technique. In our experiment, a grating monochromator delivers tunable photon energies up to 40 eV. A photon energy bandwidth of 150 meV and a pulse duration of 100 fs FWHM allow us to cover the k-space necessary to map valence bands at different k{sub z} and detect outer core states.

  15. Angularly resolved X-ray photoelectron spectroscopy investigation of PTFE after prolonged space exposure

    NASA Technical Reports Server (NTRS)

    Dalins, I.; Karimi, M.

    1992-01-01

    Monochromatized angularly resolved X-ray photoelectron spectroscopy (ARXPS) was used to study PTFE (Teflon) that had been exposed to an earth orbital environment for approximately six years. The primary interest of the research is on a very reactive component of this environment (atomic oxygen) which, because of the typical orbital velocities of a spacecraft, impinge on exposed surfaces with 5 eV energy. This presentation deals with the method of analysis, the findings as they pertain to a rather complex carbon, oxygen, and fluorine XPS peak analysis, and the character of the valence bands. An improved bias referencing method, based on ARXPS, is also demonstrated for evaluating specimen charging effects. It was found that the polymer molecule tends to resist the atomic oxygen attack by reorienting itself, so that the most electronegative CF3 groups are facing the incoming hyperthermal oxygen atoms. The implications of these findings to ground-based laboratory studies are discussed.

  16. Muscle oxygenation during exercise under hypoxic conditions assessed by spatially resolved broadband NIR spectroscopy

    NASA Astrophysics Data System (ADS)

    Geraskin, Dmitri; Platen, Petra; Franke, Julia; Andre, Christiane; Bloch, Wilhelm; Kohl-Bareis, Matthias

    2005-08-01

    Near-infrared spectroscopy (NIRS) is used for the non-invasive measurement of muscle oxygenation during an incremental cycle test in healthy volunteers. A broad band spatially resolved system is used that allows the reliability of current algorithms to be inspected with the main emphasis on tissue oxygen saturation (SO2) and oxygenated and deoxygenated haemoglobin concentrations. Physiological conditions were modulated by changing oxygen supply from normal (21 % O2 in inspired air) to conditions corresponding to 2000 and 4000 m altitude above sea level (15.4 and 11.9 % O2). Under these hypoxic conditions the decrease in SO2 with increased exercise power is highly correlated with the oxygen content of the inspired air. There is a clear correlation with physiological parameters (heart rate, pulse oxymetry, blood gas, lactate, spirometric data). Skin oxygenation parameters are compared to those of muscle.

  17. Revealing the photophysics of gold-nanobeacons via time-resolved fluorescence spectroscopy.

    PubMed

    Wei, Guoke; Simionesie, Dorin; Sefcik, Jan; Sutter, Jens U; Xue, Qingjiang; Yu, Jun; Wang, Jinliang; Birch, David J S; Chen, Yu

    2015-12-15

    We demonstrate that time-resolved fluorescence spectroscopy is a powerful tool to investigate the conformation states of hairpin DNA on the surface of gold nanoparticles (AuNPs) and energy transfer processes in Au-nanobeacons. Long-range fluorescence quenching of Cy5 by AuNPs has been found to be in good agreement with electrodynamics modeling. Moreover, time-correlated single-photon counting (TCSPC) is shown to be promising for real-time monitoring of the hybridization kinetics of Au-nanobeacons, with up to 60% increase in decay time component and 300% increase in component fluorescence fraction observed. Our results also indicate the importance of the stem and spacer designs for the performance of Au-nanobeacons. PMID:26670500

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

    NASA Astrophysics Data System (ADS)

    Beauvoit, Bertrand; Kitai, Toshiyuki; Liu, Hanli; Chance, Britton

    1995-01-01

    In this study, the detailed dependence of the light scattering on the tissue architecture and intracellular composition was investigated. The reduced scattering coefficient ((mu) s') of isolated rat liver mitochondria, isolated liver cells and various rat tissues was measured at 780 nm by using time-resolved spectroscopy and a sample-substitution protocol. In a first part, extrapolations of the in vitro data to the in vivo situation showed that the mitochondrial compartment contributes for 73% of the scattering of the hepatocytes and about 100% of that of the whole liver. Finally, by analyzing different normal rat tissues and tumors, we have shown that the tissue (mu) s' is independent on the cell concentration in the tissue but is roughly proportional to the tissue mitochondrial content.

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

    PubMed Central

    Chai, Changhoon; Takhistov, Paul

    2010-01-01

    The real-time detection of trace concentrations of biological toxins requires significant improvement of the detection methods from those reported in the literature. To develop a highly sensitive and selective detection device it is necessary to determine the optimal measuring conditions for the electrochemical sensor in three domains: time, frequency and polarization potential. In this work we utilized a time-resolved electrochemical impedance spectroscopy for the detection of trace concentrations of Staphylococcus enterotoxin B (SEB). An anti-SEB antibody has been attached to the nano-porous aluminum surface using 3-aminopropyltriethoxysilane/glutaraldehyde coupling system. This immobilization method allows fabrication of a highly reproducible and stable sensing device. Using developed immobilization procedure and optimized detection regime, it is possible to determine the presence of SEB at the levels as low as 10 pg/mL in 15 minutes. PMID:22315560

  20. Field-resolved measurement of reaction-induced spectral densities by polarizability response spectroscopy

    NASA Astrophysics Data System (ADS)

    Moran, Andrew M.; Nome, Rene A.; Scherer, Norbert F.

    2007-11-01

    The experimental design and theoretical description of a novel five-pulse laser spectroscopy is presented with an application to a pyridinium charge transfer complex in acetonitrile and methanol. In field-resolved polarizability response spectroscopy (PORS), an electronically resonant laser pulse first excites a solvated chromophore (reactant) and off-resonant Raman spectra of the resulting nuclear motions are measured as a function of the reaction time. The present apparatus differs from our earlier design by performing the Raman probe measurement (with fixed pulse delays) in the frequency domain. In addition, the full electric fields of the signals are measured by spectral interferometry to separate nonresonant and Raman responses. Our theoretical model shows how the PORS signal arises from nuclear motions that are displaced/driven by the photoinduced reaction. The field-resolved off-resonant (of the solute's electronic transitions) probing favors detection of solvent (as opposed to solute) dynamics coupled to the reaction. The sign of the signal represents the relative strengths of polarization responses associated with the ground and photoexcited solutions. Signatures of nonresonant and PORS signal contributions to the experimental results are analyzed with numerical calculations based on a theoretical model we have developed for reaction-induced PORS. Our model identifies two mechanisms of PORS signal generation: (i) structural relaxation induced resonance; (ii) dephasing induced resonance. In the charge transfer reaction investigated, the solvent-dependent and time-evolving (solvent) polarizability spectral density (PSD) is readily obtained. The general trend of an initial broadband inertial nuclear response followed by a decrease in the linewidth of the PSD establishes that the measured PSD is inconsistent with the approximation of a linear response. Furthermore, the explicit time evolution of the PSD is important for properly describing solvent control of

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

    SciTech Connect

    Yankelevich, Diego R.; Ma, Dinglong; Liu, Jing; Sun, Yang; Sun, Yinghua; Bec, Julien; Marcu, Laura; Elson, Daniel S.

    2014-03-15

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

  2. Field-resolved measurement of reaction-induced spectral densities by polarizability response spectroscopy

    SciTech Connect

    Moran, Andrew M.; Nome, Rene A.; Scherer, Norbert F.

    2007-11-14

    The experimental design and theoretical description of a novel five-pulse laser spectroscopy is presented with an application to a pyridinium charge transfer complex in acetonitrile and methanol. In field-resolved polarizability response spectroscopy (PORS), an electronically resonant laser pulse first excites a solvated chromophore (reactant) and off-resonant Raman spectra of the resulting nuclear motions are measured as a function of the reaction time. The present apparatus differs from our earlier design by performing the Raman probe measurement (with fixed pulse delays) in the frequency domain. In addition, the full electric fields of the signals are measured by spectral interferometry to separate nonresonant and Raman responses. Our theoretical model shows how the PORS signal arises from nuclear motions that are displaced/driven by the photoinduced reaction. The field-resolved off-resonant (of the solute's electronic transitions) probing favors detection of solvent (as opposed to solute) dynamics coupled to the reaction. The sign of the signal represents the relative strengths of polarization responses associated with the ground and photoexcited solutions. Signatures of nonresonant and PORS signal contributions to the experimental results are analyzed with numerical calculations based on a theoretical model we have developed for reaction-induced PORS. Our model identifies two mechanisms of PORS signal generation: (i) structural relaxation induced resonance; (ii) dephasing induced resonance. In the charge transfer reaction investigated, the solvent-dependent and time-evolving (solvent) polarizability spectral density (PSD) is readily obtained. The general trend of an initial broadband inertial nuclear response followed by a decrease in the linewidth of the PSD establishes that the measured PSD is inconsistent with the approximation of a linear response. Furthermore, the explicit time evolution of the PSD is important for properly describing solvent control of

  3. Use of time-resolved fluorescence spectroscopy to evaluate diagnostic value of collagen degradation products.

    PubMed

    Sikora, Joanna; Cyrankiewicz, Michał; Wybranowski, Tomasz; Ziomkowska, Blanka; Ośmiałowski, Borys; Obońska, Ewa; Augustyńska, Beata; Kruszewski, Stefan; Kubica, Jacek

    2015-05-01

    The concentration of collagen degradation products (CDPs) may reflect the process of left ventricular remodeling (LVR). The aim of this study was to evaluate the potential diagnostic usefulness of time-resolved fluorescence spectroscopy (TRFS) in assessment of CDPs. The preliminary experiment was designed to establish if CDPs’ characteristics might be visible by mean fluorescence lifetime (FLT) in determined conditions. The in vitro model of CDPs was prepared by conducting the hydrolysis of type III collagen. The FLT of samples was measured by the time-resolved spectrometer Life Spec II with the subnanosecond pulsed 360-nm EPLED diode. The FLTs were obtained by deconvolution analysis of the data using a multiexponential model of fluorescence decay. In order to determine the limit of traceability of CDPs, a comparison of different collagen/plasma ratio in samples was performed. The results of our study showed that the increase of added plasma to hydrolyzed collagen extended the mean FLT. Thus, the diagnosis of LVR based on measurements using TRFS is possible. However, it is important to point out the experiment was preliminary and further investigation in this field of research is crucial. PMID:25764396

  4. Distinction of brain tissue, low grade and high grade glioma with time-resolved fluorescence spectroscopy.

    PubMed

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

    2006-01-01

    Neuropathology frozen section diagnoses are difficult in part because of the small tissue samples and the paucity of adjunctive rapid intraoperative stains. This study aims to explore the use of time-resolved laser-induced fluorescence spectroscopy as a rapid adjunctive tool for the diagnosis of glioma specimens and for distinction of glioma from normal tissues intraoperatively. Ten low grade gliomas, 15 high grade gliomas without necrosis, 6 high grade gliomas with necrosis and/or radiation effect, and 14 histologically uninvolved "normal" brain specimens are spectroscopicaly analyzed and contrasted. Tissue autofluorescence was induced with a pulsed Nitrogen laser (337 nm, 1.2 ns) and the transient intensity decay profiles were recorded in the 370-500 nm spectral range with a fast digitized (0.2 ns time resolution). Spectral intensities and time-dependent parameters derived from the time-resolved spectra of each site were used for tissue characterization. A linear discriminant analysis diagnostic algorithm was used for tissue classification. Both low and high grade gliomas can be distinguished from histologically uninvolved cerebral cortex and white matter with high accuracy (above 90%). In addition, the presence or absence of treatment effect and/or necrosis can be identified in high grade gliomas. Taking advantage of tissue autofluorescence, this technique facilitates a direct and rapid investigation of surgically obtained tissue. PMID:16368511

  5. Phase-resolved spectroscopy of Type B quasi-periodic oscillations in GX 339-4

    NASA Astrophysics Data System (ADS)

    Stevens, Abigail L.; Uttley, Phil

    2016-08-01

    We present a new spectral-timing technique for phase-resolved spectroscopy and apply it to the low-frequency Type B quasi-periodic oscillation (QPO) from the black hole X-ray binary GX 339-4. We show that on the QPO time-scale the spectrum changes not only in normalization, but also in spectral shape. Using several different spectral models which parametrize the blackbody and power-law components seen in the time-averaged spectrum, we find that both components are required to vary, although the fractional rms amplitude of blackbody emission is small, ˜1.4 per cent compared to ˜25 per cent for the power-law emission. However, the blackbody variation leads the power-law variation by ˜0.3 in relative phase (˜110°), giving a significant break in the Fourier lag-energy spectrum that our phase-resolved spectral models are able to reproduce. Our results support a geometric interpretation for the QPO variations where the blackbody variation and its phase relation to the power-law are explained by quasi-periodic heating of the approaching and receding sides of the disc by a precessing Comptonizing region. The small amplitude of blackbody variations suggests that the Comptonizing region producing the QPO has a relatively large scaleheight, and may be linked to the base of the jet, as has previously been suggested to explain the binary orbit inclination-dependence of Type B QPO amplitudes.

  6. Phase-Resolved Spectroscopy of Type B Quasi-Periodic Oscillations in GX 339-4

    NASA Astrophysics Data System (ADS)

    Stevens, Abigail L.; Uttley, Phil

    2016-05-01

    We present a new spectral-timing technique for phase-resolved spectroscopy and apply it to the low-frequency Type B quasi-periodic oscillation (QPO) from the black hole X-ray binary GX 339-4. We show that on the QPO time-scale the spectrum changes not only in normalisation, but also in spectral shape. Using several different spectral models which parameterise the blackbody and power-law components seen in the time-averaged spectrum, we find that both components are required to vary, although the fractional rms amplitude of blackbody emission is small, ˜ 1.4 per cent compared to ˜ 25 per cent for the power-law emission. However the blackbody variation leads the power-law variation by ˜ 0.3 in relative phase (˜ 110 degrees), giving a significant break in the Fourier lag-energy spectrum that our phase-resolved spectral models are able to reproduce. Our results support a geometric interpretation for the QPO variations where the blackbody variation and its phase relation to the power-law are explained by quasi-periodic heating of the approaching and receding sides of the disk by a precessing Comptonising region. The small amplitude of blackbody variations suggests that the Comptonising region producing the QPO has a relatively large scale-height, and may be linked to the base of the jet, as has previously been suggested to explain the binary orbit inclination-dependence of Type B QPO amplitudes.

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

    NASA Astrophysics Data System (ADS)

    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.

  8. Modelling Time-Resolved Two-Dimensional Electronic Spectroscopy of the Primary Photoisomerization Event in Rhodopsin

    PubMed Central

    2015-01-01

    Time-resolved two-dimensional (2D) electronic spectra (ES) tracking the evolution of the excited state manifolds of the retinal chromophore have been simulated along the photoisomerization pathway in bovine rhodopsin, using a state-of-the-art hybrid QM/MM approach based on multiconfigurational methods. Simulations of broadband 2D spectra provide a useful picture of the overall detectable 2D signals from the near-infrared (NIR) to the near-ultraviolet (UV). Evolution of the stimulated emission (SE) and excited state absorption (ESA) 2D signals indicates that the S1 → SN (with N ≥ 2) ESAs feature a substantial blue-shift only after bond inversion and partial rotation along the cis → trans isomerization angle, while the SE rapidly red-shifts during the photoinduced skeletal relaxation of the polyene chain. Different combinations of pulse frequencies are proposed in order to follow the evolution of specific ESA signals. These include a two-color 2DVis/NIR setup especially suited for tracking the evolution of the S1 → S2 transitions that can be used to discriminate between different photochemical mechanisms of retinal photoisomerization as a function of the environment. The reported results are consistent with the available time-resolved pump–probe experimental data, and may be used for the design of more elaborate transient 2D electronic spectroscopy techniques. PMID:24794143

  9. Angle resolved photoemission spectroscopy study on the non-saturate magnetoresistance material WTe2

    NASA Astrophysics Data System (ADS)

    Jiang, Juan; Niu, Xiaohai; Xie, Binping; Zhang, Tong; Feng, Donglai

    2015-03-01

    By performing high resolution angle-resolved photoemission spectroscopy, we obtain the detailed electronic structure of WTe2, which has an extremely large non-saturated magnetoresistance. Unlike the simple one electron and one hole pocket as expected, we resolved a rather complicated Fermi surface in WTe2. There is a hole pocket around the Brillouin zone center Γ, two hole pockets and two electron pockets along the tungsten chain direction. Thus the large magnetoresistance cannot be simply attributed to the electron-hole compensation, since this is based on a two carrier assumption model, the real case in WTe2 should be more complicated. Surprisingly, the circular dichroism ARPES result shows a strong intensity inversion between the data under the right-circular polarized light and the left-circular polarized light. This, indicates a proper different orbital angular momentum along the tungsten chain direction, which might also related to the different spin angular momentum since there're coupled with each other. Therefore, we propose that to fully understand the large magnetoresistance in WTe2, spin channel should also be involved where backscattering are forbidden under zero field.

  10. Phase-resolved spectroscopy of Type B quasi-periodic oscillations in GX 339-4

    NASA Astrophysics Data System (ADS)

    Stevens, Abigail L.; Uttley, Phil

    2016-08-01

    We present a new spectral-timing technique for phase-resolved spectroscopy and apply it to the low-frequency Type B quasi-periodic oscillation (QPO) from the black hole X-ray binary GX 339-4. We show that on the QPO time-scale the spectrum changes not only in normalisation, but also in spectral shape. Using several different spectral models which parameterise the blackbody and power-law components seen in the time-averaged spectrum, we find that both components are required to vary, although the fractional rms amplitude of blackbody emission is small, ~1.4 per cent compared to ~25 per cent for the power-law emission. However the blackbody variation leads the power-law variation by ~0.3 in relative phase (~110 degrees), giving a significant break in the Fourier lag-energy spectrum that our phase-resolved spectral models are able to reproduce. Our results support a geometric interpretation for the QPO variations where the blackbody variation and its phase relation to the power-law are explained by quasi-periodic heating of the approaching and receding sides of the disc by a precessing Comptonising region. The small amplitude of blackbody variations suggests that the Comptonising region producing the QPO has a relatively large scale-height, and may be linked to the base of the jet, as has previously been suggested to explain the binary orbit inclination-dependence of Type B QPO amplitudes.

  11. Simple photomultiplier tube internal-gating method for use in subnanosecond time-resolved spectroscopy.

    PubMed

    Iwata, Tetsuo; Takasu, Tsuyoshi; Araki, Tsutomu

    2003-09-01

    We propose a simple photomultiplier tube (PMT) internal-gating method for use in the field of subnanosecond time-resolved spectroscopy. In the proposed method, we control two dynodes in the PMT by applying a gate signal whose pulse width is Tg. When controlling the mth and the n(> m)th dynodes, a resolution time delta t is approximately given by delta t = Tg-(n-m) tau, where tau is a transit time of a lump of secondary electrons traveling between the two dynodes in the PMT. In principle, the resolution time delta t shorter than the pulse width Tg of the gate signal can be easily obtained. From a fundamental performance test, we found that a subnanosecond resolution time delta t = 0.31 ns was obtained for the case of m = 2 and n = 5. To demonstrate the effectiveness of the proposed method, we carried out a time-resolved spectroscopic measurement of emission obtained from a white-light-emitting diode (LED) driven by a nanosecond current pulse. PMID:14611045

  12. Time-resolved Fourier transform infrared spectroscopy: Application to pulsed discharges

    NASA Astrophysics Data System (ADS)

    Kawaguchi, Kentarou; Hama, Yoichi; Nishida, Shigeki

    2005-07-01

    Time-resolved Fourier transform spectroscopy (TR-FTS) is reviewed, with emphasis on synchronous FTS using continuously scanning interferometers. By using a high-resolution Bruker IFS 120 HR, a TR-FTS method has been developed with the help of a microcontroller SX, where a maximum of 64 time-resolved data are recorded with a preset time interval in a single scan of the interferometer. The time resolution is 1 μs, limited by the response time of the detector system used. This method has been applied to a pulsed discharge in an Ar and H 2 mixture to observe time profiles of ArH + and ArH emission spectra. Electronic transitions of He 2 have been observed in the infrared region with this method, and from the time profiles, He 2 in Rydberg states with higher energy than the b3Π state is found to be produced efficiently in afterglow plasma. Fifteen bands in the 2300-8000 cm -1 region have been assigned by using previously reported data from the optical region. A new band from the 5 f state has been assigned for the first time through the 5 f-4 d band in the 2600 cm -1 region.

  13. Quantitatively Resolving Ligand–Receptor Bonds on Cell Surfaces Using Force-Induced Remnant Magnetization Spectroscopy

    PubMed Central

    2016-01-01

    Molecule-specific noncovalent bonding on cell surfaces is the foundation for cellular recognition and functioning. A major challenge in probing these bonds is to resolve the specific bonds quantitatively and efficiently from the nonspecific interactions in a complex environment. Using force-induced remnant magnetization spectroscopy (FIRMS), we were able to resolve quantitatively three different interactions for magnetic beads bearing anti-CD4 antibodies with CD4+ T cell surfaces based upon their binding forces. The binding force of the CD4 antibody–antigen bonds was determined to be 75 ± 3 pN. For comparison, the same bonds were also studied on a functionalized substrate surface, and the binding force was determined to be 90 ± 6 pN. The 15 pN difference revealed by high-resolution FIRMS illustrates the significant impact of the bonding environment. Because the force difference was unaffected by the cell number or the receptor density on the substrate, we attributed it to the possible conformational or local environmental differences of the CD4 antigens between the cell surface and substrate surface. Our results show that the high force resolution and detection efficiency afforded by FIRMS are valuable for studying protein–protein interactions on cell surfaces. PMID:27163031

  14. Probing Kinetic Mechanisms of Protein Function and Folding with Time-Resolved Natural and Magnetic Chiroptical Spectroscopies

    PubMed Central

    Kliger, David S.; Chen, Eefei; Goldbeck, Robert A.

    2012-01-01

    Recent and ongoing developments in time-resolved spectroscopy have made it possible to monitor circular dichroism, magnetic circular dichroism, optical rotatory dispersion, and magnetic optical rotatory dispersion with nanosecond time resolution. These techniques have been applied to determine structural changes associated with the function of several proteins as well as to determine the nature of early events in protein folding. These studies have required new approaches in triggering protein reactions as well as the development of time-resolved techniques for polarization spectroscopies with sufficient time resolution and sensitivity to probe protein structural changes. PMID:22312279

  15. Scanning Tunneling Microscopy and Spectroscopy: I. Semimetals and Semiconductors. I. Atom-Resolved Imaging of DNA.

    NASA Astrophysics Data System (ADS)

    Driscoll, Robert James

    1993-01-01

    The topographic and electronic structure of semimetal and semiconductor surfaces were investigated using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS), respectively. The long-range morphology and atomic -scale characteristics of cleaved materials, including highly oriented pyrolitic graphite (HOPG), boronated pyrolitic graphite (BPG), titanium disulfide, and gallium arsenide (GaAs), were revealed by STM performed in ultrahigh vacuum (UHV). Atom-resolved constant current topographs and current -imaging data, as well as barrier height information, are presented. Both point and line defects were observed on these surfaces. Visual evidence of coulombic screening caused by adsorption of charged species on n-GaAs(110) is provided. On BPG samples, containing up to 0.5% boron, boron substituent atoms appeared as protrusions approximately 3 A in diameter, with a density consistent with the known concentration. The BPG surface contained numerous line defects, including large-angle grain boundaries, and monolayer -deep etch pits. The effects of stress on the morphology of an annealed vicinal Si(111) wafer were explored. The height and orientation of step bunches, as well as terrace widths, on the (7 x 7) surface were determined. Line fault defects at step kinks were observed; theories for the origin and structure of these features based on stress relief are proposed. Current imaging tunneling spectroscopy (CITS) revealed differences between the adatom sites of the (7 x 7) surface. Atom-resolved barrier height images were also obtained. The measured barrier height was seen to depend strongly on the "cleanliness" of the STM tip. In addition, atom-resolved STM images of duplex DNA supported on a HOPG surface were obtained in UHV. These images revealed double-helical structure, major and minor groove alternation, base pairs, and atomic-scale substructure. The DNA dimensions derived from the STM data were in agreement with dimensions from x

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

    PubMed Central

    Chergui, Majed

    2016-01-01

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

  17. Time-resolved reflectance spectroscopy for nondestructive assessment of fruit and vegetable quality

    NASA Astrophysics Data System (ADS)

    Torricelli, Alessandro; Spinelli, Lorenzo; Vanoli, Maristella; Rizzolo, Anna; Eccher Zerbini, Paola

    2007-09-01

    In the majority of food and feed, due to the microscopic spatial changes in the refractive index, visible (VIS) and near infrared (NIR) light undergoes multiple scattering events and the overall light distribution is determined more by scattering rather than absorption. Conventional steady state VIS/NIR reflectance spectroscopy can provide information on light attenuation, which depends both on light absorption and light scattering, but cannot discriminate these two effects. On the contrary, time-resolved reflectance spectroscopy (TRS) provides a complete optical characterisation of diffusive media in terms of their absorption coefficient and reduced scattering coefficient. From the assessment of the absorption and reduced scattering coefficients, information can then be derived on the composition and internal structure of the medium. Main advantages of the technique are the absolute non-invasiveness, the potentiality for non-contact measurements, and the capacity to probe internal properties with no influence from the skin. In this work we review the physical and technical issues related to the use of TRS for nondestructive quality assessment of fruit and vegetable. A laboratory system for broadband TRS, based on tunable mode-locked lasers and fast microchannel plate photomultiplier, and a portable setup for TRS measurements, based on pulsed diode lasers and compact metal-channel photomultiplier, will be described. Results on broadband optical characterisation of fruits and applications of TRS to the detection of internal defects in pears and to maturity assessment in nectarines will be presented.

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

    SciTech Connect

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

    2008-06-04

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

  19. Energy resolved electrochemical impedance spectroscopy for electronic structure mapping in organic semiconductors

    SciTech Connect

    Nádaždy, V. Gmucová, K.; Schauer, F.

    2014-10-06

    We introduce an energy resolved electrochemical impedance spectroscopy method to map the electronic density of states (DOS) in organic semiconductor materials. The method consists in measurement of the charge transfer resistance of a semiconductor/electrolyte interface at a frequency where the redox reactions determine the real component of the impedance. The charge transfer resistance value provides direct information about the electronic DOS at the energy given by the electrochemical potential of the electrolyte, which can be adjusted using an external voltage. A simple theory for experimental data evaluation is proposed, along with an explanation of the corresponding experimental conditions. The method allows mapping over unprecedentedly wide energy and DOS ranges. Also, important DOS parameters can be determined directly from the raw experimental data without the lengthy analysis required in other techniques. The potential of the proposed method is illustrated by tracing weak bond defect states induced by ultraviolet treatment above the highest occupied molecular orbital in a prototypical σ-conjugated polymer, poly[methyl(phenyl)silylene]. The results agree well with those of our previous DOS reconstruction by post-transient space-charge-limited-current spectroscopy, which was, however, limited to a narrow energy range. In addition, good agreement of the DOS values measured on two common π-conjugated organic polymer semiconductors, polyphenylene vinylene and poly(3-hexylthiophene), with the rather rare previously published data demonstrate the accuracy of the proposed method.

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

    PubMed

    Chergui, Majed

    2016-05-01

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

  1. Dirac Fermions in graphene and graphite---a view from angle-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhou, Shuyun

    The research in graphene has exploded in the past few years, due to its intriguing physics as an emerging paradigm for relativistic condensed matter physics as well as its great promise for application in next generation electronics. Understanding the low energy electronic structure of graphene is fundamental as most of the intriguing properties of graphene arise from its peculiar electronic dispersion, which resembles that of relativistic Dirac Fermions. This thesis presents a detailed study of the low energy electronic structure of graphene and its related three dimensional material - graphite - by using angle-resolved photoemission spectroscopy (ARPES), a direct probe of the electronic structure. In particular, the evolution of the Dirac Fermions in graphene and graphite as well as the effect of impurities is the focus of this thesis. This thesis is organized as follows. The first chapter is an introduction of the electronic structure of graphene and graphite, and the specialty of Dirac fermions compared to quasiparticles in conventional condensed matter systems. Chapter 2 is an introduction of the techniques used throughout this thesis - angle resolved photoemission spectroscopy (ARPES), X-ray photoemission spectroscopy (XPS) and low energy electron microscopy (LEEM). Chapter 3 discusses the growth and characterization of epitaxial graphene on SiC wafers. Chapters 4 and 5 present the ARPES results on epitaxial graphene, the evolution of the low energy electronic dynamics as a function of sample thickness and how to make graphene a finite band gap semiconductor. More specifically, chapter 4 discusses how a gap is induced between the valence and conduction bands by graphene-substrate interaction and chapter 6 shows how a reversible metal-insulator transition can be possibly induced in epitaxial graphene by hole doping. Chapters 6 and 7 show the ARPES results on three dimensional graphite samples. Chapter 6 shows the coexistence of Dirac fermions with massive

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

    SciTech Connect

    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.

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

    SciTech Connect

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

    2010-05-02

    We report the first time-resolved soft x-ray measurements of solvated transition-metal complexes. L-edge spectroscopy directly probes dynamic changes in ligand-field splitting of 3d orbitals associated with the spin transition, and mediated by changes in ligand-bonding.

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

    NASA Technical Reports Server (NTRS)

    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.

  5. SPATIALLY RESOLVED SPECTROSCOPY OF SDSS J0952+2552: A CONFIRMED DUAL ACTIVE GALACTIC NUCLEUS

    SciTech Connect

    McGurk, R. C.; Max, C. E.; Rosario, D. J.; Shields, G. A.; Smith, K. L.; Wright, S. A. E-mail: max@ucolick.org E-mail: shieldsga@mail.utexas.edu E-mail: saw@astro.berkeley.edu

    2011-09-01

    Most massive galaxies contain supermassive black holes (SMBHs) in their cores. When galaxies merge, gas is driven to nuclear regions and can accrete onto the central black hole. Thus, one expects to see dual active galactic nuclei (AGNs) in a fraction of galaxy mergers. Candidates for galaxies containing dual AGNs have been identified by the presence of double-peaked narrow [O III] emission lines and by high spatial resolution images of close galaxy pairs. Spatially resolved spectroscopy is needed to confirm these galaxy pairs as systems with spatially separated double SMBHs. With the Keck 2 Laser Guide Star Adaptive Optics system and the OH Suppressing InfraRed Imaging Spectrograph near-infrared integral field spectrograph, we obtained spatially resolved spectra for SDSS J09527.62+255257.2, a radio-quiet quasar shown by previous imaging to consist of a galaxy and its close (1.''0) companion. We find that the main galaxy is a Type 1 AGN with both broad and narrow AGN emission lines in its spectrum, while the companion galaxy is a Type 2 AGN with narrow emission lines only. The two AGNs are separated by 4.8 kpc, and their redshifts correspond to those of the double peaks of the [O III] emission line seen in the Sloan Digital Sky Survey spectrum. Line diagnostics indicate that both components of the double emission lines are due to AGN photoionization. These results confirm that J0952+2552 contains two spatially separated AGNs. As one of the few confirmed dual AGNs at an intermediate separation of <10 kpc, this system offers a unique opportunity to study galaxy mergers and their effect on black hole growth.

  6. Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy

    SciTech Connect

    Grunwaldt, Jan-Dierk; Kimmerle, Bertram; Baiker, Alfons; Boye, Pit; Schroer, Christian G.; Glatzel, Pieter; Borca, Camelia N.; Beckmann, Felix

    2009-09-25

    Spectroscopic studies on heterogeneous catalysts have mostly been done in an integral mode. However, in many cases spatial variations in catalyst structure can occur, e.g. during impregnation of pre-shaped particles, during reaction in a catalytic reactor, or in microstructured reactors as the present overview shows. Therefore, spatially resolved molecular information on a microscale is required for a comprehensive understanding of theses systems, partly in ex situ studies, partly under stationary reaction conditions and in some cases even under dynamic reaction conditions. Among the different available techniques, X-ray absorption spectroscopy (XAS) is a well-suited tool for this purpose as the different selected examples highlight. Two different techniques, scanning and full-field X-ray microscopy/tomography, are described and compared. At first, the tomographic structure of impregnated alumina pellets is presented using full-field transmission microtomography and compared to the results obtained with a scanning X-ray microbeam technique to analyse the catalyst bed inside a catalytic quartz glass reactor. On the other hand, by using XAS in scanning microtomography, the structure and the distribution of Cu(0), Cu(I), Cu(II) species in a Cu/ZnO catalyst loaded in a quartz capillary microreactor could be reconstructed quantitatively on a virtual section through the reactor. An illustrating example for spatially resolved XAS under reaction conditions is the partial oxidation of methane over noble metal-based catalysts. In order to obtain spectroscopic information on the spatial variation of the oxidation state of the catalyst inside the reactor XAS spectra were recorded by scanning with a micro-focussed beam along the catalyst bed. Alternatively, full-field transmission imaging was used to efficiently determine the distribution of the oxidation state of a catalyst inside a reactor under reaction conditions. The new technical approaches together with quantitative data

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

    PubMed

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

    2015-03-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼10(6) photons/s, by focusing the produced x-rays with a polycapillary optic. Since the acquisition of x-ray absorption spectra requires the averaging of measurements from >10(7) laser pulses, we also present data on the source stability, including single pulse measurements of the x-ray yield and the x-ray spectral shape. In single pulse measurements, the x-ray flux has a measured standard deviation of 8%, where the laser pointing is the main cause of variability. Further, we show that the variability in x-ray spectral shape from single pulses is low, thus justifying the combining of x-rays obtained from different laser pulses into a single spectrum. Finally, we show a static x-ray absorption spectrum of a ferrioxalate solution as detected by a microcalorimeter array. Altogether, our results demonstrate that this water-jet based plasma source is a suitable candidate for laboratory-based time-resolved x-ray absorption spectroscopy experiments. PMID:26798792

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

    PubMed Central

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

    2015-01-01

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ∼106 photons/s, by focusing the produced x-rays with a polycapillary 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. PMID:26798792

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

    DOE PAGESBeta

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

    2015-03-02

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

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

    SciTech Connect

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

    2015-03-02

    We describe a laser-driven x-ray plasma source designed for ultrafast x-ray absorption spectroscopy. The source is comprised of a 1 kHz, 20 W, femtosecond pulsed infrared laser and a water target. We present the x-ray spectra as a function of laser energy and pulse duration. Additionally, we investigate the plasma temperature and photon flux as we vary the laser energy. We obtain a 75 μm FWHM x-ray spot size, containing ~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.

  11. Cerebral oxygenation monitoring during cardiac bypass surgery in infants with broad band spatially resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Soschinski, Jan; Ben Mine, Lofti; Geraskin, Dmitri; Bennink, Gerardus; Kohl-Bareis, Matthias

    2007-07-01

    Neurological impairments following cardio-pulmonary bypass (CPB) during open heart surgery can result from microembolism and ischaemia. Here we present results from monitoring cerebral haemodynamics during CPB with near infrared spatially resolved broadband spectroscopy. In particular, the study has the objective (a) to monitor oxy- and deoxy-hemoglobin concentrations (oxy-Hb, deoxy-Hb) and their changes as well as oxygen saturation during CPB surgery and (b) to develop and test algorithms for the calculation of these parameters from broad band spectroscopy. For this purpose a detection system was developed based on an especially designed lens imaging spectrograph with optimised sensitivity of recorded reflectance spectra for wavelengths between 600 and 1000 nm. The high f/#-number of 1:1.2 of the system results in about a factor of 10 higher light throughput combined with a lower astigmatism and crosstalk between channels when compared with a commercial mirror spectrometers (f/# = 1:4). For both hemispheres two independent channels each with three source-detector distances (ρ = 25 . 35 mm) were used resulting in six spectra. The broad band approach allows to investigate the influence of the wavelength range on the calculated haemoglobin concentrations and their changes and oxygen saturation when the attenuation A(λ) and its slope ΔA(λ)/Δρ are evaluated. Furthermore, the different depth sensitivities of these measurement parameters are estimated from Monte Carlo simulations and exploited for an optimization of the cerebral signals. It is demonstrated that the system does record cerebral oxygenation parameters during CPB in infants. In particular, the correlation of haemoglobin concentrations with blood supply (flow, pressure) by the heart-lung machine and the significant decreases in oxygen saturation during cardiac arrest is discussed.

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

    NASA Astrophysics Data System (ADS)

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

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

  13. Ultrafast protein dynamics of hemoglobin as studied by picosecond time-resolved resonance Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Mizutani, Yasuhisa; Nagai, Masako

    2012-03-01

    Time-resolved resonance Raman spectroscopy on human adult hemoglobin (HbA) following ligand photolysis revealed that the frequency of the iron-histidine stretching [ν(Fe-His)] mode exhibited a 2-cm-1 downshift with a time constant of about 300 ps, suggesting a structural change in the heme pocket following the ligand photolysis. Low-frequency heme modes suggested that the primary metastable form of HbA has a more disordered orientation of propionates and a less strained environment than the deoxy form. The latter fact is consistent with the experimental observation that the ν(Fe-His) frequency of the metastable form is higher than the deoxy form. The present study shows that HbA adopts a metastable structure within the instrument response time and remains little changed in the subnanosecond to nanosecond time regime. Characteristics of the primary protein response of HbA based on the comparison of the results of HbA with those of the isolated chains and myoglobin are discussed.

  14. Investigation of microstructure in additive manufactured Inconel 625 by spatially resolved neutron transmission spectroscopy

    DOE PAGESBeta

    Tremsin, Anton S.; Gao, Yan; Dial, Laura C.; Grazzi, Francesco; Shinohara, Takenao

    2016-07-08

    Non-destructive testing techniques based on neutron imaging and diffraction can provide information on the internal structure of relatively thick metal samples (up to several cm), which are opaque to other conventional non-destructive methods. Spatially resolved neutron transmission spectroscopy is an extension of traditional neutron radiography, where multiple images are acquired simultaneously, each corresponding to a narrow range of energy. The analysis of transmission spectra enables studies of bulk microstructures at the spatial resolution comparable to the detector pixel. In this study we demonstrate the possibility of imaging (with ~100 μm resolution) distribution of some microstructure properties, such as residual strain,more » texture, voids and impurities in Inconel 625 samples manufactured with an additive manufacturing method called direct metal laser melting (DMLM). Although this imaging technique can be implemented only in a few large-scale facilities, it can be a valuable tool for optimization of additive manufacturing techniques and materials and for correlating bulk microstructure properties to manufacturing process parameters. Additionally, the experimental strain distribution can help validate finite element models which many industries use to predict the residual stress distributions in additive manufactured components.« less

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

    PubMed

    Beauvoit, B; Chance, B

    1998-07-01

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

  16. Lifetime-resolved photoacoustic (LPA) spectroscopy for monitoring oxygen change and photodynamic therapy (PDT)

    NASA Astrophysics Data System (ADS)

    Jo, Janggun; Lee, Chang Heon; Kopelman, Raoul; Wang, Xueding

    2016-03-01

    The Methylene Blue loaded Polyacrylamide Nanoparticles (MB-PAA NPs) are used for oxygen sensing and Photodynamic therapy (PDT), a promising therapeutic modality employed for various tumors, with distinct advantages of delivery of biomedical agents and protection from other bio-molecules overcoming inherent limitations of molecular dyes. Lifetime-resolved photoacoustic spectroscopy using quenched-phosphorescence method is applied with MB-PAA NPs so as to sense oxygen, while the same light source is used for PDT. The dye is excited by absorbing 650 nm wavelength light from a pump laser to reach triplet state. The probe laser at 810 nm wavelength is used to excite the first triplet state at certain delayed time to measure the dye lifetime which indicates oxygen concentration. The 9L cells (106 cells/ml) incubated with MB-PAA NP solution are used for monitoring oxygen level change during PDT in situ test. The oxygen level and PDT efficacy are confirmed with a commercial oximeter, and fluorescence microscope imaging and flow cytometry results. This technique with the MB-PAA NPs allowed us to demonstrate a potential non-invasive theragnostic operation, by monitoring oxygen depletion during PDT in situ, without the addition of secondary probes. Here, we demonstrate this theragnostic operation, in vitro, performing PDT while monitoring oxygen depletion. We also show the correlation between O2 depletion and cell death.

  17. RESOLVED SPECTROSCOPY OF A BROWN DWARF BINARY AT THE T DWARF/Y DWARF TRANSITION

    SciTech Connect

    Burgasser, Adam J.; Gelino, Christopher R.; Kirkpatrick, J. Davy; Cushing, Michael C.

    2012-01-20

    We report resolved near-infrared imaging and spectroscopic observations of the T8.5 binary WISEP J045853.90+643452.6AB obtained with Keck/NIRC2, Keck/OSIRIS, and the Keck Laser Guide Star Adaptive Optics system. These data confirm common proper and radial motion for the two components, and we see the first indications of orbital motion (mostly radial) for this system. H-band spectroscopy identifies both components as very late type brown dwarfs with strong H{sub 2}O and CH{sub 4} absorption. The spectrum of WISE J0458+6434B also exhibits a compelling signature of NH{sub 3} absorption over 1.52-1.54 {mu}m when compared to the T9 dwarf UGPS J072227.51-054031.2. Comparison to T8-Y0 spectral standards and H-band spectral indices indicate classifications of T8.5 and T9.5 for these two components, approaching the boundary between the T dwarf and Y dwarf spectral classes.

  18. Spatially resolved spectroscopy of WR ring nebulae. I - NGC 2359 and RCW 78

    NASA Astrophysics Data System (ADS)

    Esteban, C.; Vilchez, J. M.; Manchado, A.; Edmunds, M. G.

    1990-01-01

    We report detailed spatially resolved spectroscopy of the WR nebulae NGC 2359 and RCW 78 surrounding the WN 5 HD 56925 and WN 8 HD 117688 stars. The aim of this work has been to study possible abundance inhomogeneities and the ionization structure of the nebulae, as well as to derive reliable values for the degree of self-enrichment. In NGC 2359 the derived ratio O2+/O+ shows localized variations resulting from the compression of the gas in the filaments with respect to the shell gas. Effective temperatures for the central stars of both nebulae have been estimated on the basis of the ionization structure; the values found appear appropriate for their spectral types. Abundances of O/H, NIH, Ne/H, and He/H have been determined in twelve different positions in NGC 2359, covering its different morphological zones. No significant differences in the N/H and O/H abundances across the nebula have been found, although He/H shows marginal evidence for localized enhancements. In the case of RCW 78 the derived value of O/H is roughly solar, but He/H and NIH may be slightly overabundant. The results suggest that the amount of chemical self-enrichment of these WR nebulae is, at most, small.

  19. Quantification of ischemic muscle deoxygenation by near infrared time-resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Hamaoka, Takatumi; Katsumura, Toshihito; Murase, Norio; Nishio, Shinya; Osada, Takuya; Sako, Takayuki; Higuchi, Hiroyuki; Kurosawa, Yuko; Shimomitsu, Teruichi; Miwa, Mitsuharu; Chance, Britton

    2000-01-01

    The purpose of this study was to quantify muscle deoxygenation in human skeletal muscles using near infrared time-resolved spectroscopy (NIRTRS) and compare NIRTRS indicators and blood saturation. The forearm muscles of five healthy males (aged 27 - 32 yrs.) were monitored for changes in hemoglobin saturation (SO2) during 12 min of arterial occlusion and recovery. SO2 was determined by measuring the temporal profile of photon diffusion at 780 and 830 nm using NIRTRS, and was defined as SO2-TRS. Venous blood samples were also obtained for measurements of SvO2, and PvO2. Interstitial PO2(PintO2) was monitored by placing an O2 electrode directly into the muscle tissue. Upon the initiation of occlusion, all parameters fell progressively until reaching a plateau in the latter half of occlusion. It was observed at the end of occlusion that SO2-TRS (24.1 +/- 5.6%) agreed with SvO2 (26.2 +/- 6.4) and that PintO2 (14.7 +/- 1.0 Torr) agreed with PvO2 (17.3 +/- 2.2 Torr). The resting O2 store (oxygenated hemoglobin) and O2 consumption rate were 290 (mu) M and 0.82 (mu) Ms-1, respectively, values which reasonably agree with the reported results. These results indicate that there was no O2 gradient between vessels and interstisium at the end of occlusion.

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

    NASA Astrophysics Data System (ADS)

    Pu, Yang; Alfano, Robert R.

    2015-03-01

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

  1. Local resolved spectroscopy at the human ocular fundus in vivo: technique and clinical examples

    NASA Astrophysics Data System (ADS)

    Hammer, Martin; Schweitzer, Dietrich; Scibor, Mateusz

    1996-01-01

    Ocular fundus reflectometry is known as a method for the determination of the optical density of pigments at the eye ground. This has been described for diagnostic investigations at single locations. The new technique of imaging spectroscopy enables the recording of one dimensional local distribution of spectra from the fundus which is illuminated confocal to the entrance slit of a spectrograph. A fundus reflectometer consisting of a Zeiss fundus camera, an imaging spectrograph, and an intensified CCD-camera are presented. The local resolved spectra gained by this apparatus are approximated by a mathematical model on the basis of the anatomy of the fundus as a structure of layers with different optical properties. Each spectrum is assumed to be described by a function of the absorption spectra of the pigments found in the retinal and choroidal tissue. Assuming the existence of parameters which are independent from the fundus location we have to approximate the measured local distribution of spectra by a system of coupled non-linear equations. By a least square fit the local distribution of the extinction of melanin, xantophyll and hemoglobin may be obtained as well as the extension of pathologic alterations at the fundus. The benefits of the method for clinical diagnostics are discussed at first measurements from physiological and pathological examples.

  2. Spatially resolved Brillouin spectroscopy for in vivo determination of the biomechanical properties of the crystalline lenses

    NASA Astrophysics Data System (ADS)

    Stachs, Oliver; Reiß, Stephan; Guthoff, Rudolf; Stolz, Heinrich

    2012-03-01

    Confocal Brillouin spectroscopy is an innovative measurement method for the noninvasive determination of rheological tissue properties. Its application in ophthalmology can offer the possibility to determine in vivo the deformation properties of eye lens with spatial resolution. This seems to be a promising approach concerning current presbyopia research. Due to the spatially resolved detection of the viscoelastic lens properties, a better understanding of the natural aging process of the lens and the influences of different lens opacities on the stiffness is expected. Based on spectral data the refractive index profile, the protein concentration and the density profile within the lens tissue can be derived. A measurement set-up for confocal Brillouin microscopy based on spectral analysis of spontaneous Brillouin scattering signals by using a high-resolution dispersive device is presented. First in vivo measurements results on rabbit eyes are presented and evaluated concerning refractive index distribution, protein concentration, density and rheological significance. These data are compared with known research results of ex vivo lenses.

  3. Time-resolved four-wave-mixing spectroscopy for inner-valence transitions.

    PubMed

    Ding, Thomas; Ott, Christian; Kaldun, Andreas; Blättermann, Alexander; Meyer, Kristina; Stooss, Veit; Rebholz, Marc; Birk, Paul; Hartmann, Maximilian; Brown, Andrew; Van Der Hart, Hugo; Pfeifer, Thomas

    2016-02-15

    Noncollinear four-wave-mixing (FWM) techniques at near-infrared (NIR), visible, and ultraviolet frequencies have been widely used to map vibrational and electronic couplings, typically in complex molecules. However, correlations between spatially localized inner-valence transitions among different sites of a molecule in the extreme ultraviolet (XUV) spectral range have not been observed yet. As an experimental step toward this goal, we perform time-resolved FWM spectroscopy with femtosecond NIR and attosecond XUV pulses. The first two pulses (XUV-NIR) coincide in time and act as coherent excitation fields, while the third pulse (NIR) acts as a probe. As a first application, we show how coupling dynamics between odd- and even-parity, inner-valence excited states of neon can be revealed using a two-dimensional spectral representation. Experimentally obtained results are found to be in good agreement with ab initio time-dependent R-matrix calculations providing the full description of multielectron interactions, as well as few-level model simulations. Future applications of this method also include site-specific probing of electronic processes in molecules. PMID:26872169

  4. Host Sensitized Luminescence and Time-Resolved Spectroscopy of YVO4: Ho3+ Nanocrystals

    NASA Astrophysics Data System (ADS)

    Mahata, Manoj Kumar; Koppe, Tristan; Hofsäss, Hans; Kumar, Kaushal; Vetter, Ulrich

    Rare earth doped phosphors have attracted much interest because of their high chemical durability and wide range of attractive applications. In this work, Ho3+ doped tetragonal YVO4 nanocrystals have been synthesized via a facile co-precipitation method. The phosphor was characterized by various methods including X-ray diffraction, photoluminescence, cathodoluminescence, time-resolved spectroscopy measurements. The frequency upconversion emission in the synthesized phosphor has been investigated under 800 nm laser excitation. UV-excited photoluminescence (PL) and cathodoluminescence (CL) measurements were performed at room temperature (300 K). A broad band which arises at ∼ 370-600 nm is attributed to the relaxation of VO43- groups from conduction band to valence band. Under UV-excitation, the presence of a sharp band at 550 nm due to the intra-4f transitions of the trivalent holmium ions suggests energy transfer from YVO4 host to RE ions. Luminescence measurements show that this material is suitable for field emission displays (FED) and fluorescent lamps. Also the conversion of UV radiation as well as IR radiation into the visible region suggests the application of this material for photon harvesting in solar cells.

  5. [Photodissociation of Acetylene and Acetone using Step-Scan Time-Resolved FTIR Emission Spectroscopy

    NASA Technical Reports Server (NTRS)

    McLaren, Ian A.; Wrobel, Jacek D.

    1997-01-01

    The photodissociation of acetylene and acetone was investigated as a function of added quenching gas pressures using step-scan time-resolved FTIR emission spectroscopy. Its main components consist of Bruker IFS88, step-scan Fourier Transform Infrared (FTIR) spectrometer coupled to a flow cell equipped with Welsh collection optics. Vibrationally excited C2H radicals were produced from the photodissociation of acetylene in the unfocused experiments. The infrared (IR) emission from these excited C2H radicals was investigated as a function of added argon pressure. Argon quenching rate constants for all C2H emission bands are of the order of 10(exp -13)cc/molecule.sec. Quenching of these radicals by acetylene is efficient, with a rate constant in the range of 10(exp -11) cc/molecule.sec. The relative intensity of the different C2H emission bands did not change with the increasing argon or acetylene pressure. However, the overall IR emission intensity decreased, for example, by more than 50% when the argon partial pressure was raised from 0.2 to 2 Torr at fixed precursor pressure of 160mTorr. These observations provide evidence for the formation of a metastable C2H2 species, which are collisionally quenched by argon or acetylene. Problems encountered in the course of the experimental work are also described.

  6. Optical analysis of cirrhotic liver by near infrared time resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Nishio, Toshihiro; Kitai, Toshiyuki; Miwa, Mitsuharu; Takahashi, Rei; Yamaoka, Yoshio

    1999-10-01

    The severity of liver cirrhosis was related with the optical properties of liver tissue. Various grades of liver cirrhosis were produced in rats by intraperitoneal injection of thioacetamide (TAA) for different periods: 4 weeks, 8 weeks, 12 weeks, and 16 weeks. Optical properties of the liver, absorption, coefficient ((mu) a) and scattering coefficient (microsecond(s) '), were measured by near-infrared time- resolved spectroscopy. Histological examination confirmed cirrhotic changes in the liver, which were more severe in rats with TAA administration for longer periods. The (mu) a increased in 4- and 8-week rats, and then decreased in 12- and 16-week rats. The (mu) a of blood-free liver decreased as liver cirrhosis progressed. The hemoglobin content in the liver calculated from the (mu) a values increased in 4- and 8-week rats and decreased in 12- and 16-week rats. The microsecond(s) ' decreased in the cirrhotic liver, probably reflecting the decrease in the mitochondria content. It was shown that (mu) a and microsecond(s) ' determination is useful to assess the severity of liver cirrhosis.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  8. Time-Resolved Photoelectron Spectroscopy of Dissociating 1,2-Butadiene Molecules by High Harmonic Pulses.

    PubMed

    Iikubo, Ryo; Fujiwara, Takehisa; Sekikawa, Taro; Harabuchi, Yu; Satoh, Sota; Taketsugu, Tetsuya; Kayanuma, Yosuke

    2015-07-01

    Using 42 nm high harmonic pulses, the dissociation dynamics of 1,2-butadiene was investigated by time-resolved photoelectron spectroscopy (TRPES), enabling us to observe dynamical changes of multiple molecular orbitals (MOs) with higher temporal resolution than conventional light sources. Because each lower-lying occupied MO has particular spatial electron distribution, the structural dynamics of photochemical reaction can be revealed. On the femtosecond time scale, a short-lived excited state with a lifetime of 37 ± 15 fs and the coherent oscillation of the photoelectron yield stimulated by Hertzberg-Teller coupling were observed. Ab initio molecular dynamics simulations in the electronically excited state find three relaxation pathways from the vertically excited structure in S1 to the ground state, and one of them is the dominant relaxation pathway, observed as the short-lived excited state. On the picosecond time scale, the photoelectron yields related to the C-C bond decreased upon photoexcitation, indicating C-C bond cleavage. PMID:26266720

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  10. Toward reliable retrieval of functional information of papillary dermis using spatially resolved diffuse reflectance spectroscopy.

    PubMed

    Chen, Yu-Wen; Guo, Jun-Yen; Tzeng, Shih-Yu; Chou, Ting-Chun; Lin, Ming-Jen; Huang, Lynn Ling-Huei; Yang, Chao-Chun; Hsu, Chao-Kai; Tseng, Sheng-Hao

    2016-02-01

    Spatially resolved diffuse reflectance spectroscopy (SRDRS) has been employed to quantify tissue optical properties and its interrogation volume is majorly controlled by the source-to-detector separations (SDSs). To noninvasively quantify properties of dermis, a SRDRS setup that includes SDS shorter than 1 mm is required. It will be demonstrated in this study that Monte Carlo simulations employing the Henyey-Greenstein phase function cannot always precisely predict experimentally measured diffuse reflectance at such short SDSs, and we speculated this could be caused by the non-negligible backward light scattering at short SDSs that cannot be properly modeled by the Henyey-Greenstein phase function. To accurately recover the optical properties and functional information of dermis using SRDRS, we proposed the use of the modified two-layer (MTL) geometry. Monte Carlo simulations and phantom experiment results revealed that the MTL probing geometry was capable of faithfully recovering the optical properties of upper dermis. The capability of the MTL geometry in probing the upper dermis properties was further verified through a swine study, and it was found that the measurement results were reasonably linked to histological findings. Finally, the MTL probe was utilized to study psoriatic lesions. Our results showed that the MTL probe was sensitive to the physiological condition of tissue volumes within the papillary dermis and could be used in studying the physiology of psoriasis. PMID:26977361

  11. Reactivity of Binuclear Tantalum Clusters on Silica: Characterization by Transient Time-Resolved Spectroscopy

    SciTech Connect

    Nemana, Sailendra; Sun, Junming; Gates, Bruce C.

    2008-05-08

    Binuclear tantalum clusters were synthesized from Ta(CH{sub 2}Ph){sub 5} (Ph is phenyl) on the surface of nonporous SiO{sub 2} (Aerosil), and their reactions with H{sub 2}, D{sub 2}, and ethylene were characterized by time-resolved infrared (IR), extended X-ray absorption fine structure (EXAFS), and X-ray absorption near edge spectroscopies. The EXAFS data indicate the formation in H{sub 2} of clusters with a Ta-Ta coordination number of approximately 1 and a bonding distance of 2.74 {angstrom}. Reactions of the supported clusters with D{sub 2} and H{sub 2} facilitate the interconversion of O-H and O-D groups on the SiO{sub 2} surface. Reaction of these clusters with ethylene led to their rapid fragmentation to give mononuclear tantalum complexes, as the tantalum was oxidized and new ligands formed, suggested by IR spectra to be ethyl. The results demonstrate a rough analogy between the chemistry of tantalum clusters on the SiO{sub 2} surface and their chemistry in solution. Because alkenes are suggested intermediates in the catalytic disproportionation of alkanes on supported tantalum, our results indicate how these intermediates might influence the nature of the catalytically active species.

  12. A compact time-resolved system for near infrared spectroscopy based on wavelength space multiplexing

    NASA Astrophysics Data System (ADS)

    Re, Rebecca; Contini, Davide; Caffini, Matteo; Cubeddu, Rinaldo; Spinelli, Lorenzo; Torricelli, Alessandro

    2010-11-01

    We designed and developed a compact dual-wavelength and dual-channel time-resolved system for near-infrared spectroscopy studies of muscle and brain. The system employs pulsed diode lasers as sources, compact photomultipliers, and time-correlated single photon counting boards for detection. To exploit the full temporal and dynamic range of the acquisition technique, we implemented an approach based on wavelength space multiplexing: laser pulses at the two wavelengths are alternatively injected into the two channels by means of an optical 2×2 switch. In each detection line (i.e., in each temporal window), the distribution of photon time-of-flights at one wavelength is acquired. The proposed approach increases the signal-to-noise ratio and avoids wavelength cross-talk with respect to the typical approach based on time multiplexing. The instrument was characterized on tissue phantoms to assess its properties in terms of linearity, stability, noise, and reproducibility. Finally, it was successfully tested in preliminary in vivo measurements on muscle during standard cuff occlusion and on the brain during a motor cortex response due to hand movements.

  13. Spatially resolved spectroscopy for nondestructive quality measurements of Braeburn apples cultivated in sub-fertilization condition

    NASA Astrophysics Data System (ADS)

    Nguyen Do Trong, Nghia; Erkinbaev, Chyngyz; Nicolaï, Bart; Saeys, Wouter; Tsuta, Mizuki; De Baerdemaeker, Josse

    2013-05-01

    A contact spatially resolved spectroscopy (SRS) setup based on a fiber-optics probe in the Vis/NIR range (400-1000 nm) was developed, calibrated, and validated for its measurements and optical properties estimation by means of a metamodeling method on a set of liquid optical phantoms. Thirty Braeburn apples cultivated in sub-fertilization condition were harvested and measured before and after shelf-life storage (2 weeks at 18 °C) by the setup and were analyzed for quality attributes (firmness and soluble solids contents (SSC)) by destructive reference methods. Estimated optical properties (absorption and reduced scattering coefficients) acquired from SRS measurements at the beginning and the end of the shelf-life indicated changes in chemical composition of the apples. Partial Least Squares Regression (PLSR) was employed to construct calibration models relating the estimated optical properties to the reference quality attributes. The constructed PLS models based on the absorption coefficient spectra gave good prediction performance for the quality attributes of the apples in the validation set with correlation coefficients r of 0.901 and r of 0.844, respectively for SSC and firmness. The obtained results clearly show the potential of the SRS measurements for nondestructive quality evaluation of apples.

  14. Time-Resolved Ultraviolet Spectroscopy of the Missing Link Pulsar/LMXB PSR J1023

    NASA Astrophysics Data System (ADS)

    Knigge, Christian

    2013-10-01

    PSR J1023 is one of only three known ''missing link'' binary pulsars. These systems have been observed to switch at least once between a milli-second pulsar {MSP} state and a low-mass X-ray binary {LMXB} state. PSR J1023, in particular, was originally classified as an LMXB, but later {re-}discovered as a diskless 1.7 ms MSP. In June 2013, the system transitioned back to its X-ray- and optically bright LMXB state. There is an ongoing extensive X-ray, radio and optical monitoring campaign, but the critical ultraviolet {UV} waveband has so far remained largely unexplored. Since the system could return to a long-lasting low state at any time, and since the UV capability offered by HST may not be available for much longer, we here request DD time to obtain time-resolved UV spectroscopy of this system before it fades into the MSP state again. These observations will allow us to: {i} measure the spectral energy distribution of the accretion disk; {ii} search for evidence of an accretion disk wind; {iii} search for UV variability, including UV pulsations on the neutron star spin period; {iv} determine the reddening and extinction towards the system, and hence its luminosity and mass accretion rate.

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

    PubMed

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

    2011-11-15

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

  16. Adsorption of Uranyl on Gibbsite: A Time-Resolved Laser-Induced Fluorescence Spectroscopy Study

    SciTech Connect

    Chang, Hyun-shik; Korshin, Gregory V.; Wang, Zheming; Zachara, John M.

    2006-02-15

    Uranyl adsorbed on gibbsite at pH 4.0-8.0 and ionic strengths (ISs) 0.001-0.4 M (NaClO4) in the absence of carbonate was studied using time-resolved laser-induced fluorescence spectroscopy (TRLIFS) under cryogenic conditions. TRLIFS data showed the presence of several distinct emission components. Their contributions were determined using the evolving factor analysis approach. Four components denoted as species A, B, C, and D were discerned. Each of them was characterized by a characteristic response to pH and IS changes and also by a unique combination of the values of the fundamental transition energy E0,0, vibronic spacing E, and half-width of the vibronic lines W. Species A and B were major contributors to the overall emission. They were mainly affected by the pH and predominated below and above pH 5.0, respectively. In contrast with that, the contribution of species C was noticeable only at IS = 0.001 M, while it was suppressed or absent at high IS values. It was concluded that species A and B are likely to correspond to inner-sphere surface aluminol complexes AlO-(UO2)+ and AlO-(UO2)OH, while species C was hypothesized to correspond to electrostatically bound uranyl complexes (predominantly [UO2(OH)3]-).

  17. DARK MATTER SUBSTRUCTURE DETECTION USING SPATIALLY RESOLVED SPECTROSCOPY OF LENSED DUSTY GALAXIES

    SciTech Connect

    Hezaveh, Yashar; Holder, Gilbert; Dalal, Neal; Kuhlen, Michael; Marrone, Daniel; Murray, Norman; Vieira, Joaquin

    2013-04-10

    We investigate how strong lensing of dusty, star-forming galaxies (DSFGs) by foreground galaxies can be used as a probe of dark matter halo substructure. We find that spatially resolved spectroscopy of lensed sources allows dramatic improvements to measurements of lens parameters. In particular, we find that modeling of the full, three-dimensional (angular position and radial velocity) data can significantly facilitate substructure detection, increasing the sensitivity of observables to lower mass subhalos. We carry out simulations of lensed dusty sources observed by early ALMA (Cycle 1) and use a Fisher matrix analysis to study the parameter degeneracies and mass detection limits of this method. We find that even with conservative assumptions, it is possible to detect galactic dark matter subhalos of {approx}10{sup 8} M{sub Sun} with high significance in most lensed DSFGs. Specifically, we find that in typical DSFG lenses, there is a {approx}55% probability of detecting a substructure with M > 10{sup 8} M{sub Sun} with more than 5{sigma} detection significance in each lens, if the abundance of substructure is consistent with previous lensing results. The full ALMA array, with its significantly enhanced sensitivity and resolution, should improve these estimates considerably. Given the sample of {approx}100 lenses provided by surveys such as the South Pole Telescope, our understanding of dark matter substructure in typical galaxy halos is poised to improve dramatically over the next few years.

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

    PubMed

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

    2015-08-01

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

  19. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy

    SciTech Connect

    Hager, J. D. Lanier, N. E.; Kline, J. L.; Flippo, K. A.; Bruns, H. C.; Schneider, M.; Saculla, M.; McCarville, T.

    2014-11-15

    We present a temporally and a spatially resolved spectrometer for titanium x-ray absorption spectroscopy along 2 axial symmetric lines-of-sight. Each line-of-sight of the instrument uses an elliptical crystal to acquire both the 2p and 3p Ti absorption lines on a single, time gated channel of the instrument. The 2 axial symmetric lines-of-sight allow the 2p and 3p absorption features to be measured through the same point in space using both channels of the instrument. The spatially dependent material temperature can be inferred by observing the 2p and the 3p Ti absorption features. The data are recorded on a two strip framing camera with each strip collecting data from a single line-of-sight. The design is compatible for use at both the OMEGA laser and the National Ignition Facility. The spectrometer is intended to measure the material temperature behind a Marshak wave in a radiatively driven SiO{sub 2} foam with a Ti foam tracer. In this configuration, a broad band CsI backlighter will be used for a source and the Ti absorption spectrum measured.

  20. Electronic structure dynamics in a low bandgap polymer studied by time-resolved photoelectron spectroscopy.

    PubMed

    Cappel, Ute B; Plogmaker, Stefan; Terschlüsen, Joachim A; Leitner, Torsten; Johansson, Erik M J; Edvinsson, Tomas; Sandell, Anders; Karis, Olof; Siegbahn, Hans; Svensson, Svante; Mårtensson, Nils; Rensmo, Håkan; Söderström, Johan

    2016-08-01

    Means to measure the temporal evolution following a photo-excitation in conjugated polymers are a key for the understanding and optimization of their function in applications such as organic solar cells. In this paper we study the electronic structure dynamics by direct pump-probe measurements of the excited electrons in such materials. Specifically, we carried out a time-resolved photoelectron spectroscopy (TRPES) study of the polymer PCPDTBT by combining an extreme ultraviolet (XUV) high harmonic generation source with a time-of-flight spectrometer. After excitation to either the 1st excited state or to a higher excited state, we follow how the electronic structure develops and relaxes on the electron binding energy scale. Specifically, we follow a less than 50 fs relaxation of the higher exited state and a 10 times slower relaxation of the 1st excited state. We corroborate the results using DFT calculations. Our study demonstrates the power of TRPES for studying photo-excited electron energetics and dynamics of solar cell materials. PMID:27440450

  1. The vinyl + NO reaction : determining the products with time-resolved Fourier transform spectroscopy.

    SciTech Connect

    Osborn, David L; Zou, Peng; Klippenstein, Stephen J.

    2005-01-01

    We have studied the vinyl + NO reaction using time-resolved Fourier transform emission spectroscopy, complemented by electronic structure and microcanonical RRKM rate coefficient calculations. To unambiguously determine the reaction products, three precursors are used to produce the vinyl radical by laser photolysis: vinyl bromide, methyl vinyl ketone, and vinyl iodide. The emission spectra and theoretical calculations indicate that HCN + CH{sub 2}O is the only significant product channel for the C{sub 2}H{sub 3} + NO reaction near room temperature, in contradiction to several reports in the literature. Although CO emission is observed when vinyl bromide is used as the precursor, it arises from the reaction of NO with photofragments other than vinyl. This conclusion is supported by the absence of CO emission when vinyl iodide or methyl vinyl ketone is used. Prompt emission from vibrationally excited NO is evidence of the competition between back dissociation and isomerization of the initially formed nitrosoethylene adduct, consistent with previous work on the pressure dependence of this reaction. Our calculations indicate that production of products is dominated by the low energy portion of the energy distribution. The calculation also predicts an upper bound of 0.19% for the branching ratio of the H{sub 2}CNH + CO channel, which is consistent with our experimental results.

  2. New Insights from Phase-Resolved Spectroscopy of QPOs in GX 339—4

    NASA Astrophysics Data System (ADS)

    Stevens, Abigail L.; Uttley, Phil; van der Klis, Michiel

    2016-04-01

    We present a new spectral-timing technique for phase-resolved spectroscopy of low-frequency Type B quasi-periodic oscillations (QPOs) from the black hole X-ray binary GX 339--4. Evidence suggests that low-frequency QPOs originate from near-periodic geometric changes in the inner accretion flow, possibly due to general relativistic precession. The physical model predicts spectral energy distribution changes on the QPO timescale, but it is not possible to probe these changes using strictly spectral or timing analysis. Our new technique shows that for these data, the spectral energy distribution changes not only in normalization, but in spectral shape also, on the QPO timescale. We find that a blackbody spectral component and power law spectral component are both required to vary on the QPO timescale, and the blackbody variations are out of phase with the power law. With these findings we suggest a geometry for the precessing flow in the strong-gravity regime close to black holes.

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

    PubMed

    Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

    2016-02-01

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

  4. A split imaging spectrometer for temporally and spatially resolved titanium absorption spectroscopy.

    PubMed

    Hager, J D; Lanier, N E; Kline, J L; Flippo, K A; Bruns, H C; Schneider, M; Saculla, M; McCarville, T

    2014-11-01

    We present a temporally and a spatially resolved spectrometer for titanium x-ray absorption spectroscopy along 2 axial symmetric lines-of-sight. Each line-of-sight of the instrument uses an elliptical crystal to acquire both the 2p and 3p Ti absorption lines on a single, time gated channel of the instrument. The 2 axial symmetric lines-of-sight allow the 2p and 3p absorption features to be measured through the same point in space using both channels of the instrument. The spatially dependent material temperature can be inferred by observing the 2p and the 3p Ti absorption features. The data are recorded on a two strip framing camera with each strip collecting data from a single line-of-sight. The design is compatible for use at both the OMEGA laser and the National Ignition Facility. The spectrometer is intended to measure the material temperature behind a Marshak wave in a radiatively driven SiO2 foam with a Ti foam tracer. In this configuration, a broad band CsI backlighter will be used for a source and the Ti absorption spectrum measured. PMID:25430177

  5. Time-resolved spectroscopy of LiF:Mg,Cu,P.

    PubMed

    Mathur, V K; Barkyoumb, J H; Jarrett, Andrew

    2006-01-01

    Time-resolved spectroscopy measurements of LiF:Mg,Cu,P luminescence are presented to obtain a better understanding of the emission characteristics of this material. The intensities and decay of the emission bands were studied as a function of annealing temperature and ionising radiation (gamma) dose. Two peaks in the emission were observed at 367 and 466 nm when excited by the 266 nm laser radiation. The luminescence spectrum under band-to-band X-ray excitation shows a dominant emission approximately 390-400 nm, which resembles the reported thermoluminescence emission and is clearly different from the spectrum obtained using the 266 nm pulsed laser excitation. Annealing of the material to 300 degrees C increases the intensity of the 367 and 466 nm emission bands by an order of magnitude as well as changes the relative intensity of the bands. Additional emission bands, which are not evident in the thermoluminescence emission spectra, are seen at longer wavelengths that also increase with dose. Possible explanations for the observed emission spectra are discussed in this paper. PMID:16644981

  6. Fast Pyrolysis of Wood for Biofuels: Spatiotemporally Resolved Diffuse Reflectance In situ Spectroscopy of Particles.

    PubMed

    Paulsen, Alex D; Hough, Blake R; Williams, C Luke; Teixeira, Andrew R; Schwartz, Daniel T; Pfaendtner, Jim; Dauenhauer, Paul J

    2014-02-20

    Fast pyrolysis of woody biomass is a promising process capable of producing renewable transportation fuels to replace gasoline, diesel, and chemicals currently derived from nonrenewable sources. However, biomass pyrolysis is not yet economically viable and requires significant optimization before it can contribute to the existing oil-based transportation system. One method of optimization uses detailed kinetic models for predicting the products of biomass fast pyrolysis, which serve as the basis for the design of pyrolysis reactors capable of producing the highest value products. The goal of this work is to improve upon current pyrolysis models, usually derived from experiments with low heating rates and temperatures, by developing models that account for both transport and pyrolysis decomposition kinetics at high heating rates and high temperatures (>400 °C). A new experimental technique is proposed herein: spatiotemporally resolved diffuse reflectance in situ spectroscopy of particles (STR-DRiSP), which is capable of measuring biomass composition during fast pyrolysis with high spatial (10 μm) and temporal (1 ms) resolution. Compositional data were compared with a comprehensive 2D single-particle model, which incorporated a multistep, semiglobal reaction mechanism, prescribed particle shrinkage, and thermophysical properties that varied with temperature, composition, and orientation. The STR-DRiSP technique can be used to determine the transport-limited kinetic parameters of biomass decomposition for a wide variety of biomass feedstocks. PMID:24678023

  7. Toward reliable retrieval of functional information of papillary dermis using spatially resolved diffuse reflectance spectroscopy

    PubMed Central

    Chen, Yu-Wen; Guo, Jun-Yen; Tzeng, Shih-Yu; Chou, Ting-Chun; Lin, Ming-Jen; Huang, Lynn Ling-Huei; Yang, Chao-Chun; Hsu, Chao-Kai; Tseng, Sheng-Hao

    2016-01-01

    Spatially resolved diffuse reflectance spectroscopy (SRDRS) has been employed to quantify tissue optical properties and its interrogation volume is majorly controlled by the source-to-detector separations (SDSs). To noninvasively quantify properties of dermis, a SRDRS setup that includes SDS shorter than 1 mm is required. It will be demonstrated in this study that Monte Carlo simulations employing the Henyey-Greenstein phase function cannot always precisely predict experimentally measured diffuse reflectance at such short SDSs, and we speculated this could be caused by the non-negligible backward light scattering at short SDSs that cannot be properly modeled by the Henyey-Greenstein phase function. To accurately recover the optical properties and functional information of dermis using SRDRS, we proposed the use of the modified two-layer (MTL) geometry. Monte Carlo simulations and phantom experiment results revealed that the MTL probing geometry was capable of faithfully recovering the optical properties of upper dermis. The capability of the MTL geometry in probing the upper dermis properties was further verified through a swine study, and it was found that the measurement results were reasonably linked to histological findings. Finally, the MTL probe was utilized to study psoriatic lesions. Our results showed that the MTL probe was sensitive to the physiological condition of tissue volumes within the papillary dermis and could be used in studying the physiology of psoriasis. PMID:26977361

  8. Resolving dual binding conformations of cellulosome cohesin-dockerin complexes using single-molecule force spectroscopy

    PubMed Central

    Jobst, Markus A; Milles, Lukas F; Schoeler, Constantin; Ott, Wolfgang; Fried, Daniel B; Bayer, Edward A; Gaub, Hermann E; Nash, Michael A

    2015-01-01

    Receptor-ligand pairs are ordinarily thought to interact through a lock and key mechanism, where a unique molecular conformation is formed upon binding. Contrary to this paradigm, cellulosomal cohesin-dockerin (Coh-Doc) pairs are believed to interact through redundant dual binding modes consisting of two distinct conformations. Here, we combined site-directed mutagenesis and single-molecule force spectroscopy (SMFS) to study the unbinding of Coh:Doc complexes under force. We designed Doc mutations to knock out each binding mode, and compared their single-molecule unfolding patterns as they were dissociated from Coh using an atomic force microscope (AFM) cantilever. Although average bulk measurements were unable to resolve the differences in Doc binding modes due to the similarity of the interactions, with a single-molecule method we were able to discriminate the two modes based on distinct differences in their mechanical properties. We conclude that under native conditions wild-type Doc from Clostridium thermocellum exocellulase Cel48S populates both binding modes with similar probabilities. Given the vast number of Doc domains with predicteddual binding modes across multiple bacterial species, our approach opens up newpossibilities for understanding assembly and catalytic properties of a broadrange of multi-enzyme complexes. DOI: http://dx.doi.org/10.7554/eLife.10319.001 PMID:26519733

  9. Probing Ternary Complex Equilibria of Crown Ether Ligands by Time-Resolved Fluorescence Spectroscopy

    PubMed Central

    2015-01-01

    Ternary complex formation with solvent molecules and other adventitious ligands may compromise the performance of metal-ion-selective fluorescent probes. As Ca(II) can accommodate more than 6 donors in the first coordination sphere, commonly used crown ether ligands are prone to ternary complex formation with this cation. The steric strain imposed by auxiliary ligands, however, may result in an ensemble of rapidly equilibrating coordination species with varying degrees of interaction between the cation and the specific donor atoms mediating the fluorescence response, thus diminishing the change in fluorescence properties upon Ca(II) binding. To explore the influence of ligand architecture on these equilibria, we tethered two structurally distinct aza-15-crown-5 ligands to pyrazoline fluorophores as reporters. Due to ultrafast photoinduced electron-transfer (PET) quenching of the fluorophore by the ligand moiety, the fluorescence decay profile directly reflects the species composition in the ground state. By adjusting the PET driving force through electronic tuning of the pyrazoline fluorophores, we were able to differentiate between species with only subtle variations in PET donor abilities. Concluding from a global analysis of the corresponding fluorescence decay profiles, the coordination species composition was indeed strongly dependent on the ligand architecture. Altogether, the combination of time-resolved fluorescence spectroscopy with selective tuning of the PET driving force represents an effective analytical tool to study dynamic coordination equilibria and thus to optimize ligand architectures for the design of high-contrast cation-responsive fluorescence switches. PMID:25313708

  10. Nanosecond Time-Resolved Polarization Spectroscopies: Tools for Probing Protein Reaction Mechanisms

    PubMed Central

    Chen, Eefei; Goldbeck, Robert A.; Kliger, David S.

    2010-01-01

    Polarization methods, introduced in the 1800’s, offered one of the earliest ways to examine protein structure. Since then, many other structure-sensitive probes have been developed, but circular dichroism (CD) remains a powerful technique because of its versatility and the specificity of protein structural information that can be explored. With improvements in time-resolution, from millisecond to picosecond CD measurements, it has proven to be an important tool for studying the mechanism of folding and function in many biomolecules. For example, nanosecond time-resolved CD (TRCD) studies of the sub-microsecond events of reduced cytochrome c folding have provided direct experimental evidence of kinetic heterogeneity, which is an inherent property of the diffusional nature of early folding dynamics on the energy landscape. In addition, TRCD has been applied to the study of many biochemical processes, such as ligand rebinding in hemoglobin and myoglobin and signaling state formation in photoactive yellow protein and prototropin 1 LOV2. The basic approach to TRCD has also been extended to include a repertoire of nanosecond polarization spectroscopies: optical rotatory dispersion (ORD), magnetic CD and ORD, and linear dichroism. This article will discuss the details of the polarization methods used in this laboratory, as well as the coupling of timeresolved ORD with the temperature-jump trigger so that protein folding can be studied in a larger number of proteins. PMID:20438842

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

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    The NASA Mars2020 rover will be searching for signs of past habitability and past life on Mars. Additionally, the rover mission will prepare a cache of highly significant samples for a future sample return mission. NASA requires these samples to be well characterized; the instruments on the rover must be capable of fine-scale in situ mineralogical or elemental analysis with emphasis on biosignature detection or characterization. We have been developing multiple standoff laser-based instruments at the University of Hawaii, Manoa that are capable of fine-scale in situ chemical analysis and biosignatures detection. By employing a time-resolved spectroscopy, we can perform elemental analysis with Laser-Induced Breakdown Spectroscopy (LIBS), mineral and organic analysis with Raman spectroscopy, and biosignature detection with Laser-Induced Fluorescence (LIF). Each of these techniques share the same optics and detection equipment, allowing us to integrate them into a single, compact instrument. High time-resolution (~100 ns/pulse) is the key to this instrument; with it, the detector only records data when the signal is the brightest. Spectra can be taken during the day, LIBS can be measured without a plasma light background, and the Raman signal can be separated from the mineral fluorescence signal. Since bio-organics have very short fluorescence lifetimes, the new instrument can be used to unambiguously detect bio-organics. The prototype uses a low power (0.5 mJ/pulse) 532 nm laser with a detection limit of < 30 ppm of organics in a sample of Antarctica Dry Valley soil measured from 8 m. Another LIF instrument under development in our lab, called the Biofinder, takes advantage of the extremely intense fluorescence signal produced by organics by using a wide laser spot and a camera to produce LIF images of wide area (25 cm area from 2 m distance with 2 mm/pixel resolution). The Biofinder can quickly assess the area around the rover (at 10 frames/s) by imaging sample

  12. Vacuum ultraviolet luminescence of wide band-gap solids studied using time-resolved spectroscopy with synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Makhov, V. N.

    2014-04-01

    Some highlights of the time-resolved vacuum ultraviolet (VUV) luminescence spectroscopy of solids using synchrotron radiation (SR) are outlined, including studies of the unique phenomenon crossluminescence (CL) and the contribution of time-resolved VUV spectroscopy to the understanding of 5d-4f transitions of rare earth ions in solids. The main properties of CL studied at different SR sources are described and some unclear aspects of CL are pointed out. The results of recent studies of some CL-active nanosize materials are presented. We describe the time-resolved experiments which led to the discovery of 5d-4f luminescence in the deep VUV region (near 10 eV) of Gd3+ and Lu3+ ions incorporated into some wide band-gap fluoride hosts. The results of high-resolution (Δλ ˜ 0.5 Å) studies of 5d-4f emission and 4f-5d excitation spectra of Gd3+ and Lu3+, which allowed the detailed analysis of electron-lattice coupling in these systems, are presented. Possible new developments in the femtosecond time-resolved spectroscopy of solids with a free electron laser are discussed.

  13. Time-Resolved Light Scattering and Fluorescence Spectroscopy in Biomedical and Model Random Media

    NASA Astrophysics Data System (ADS)

    Das, Bidyut Baran

    Optical spectroscopy, light scattering and ultrafast time-gated imaging have been shown to offer novel approaches to study the optical characteristics of various biomedical and other random media. Fluorescence spectra from human malignant and nonmalignant breast tissues were measured at 300 nm excitation and a significant spectral difference was found between the two tissue types by using the ratio of fluorescence intensities at 340 and 440 nm. Optical density measurements on thin breast tissues show that the scattering cross-sections of breast tissues are relatively constant over the visible and the uv region. Transport mean free paths and the absorption lengths for various tissues and model random media were measured using time-resolved transmission. The scattering coefficients for human breast and chicken tissues were found to remain relatively constant in 570-630 nm wavelength region while they change significantly at 1064 nm. Chicken breast and fat tissues were found to be good models for human breast tissues as the values of the optical parameters of the two tissue types are about the same. The less scattering observed at 1064 nm makes tissues more transparent in the NIR region making it easier to image in thick tissues. Time-resolved backscattering measurements show that the scattering and the absorption parameters of a random medium can be obtained accurately in a two-fiber configuration as long as the radial distance is more than about seven times the transport mean free path of the sample. The single point source-detection configuration provides a tool to diagnose breast malignancy though it fails to give accurate values of the optical parameters of tissues. This failure is attributed to the invalidity of the diffusion approximation in this experimental configuration. A 2.5 mm thin chicken fat strip was imaged inside a 40 mm thick chicken breast tissue using snake photons at 625 nm with ultrafast time-gated detection. A simple model to describe the effect

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

    PubMed

    Souvignier, G; Gerwert, K

    1992-11-01

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

  15. Tubulin equilibrium unfolding followed by time-resolved fluorescence and fluorescence correlation spectroscopy

    PubMed Central

    Sánchez, Susana A.; Brunet, Juan E.; Jameson, David M.; Lagos, Rosalba; Monasterio, Octavio

    2004-01-01

    The pathway for the in vitro equilibrium unfolding of the tubulin heterodimer by guanidinium chloride (GdmCl) has been studied using several spectroscopic techniques, specifically circular dichroism (CD), two-photon Fluorescence Correlation Spectroscopy (FCS), and time-resolved fluorescence, including lifetime and dynamic polarization. The results show that tubulin unfolding is characterized by distinct processes that occur in different GdmCl concentration ranges. From 0 to 0.5 M GdmCl, a slight alteration of the tubulin heterodimer occurs, as evidenced by a small, but reproducible increase in the rotational correlation time of the protein and a sharp decrease in the secondary structure monitored by CD. In the range 0.5–1.5 M GdmCl, significant decreases in the steady-state anisotropy and average lifetime of the intrinsic tryptophan fluorescence occur, as well as a decrease in the rotational correlation time, from 48 to 26 nsec. In the same GdmCl range, the number of protein molecules (labeled with Alexa 488), as determined by two-photon FCS measurements, increases by a factor of two, indicating dissociation of the tubulin dimer into monomers. From 1.5 to 4 M GdmCl, these monomers unfold, as evidenced by the continual decrease in the tryptophan steady-state anisotropy, average lifetime, and rotational correlation time, concomitant with secondary structural changes. These results help to elucidate the unfolding pathway of the tubulin heterodimer and demonstrate the value of FCS measurements in studies on oligomeric protein systems. PMID:14691224

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

    PubMed

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

    2010-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2010-03-01

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

  18. Computational optimization of the configuration of a spatially resolved spectroscopy sensor for milk analysis.

    PubMed

    Watté, Rodrigo; Aernouts, Ben; Van Beers, Robbe; Postelmans, Annelies; Saeys, Wouter

    2016-04-21

    A global optimizer has been developed, capable of computing the optimal configuration in a probe for spatially resolved reflectance spectroscopy (SRS). The main objective is to minimize the number of detection fibers, while maintaining an accurate estimation of both absorption and scattering profiles. Multiple fibers are necessary to robustify the estimation of optical properties against noise, which is typically present in the measured signals and influences the accuracy of the inverse estimation. The optimizer is based on a robust metamodel-based inverse estimation of the absorption coefficient and a reduced scattering coefficient from the acquired SRS signals. A genetic algorithm is used to evaluate the effect of the fiber placement on the performance of the inverse estimator to find the bulk optical properties of raw milk. The algorithm to find the optimal fiber placement was repeatedly executed for cases with a different number of detection fibers, ranging from 3 to 30. Afterwards, the optimal designs for each considered number of fibers were compared based on their performance in separating the absorption and scattering properties, and the significance of the differences was tested. A sensor configuration with 13 detection fibers was found to be the combination with the lowest number of fibers which provided an estimation performance which was not significantly worse than the one obtained with the best design (30 detection fibers). This design resulted in the root mean squared error of prediction (RMSEP) of 1.411 cm(-1) (R(2) = 0.965) for the estimation of the bulk absorption coefficient values, and 0.382 cm(-1) (R(2) = 0.996) for the reduced scattering coefficient values. PMID:27026600

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

    NASA Astrophysics Data System (ADS)

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

    2006-06-01

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

  20. Spectral properties of transition metal pnictides and chalcogenides: Angle-resolved photoemission spectroscopy and dynamical mean-field theory

    NASA Astrophysics Data System (ADS)

    van Roekeghem, Ambroise; Richard, Pierre; Ding, Hong; Biermann, Silke

    2016-01-01

    Electronic Coulomb correlations lead to characteristic signatures in the spectroscopy of transition metal pnictides and chalcogenides: quasi-particle renormalizations, lifetime effects or incoherent badly metallic behavior above relatively low coherence temperatures are measures of many-body effects due to local Hubbard and Hund's couplings. We review and compare the results of angle-resolved photoemission spectroscopy experiments (ARPES) and of combined density functional/dynamical mean-field theory (DFT+DMFT) calculations. We emphasize the doping-dependence of the quasi-particle mass renormalization and coherence properties.

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

    SciTech Connect

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

    2011-10-08

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

  2. Time-resolved spectroscopy and near infrared imaging enhanced by receptor-targeted contrast agents for prostate cancer detection

    NASA Astrophysics Data System (ADS)

    Pu, Y.; Wang, W. B.; Tang, G. C.; Achilefu, S.; Alfano, R. R.

    2011-03-01

    Time-resolved spectroscopy and near infrared imaging enhanced by receptor-targeted contrast agents for prostate cancer detection will be presented. Two contrast agents, Cybesin and Cytate, were investigated using time-resolved spectroscopy in aqueous solution and cancerous and normal prostate tissues. The time evolution of the fluorescent dipole in solution was studied using a system of first-order linear differential equations containing two main parameters: the decay rate of emission and the rate of one orthogonal emission component transferring to another. An analytical polarization model was developed and used to extract rotational times and fluorescence anisotropies of the contrast agents in prostate tissues. The differences of rotational times and polarization anisotropies were observed for Cybesin (Cytate) in cancerous and normal prostate tissue, which reflect preferred bond of contrast agents and cancerous tissue cells. The conjugation of Cybesin (Cytate) to prostate cancerous cells offers high contrast between normal and cancerous tissues.

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

    PubMed

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

    2011-02-21

    Time-resolved terahertz spectroscopy and combination of quantum chemistry modeling and molecular dynamics simulations were used for the determination of charge carrier mobility in poly[methyl(phenyl)silylene]. Using time-resolved THz spectroscopy we established the on-chain charge carrier drift mobility in PMPSi as 0.02 cm(2) V(-1) s(-1). This value is low due to the formation of polarons: the hole is self-trapped in a potential formed by local chain distortion and the transient THz conductivity spectra show signatures of its oscillations within this potential well. This view is supported by the agreement between experimental and calculated values of the on-chain charge carrier mobility. PMID:21305068

  4. Quantification of joint inflammation in rheumatoid arthritis by time-resolved diffuse optical spectroscopy and tracer kinetic modeling

    NASA Astrophysics Data System (ADS)

    Ioussoufovitch, Seva; Morrison, Laura B.; Lee, Ting-Yim; St. Lawrence, Keith; Diop, Mamadou

    2015-03-01

    Rheumatoid arthritis (RA) is characterized by chronic synovial inflammation, which can cause progressive joint damage and disability. Diffuse optical spectroscopy (DOS) and imaging have the potential to become potent monitoring tools for RA. We devised a method that combined time-resolved DOS and tracer kinetics modeling to rapidly and reliably quantify blood flow in the joint. Preliminary results obtained from two animals show that the technique can detect joint inflammation as early as 5 days after onset.

  5. Hot photocarrier dynamics in organic solar cells measured by transient absorption and time-resolved terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Lane, Paul A.; Cunningham, Paul D.; Melinger, Joseph S.; Heilweil, Edwin J.

    2014-10-01

    We present a study of charge transfer and carrier dynamics in films of zinc phthalocyanine (ZnPc) and buckmisnsterfullerene (C60) by investigated by time-resolved terahertz spectroscopy (TRTS). We compare terahertz photoconductivity dynamics in composite and multi-layered films of C60 and ZnPc. The few picosecond terahertz photoconductivity dynamics arise from autoionization and recombination between C60 molecules and cooling of hot photocarriers following from charge transfer between C60 and ZnPc.

  6. Chemical state of Ag in Conducting Bridge Random Access Memory cells: a depth resolved X-ray Absorption Spectroscopy investigation.

    NASA Astrophysics Data System (ADS)

    d'Acapito, F.; Souchier, E.; Noe, P.; Blaise, P.; Bernard, M.; Jousseaume, V.

    2016-05-01

    Conducting Bridge Random Access Memories (CBRAM) are a promising substitute for FLASH technology but problems with limited retention of the low resistance ON state still hamper their massive deployment. Depth resolved X-ray Absorption Spectroscopy has been used to describe the chemical state of the atoms of the active electrode (in this case Ag) and to reveal the role of Sb as stabilizer of the metallic state.

  7. Time-resolved spectroscopy of nucleic acid systems using synchrotron radiation from 230 nm to 354 nm

    NASA Astrophysics Data System (ADS)

    Daniels, Malcolm; Ballini, Jean-Pierre; Vigny, Paul

    1992-07-01

    The excited states of nucleic acids are complex, both at the individual chromophore level and because of the effect of stacking interactions on the electronic states. Considerable progress has been made recently by studying the lifetimes of the stacked states and by utilizing the technique of time-resolved spectroscopy. Experimental results obtained using the ACO synchrotron at LURE, Orsay, will be presented. Resolution of the decay data gives a model-based estimate of the number of emitting species and their lifetimes, and this information is then used to deconvolate experimental time-windowed spectra (time-delayed spectra) to give true time-resolved spectra. It is a unique feature of the synchrotron, compared with the laser, that the combination of delayed detection (photon counting) with the continuous wavelength distribution of the synchrotron allows the acquisition of excitation spectra by uninterrupted repetitive scanning over a wide range of UV exciting wavelengths, in the present work from 230 nm to 354 nm. Such time-delayed excitation spectra can also be deconvoluted into components corresponding to the various time-resolved emission spectra. In this way we are able to demonstrate for the first time that ground state stacking interactions are directly responsible for excimer-like emissions. Time-resolved emission spectra and time-resolved excitation spectra will be presented for the dinucleoside phosphate d(CG) and the synthetic alternating polynucleotide poly d(GC), a `B-type' DNA structure.

  8. Band structures of 4f and 5f materials studied by angle-resolved photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Fujimori, Shin-ichi

    2016-04-01

    Recent remarkable progress in angle-resolved photoelectron spectroscopy (ARPES) has enabled the direct observation of the band structures of 4f and 5f materials. In particular, ARPES with various light sources such as lasers (hν ∼ 7~\\text{eV} ) or high-energy synchrotron radiations (hν ≳ 400~\\text{eV} ) has shed light on the bulk band structures of strongly correlated materials with energy scales of a few millielectronvolts to several electronvolts. The purpose of this paper is to summarize the behaviors of 4f and 5f band structures of various rare-earth and actinide materials observed by modern ARPES techniques, and understand how they can be described using various theoretical frameworks. For 4f-electron materials, ARPES studies of \\text{Ce}M\\text{I}{{\\text{n}}5} (M=\\text{Rh} , \\text{Ir} , and \\text{Co} ) and \\text{YbR}{{\\text{h}}2}\\text{S}{{\\text{i}}2} with various incident photon energies are summarized. We demonstrate that their 4f electronic structures are essentially described within the framework of the periodic Anderson model, and that the band-structure calculation based on the local density approximation cannot explain their low-energy electronic structures. Meanwhile, electronic structures of 5f materials exhibit wide varieties ranging from itinerant to localized states. For itinerant \\text{U}~5f compounds such as \\text{UFeG}{{\\text{a}}5} , their electronic structures can be well-described by the band-structure calculation assuming that all \\text{U}~5f electrons are itinerant. In contrast, the band structures of localized \\text{U}~5f compounds such as \\text{UP}{{\\text{d}}3} and \\text{U}{{\\text{O}}2} are essentially explained by the localized model that treats \\text{U}~5f electrons as localized core states. In regards to heavy fermion \\text{U} -based compounds such as the hidden-order compound \\text{UR}{{\\text{u}}2}\\text{S}{{\\text{i}}2} , their electronic structures exhibit complex behaviors. Their overall band structures

  9. Dynamics and Flexibility of Human Aromatase Probed by FTIR and Time Resolved Fluorescence Spectroscopy

    PubMed Central

    Sadeghi, Sheila J.; Castrignanò, Silvia; Mei, Giampiero; Di Venere, Almerinda; Nicolai, Eleonora; Allegra, Paola; Gilardi, Gianfranco

    2013-01-01

    Human aromatase (CYP19A1) is a steroidogenic cytochrome P450 converting androgens into estrogens. No ligand-free crystal structure of the enzyme is available to date. The crystal structure in complex with the substrate androstenedione and the steroidal inhibitor exemestane shows a very compact conformation of the enzyme, leaving unanswered questions on the conformational changes that must occur to allow access of the ligand to the active site. As H/D exchange kinetics followed by FTIR spectroscopy can provide information on the conformational changes in proteins where solvent accessibility is affected, here the amide I region was used to measure the exchange rates of the different elements of the secondary structure for aromatase in the ligand-free form and in the presence of the substrate androstenedione and the inhibitor anastrozole. Biphasic exponential functions were found to fit the H/D exchange data collected as a function of time. Two exchange rates were assigned to two populations of protons present in different flexible regions of the protein. The addition of the substrate androstenedione and the inhibitor anastrozole lowers the H/D exchange rates of the α-helices of the enzyme when compared to the ligand-free form. Furthermore, the presence of the inhibitor anastrozole lowers exchange rate constant (k1) for β-sheets from 0.22±0.06 min−1 for the inhibitor-bound enzyme to 0.12±0.02 min−1 for the free protein. Dynamics effects localised in helix F were studied by time resolved fluorescence. The data demonstrate that the fluorescence lifetime component associated to Trp224 emission undergoes a shift toward longer lifetimes (from ≈5.0 to ≈5.5 ns) when the substrate or the inhibitor are present, suggesting slower dynamics in the presence of ligands. Together the results are consistent with different degrees of flexibility of the access channel and therefore different conformations adopted by the enzyme in the free, substrate- and inhibitor

  10. Spatially Resolved Far-Ultraviolet Spectroscopy of the Nuclear Region of NGC 1068

    NASA Astrophysics Data System (ADS)

    Zheng, Wei; Wang, Jun-Xian; Kriss, Gerard A.; Sahnow, David; Allen, Mark; Dopita, Michael; Tsvetanov, Zlatan; Bicknell, Geoffrey

    2008-10-01

    We carry out high-resolution FUSE spectroscopy of the nuclear region of NGC 1068. The first set of spectra was obtained with a 30'' square aperture that collected all emission from the narrow-line region. The data reveal a strong broad O VI component of FWHM ~3500 km s-1 and two narrow O VI λλ1031, 1037 components of ~350 km s-1. The C III λ977 and N III λ991 emission lines in this spectrum can be fitted with a narrow component of FWHM ~1000 km s-1 and a broad one of ~2500 km s-1. Another set of seven spatially resolved spectra was made using a long slit of 1.25'' × 20'' at steps of ~1'' along the axis of the emission-line cone. We find the following: (1) Major emission lines in the FUSE wavelength range consist of a broad and a narrow component. (2) There is a gradient in the velocity field for the narrow O VI component of ~200 km s-1 from ~2'' southwest of the nucleus to ~4'' northeast. A similar pattern is also observed with the broad O VI component, with a gradient of ~3000 km s-1. These are consistent with the HST STIS findings and suggest a biconical structure in which the velocity field is mainly radial outflow. (3) A major portion of the C III and N III line flux is produced in the compact core. They are therefore not effective temperature diagnostics for the conical region. (4) The best-fit UV continuum suggests virtually no reddening, and the He II I(λ1640)/I(λ1085) ratio suggests a consistently low extinction factor across the cone. At ~2'' northeast of the nucleus there is a region characterized by (a) a strong Lyα flux but normal C IV flux, (b) a broad O VI line, and (c) a significantly enhanced C III flux. Based on observations made with the NASA-CNES-CSA Far Ultraviolet Spectroscopic Explorer (FUSE), which is operated for NASA by The Johns Hopkins University under NASA contract NAS5-32985, and observations with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is operated by the Association of

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

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

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

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

    PubMed

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

    2016-05-01

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

  13. Time-resolved resonance Raman spectroscopy of radiation-chemical processes. [Pulsed irradiation

    SciTech Connect

    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.

  14. Angle-Resolved Photoemission Spectroscopy on Electronic Structure and Electron-Phonon Coupling in Cuprate Superconductors

    SciTech Connect

    Zhou, X.J.

    2010-04-30

    In addition to the record high superconducting transition temperature (T{sub c}), high temperature cuprate superconductors are characterized by their unusual superconducting properties below T{sub c}, and anomalous normal state properties above T{sub c}. In the superconducting state, although it has long been realized that superconductivity still involves Cooper pairs, as in the traditional BCS theory, the experimentally determined d-wave pairing is different from the usual s-wave pairing found in conventional superconductors. The identification of the pairing mechanism in cuprate superconductors remains an outstanding issue. The normal state properties, particularly in the underdoped region, have been found to be at odd with conventional metals which is usually described by Fermi liquid theory; instead, the normal state at optimal doping fits better with the marginal Fermi liquid phenomenology. Most notable is the observation of the pseudogap state in the underdoped region above T{sub c}. As in other strongly correlated electrons systems, these unusual properties stem from the interplay between electronic, magnetic, lattice and orbital degrees of freedom. Understanding the microscopic process involved in these materials and the interaction of electrons with other entities is essential to understand the mechanism of high temperature superconductivity. Since the discovery of high-T{sub c} superconductivity in cuprates, angle-resolved photoemission spectroscopy (ARPES) has provided key experimental insights in revealing the electronic structure of high temperature superconductors. These include, among others, the earliest identification of dispersion and a large Fermi surface, an anisotropic superconducting gap suggestive of a d-wave order parameter, and an observation of the pseudogap in underdoped samples. In the mean time, this technique itself has experienced a dramatic improvement in its energy and momentum resolutions, leading to a series of new discoveries not

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

    SciTech Connect

    Dorchies, F. Fedorov, N.; Lecherbourg, L.

    2015-07-15

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

  16. Direct Imaging of Transient Fano Resonances in N2 Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J. J.; Kornilov, Oleg

    2016-04-01

    Autoionizing Rydberg states of molecular N2 are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14 ±1 fs , while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance.

  17. Chiral-index resolved length mapping of carbon nanotubes in solution using electric-field induced differential absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Wenshan; Hennrich, Frank; Flavel, Benjamin S.; Kappes, Manfred M.; Krupke, Ralph

    2016-09-01

    The length of single-walled carbon nanotubes (SWCNTs) is an important metric for the integration of SWCNTs into devices and for the performance of SWCNT-based electronic or optoelectronic applications. In this work we propose a rather simple method based on electric-field induced differential absorption spectroscopy to measure the chiral-index-resolved average length of SWCNTs in dispersions. The method takes advantage of the electric-field induced length-dependent dipole moment of nanotubes and has been verified and calibrated by atomic force microscopy. This method not only provides a low cost, in situ approach for length measurements of SWCNTs in dispersion, but due to the sensitivity of the method to the SWCNT chiral index, the chiral index dependent average length of fractions obtained by chromatographic sorting can also be derived. Also, the determination of the chiral-index resolved length distribution seems to be possible using this method.

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

    NASA Astrophysics Data System (ADS)

    Dorchies, F.; Fedorov, N.; Lecherbourg, L.

    2015-07-01

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

  19. Direct Imaging of Transient Fano Resonances in N_{2} Using Time-, Energy-, and Angular-Resolved Photoelectron Spectroscopy.

    PubMed

    Eckstein, Martin; Yang, Chung-Hsin; Frassetto, Fabio; Poletto, Luca; Sansone, Giuseppe; Vrakking, Marc J J; Kornilov, Oleg

    2016-04-22

    Autoionizing Rydberg states of molecular N_{2} are studied using time-, energy-, and angular-resolved photoelectron spectroscopy. A femtosecond extreme ultraviolet pulse with a photon energy of 17.5 eV excites the resonance and a subsequent IR pulse ionizes the molecule before the autoionization takes place. The angular-resolved photoelectron spectra depend on pump-probe time delay and allow for the distinguishing of two electronic states contributing to the resonance. The lifetime of one of the contributions is determined to be 14±1  fs, while the lifetime of the other appears to be significantly shorter than the time resolution of the experiment. These observations suggest that the Rydberg states in this energy region are influenced by the effect of interference stabilization and merge into a complex resonance. PMID:27152799

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  1. Ultrahigh-throughput single-molecule spectroscopy and spectrally resolved super-resolution microscopy.

    PubMed

    Zhang, Zhengyang; Kenny, Samuel J; Hauser, Margaret; Li, Wan; Xu, Ke

    2015-10-01

    By developing a wide-field scheme for spectral measurement and implementing photoswitching, we synchronously obtained the fluorescence spectra and positions of ∼10(6) single molecules in labeled cells in minutes, which consequently enabled spectrally resolved, 'true-color' super-resolution microscopy. The method, called spectrally resolved stochastic optical reconstruction microscopy (SR-STORM), achieved cross-talk-free three-dimensional (3D) imaging for four dyes 10 nm apart in emission spectrum. Excellent resolution was obtained for every channel, and 3D localizations of all molecules were automatically aligned within one imaging path. PMID:26280329

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

    NASA Astrophysics Data System (ADS)

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

    1990-02-01

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

  3. Angle-resolved photoemission spectroscopy of the insulating NaxWO3: Anderson localization, polaron formation, and remnant Fermi surface.

    PubMed

    Raj, S; Hashimoto, D; Matsui, H; Souma, S; Sato, T; Takahashi, T; Sarma, D D; Mahadevan, Priya; Oishi, S

    2006-04-14

    The electronic structure of the insulating sodium tungsten bronze, Na(0.025)WO(3), is investigated by high-resolution angle-resolved photoemission spectroscopy. We find that near-E(F) states are localized due to the strong disorder arising from random distribution of Na+ ions in the WO(3) lattice, which makes the system insulating. The temperature dependence of photoemission spectra provides direct evidence for polaron formation. The remnant Fermi surface of the insulator is found to be the replica of the real Fermi surface in the metallic system. PMID:16712121

  4. Hydrogenic Rydberg States of Molecular van der Waals Complexes: Resolved Rydberg Spectroscopy of DABCO-N2

    NASA Astrophysics Data System (ADS)

    Cockett, Martin C.; Watkins, Mark J.

    2004-01-01

    The complementary threshold ionization techniques of MATI and ZEKE spectroscopy have been used to reveal well-resolved, long-lived (>10 μs) hydrogenic Rydberg series (50≤n≤98) in a van der Waals complex formed between a polyatomic molecule and a diatomic molecule for the first time. The series are observed within 50 cm-1 of the adiabatic ionization threshold as well as two core-excited thresholds corresponding to excitation of up to two quanta in the van der Waals vibra­tional mode.

  5. Interfacing a transient digitizer to a step-scan Fourier transform spectrometer for nanosecond time resolved spectroscopy

    SciTech Connect

    Letendre, L.T.; Dai, H.; McLaren, I.A.; Johnson, T.J.

    1999-01-01

    A new signal processing and data acquisition system has been developed that allows a Fourier transform spectrometer to be interfaced to external transient digitizers for time-resolved spectroscopy. Time resolution is limited only by the transient digitizer and detection system response time. For the present system it is about 1 ns. The capabilities of this system are demonstrated with visible Fourier transform spectra of both scattered laser light and fluorescence from electronically excited NO{sub 2} gas. {copyright} {ital 1999 American Institute of Physics.}

  6. Highly polarized emission in spin resolved photoelectron spectroscopy of alpha-Fe(001)/GaAs(001)

    SciTech Connect

    Tobin, James; Yu, Sung Woo; Morton, Simon; Waddill, George; Thompson, Jamie; Neal, James; Spangenberg, Matthais; Shen, T.H.

    2009-05-19

    Highly spin-polarized sources of electrons, Integrated into device design, remain of great interest to the spintronic and magneto-electronic device community Here, the growth of Fe upon GaAs(001) has been studied with photoelectron spectroscopy (PES), including Spin Resolved PES. Despite evidence of atomic level disorder such as intermixing, an over-layer with the spectroscopic signature of alpha-Fe(001), with a bcc real space ordering, Is obtained The results will be discussed in light of the possibility of using such films as a spin-polarized source in device applications.

  7. Time-Resolved Photoelectron Spectroscopy of Coupled Nuclear-Electronic Dynamics

    NASA Astrophysics Data System (ADS)

    Falge, M.; Engel, V.; Gräfe, S.

    2013-03-01

    We study the effect of nuclear-electron coupling on time-resolved photo-electron spectra, employing a model system which allows to directly comparing spectra resulting from the adiabatic approximation with those obtained within a non-Born-Oppenheimer description.

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

    NASA Astrophysics Data System (ADS)

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

    1996-07-01

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

  9. Diagnosing the plasma nonuniformity in an iron opacity experiment by spatially resolved Al 1s-2p absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Xiaoding, Zhang; Jiyan, Zhang; Yang, Zhao; Gang, Xiong; Bin, Zhao; Guohong, Yang; Jian, Zheng; Jiamin, Yang

    2012-12-01

    Generating a well-characterized hot-dense sample is of great importance to high quality opacity measurements. In this paper, we report on an experimental investigation of the plasma nonuniformity in a radiatively heated iron opacity sample by spatially resolved Al 1s-2p absorption spectroscopy. The iron sample was tamped by plastic at both sides and was heated by thermal x-ray radiation generated in a gold Hohlraum, and an Al layer attached to it was used as a tracer for temperature diagnosis. Spatially resolved 1s-2p transition absorption spectra of the Al tracer were measured by the technique of point-projection-spectroscopy, and temperatures in the sample were obtained by comparing the measured spectra with detailed-term-accounting model calculations, with the density of the sample deduced using a combination of side-on radiography and radiative hydrodynamic simulation. The results showed the existence of axial temperature nonuniformity in the sample, and these temperature variations have been used to explain the shift of iron 2p-3d transition absorption feature along the axial direction of the Hohlraum used to heat the sample successfully.

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

    NASA Astrophysics Data System (ADS)

    Oyama, Shiho; Sakai, Heisuke; Murata, Hideyuki

    2016-03-01

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

  11. Diagnosing the plasma nonuniformity in an iron opacity experiment by spatially resolved Al 1s-2p absorption spectroscopy

    SciTech Connect

    Zhang Xiaoding; Zhang Jiyan; Zhao Yang; Xiong Gang; Yang Guohong; Yang Jiamin; Zhao Bin; Zheng Jian

    2012-12-15

    Generating a well-characterized hot-dense sample is of great importance to high quality opacity measurements. In this paper, we report on an experimental investigation of the plasma nonuniformity in a radiatively heated iron opacity sample by spatially resolved Al 1s-2p absorption spectroscopy. The iron sample was tamped by plastic at both sides and was heated by thermal x-ray radiation generated in a gold Hohlraum, and an Al layer attached to it was used as a tracer for temperature diagnosis. Spatially resolved 1s-2p transition absorption spectra of the Al tracer were measured by the technique of point-projection-spectroscopy, and temperatures in the sample were obtained by comparing the measured spectra with detailed-term-accounting model calculations, with the density of the sample deduced using a combination of side-on radiography and radiative hydrodynamic simulation. The results showed the existence of axial temperature nonuniformity in the sample, and these temperature variations have been used to explain the shift of iron 2p-3d transition absorption feature along the axial direction of the Hohlraum used to heat the sample successfully.

  12. Probing reaction dynamics of transition-metal complexes in solution via time-resolved soft x-ray spectroscopy

    SciTech Connect

    Huse, N.; Kim, T.-K.; Khalil, M.; Jamula, L.; McCusker, J.K.; Schoenlein, R.W.

    2008-08-01

    We report the first time-resolved soft x-ray measurements of solvated transition-metal complexes. L-edge spectroscopy directly probes dynamic changes in ligand-field splitting of 3d orbitals associated with the spin transition, and mediated by changes in ligand-bonding. We report the first time-resolved soft x-ray spectroscopy of solution-phase molecular dynamics. Changes in ligand-field splitting and spin-state populations in 3d orbitals of the Fe{sup II} complex are directly probed via transient absorption changes of the Fe L{sub 2} and L{sub 3} edges following photo-induced metal-to-ligand charge transfer. With the emergence of high-flux ultrafast soft x-ray sources, details on interplay between atomic structure, electronic states, and spin contributions will be revealed. Our experimental approach opens the door to femtosecond soft x-ray investigations of liquid phase chemistry that have previously been inaccessible.

  13. Direct-comb molecular spectroscopy with accurate, resolved comb teeth over 43 THz.

    PubMed

    Zolot, A M; Giorgetta, F R; Baumann, E; Nicholson, J W; Swann, W C; Coddington, I; Newbury, N R

    2012-02-15

    We demonstrate a dual-comb spectrometer using stabilized frequency combs spanning 177 to 220 THz (1360 to 1690 nm) in the near infrared. Comb-tooth-resolved measurements of amplitude and phase generate over 4×10(5) individually resolved spectral elements at 100 MHz point spacing and kilohertz-level resolution and accuracy. The signal-to-noise ratio is 100 to 3000 per comb tooth. Doppler-broadened phase and amplitude spectra of CO(2), CH(4), C(2)H(2), and H(2)O in a 30 m multipass cell agree with established spectral parameters, achieving high-resolution measurements with optical bandwidth generally associated with blackbody sources. PMID:22344132

  14. Time-resolved spectroscopy of charge-transfer fluorescent molecules in polymer matrices

    NASA Astrophysics Data System (ADS)

    Hofstraat, Johannes W.; Verhey, H. J.; Verhoeven, Jan W.; Kuemke, M.; McGown, Linda B.; Novikov, Eugene G.; van Hoek, Arie; Visser, Antonie J. W. G.

    1996-03-01

    Time-resolved fluorescence measurements have been carried out on charge-transfer fluorescent molecules incorporated in polymeric lattices, consisting of polystyrene cores and polyglycidylmethacrylate shells, and in polymethylmethacrylate thin films. New approaches to the analysis of fluorescence lifetime data obtained for molecules in polymer matrices had to be applied, since conventional analysis methods appeared not suitable for such strongly heterogeneous systems. The polymer lattices could be characterized by application of phase- resolved fluorescence lifetime measurements followed by maximum-entropy methods for data analysis. The thin films were studied using time-correlated single photon counting fluorescence lifetime measurements and data analysis with a home-built program based on stretched exponential decays. Interactions of the fluorescent guest molecules could be established by combined fluorescence lifetime and depolarization measurements. Suggestions for further improvements in fluorescence lifetime methods for characterization of polymeric materials have been made.

  15. Angle-resolved scattering spectroscopy of explosives using an external cavity quantum cascade laser

    SciTech Connect

    Suter, Jonathan D.; Bernacki, Bruce E.; Phillips, Mark C.

    2012-04-01

    Investigation of angle-resolved scattering from solid explosives residues on a car door for non-contact sensing geometries. Illumination with a mid-infrared external cavity quantum cascade laser tuning between 7 and 8 microns was detected both with a sensitive single point detector and a hyperspectral imaging camera. Spectral scattering phenomena were discussed and possibilities for hyperspectral imaging at large scattering angles were outlined.

  16. Frequency-domain time-resolved four wave mixing spectroscopy of vibrational coherence transfer with single-color excitation.

    PubMed

    Pakoulev, Andrei V; Rickard, Mark A; Mathew, Nathan A; Kornau, Kathryn M; Wright, John C

    2008-07-17

    Triply vibrationally enhanced four-wave mixing spectroscopy is employed to observe vibrational coherence transfer between the asymmetric and symmetric CO-stretching modes of rhodium(I) dicarbonyl acetylacetonate (RDC). Coherence transfer is a nonradiative transition of a coherent superposition of quantum states to a different coherent superposition due to coupling of the vibrational modes through the bath. All three excitation pulses in the experiment are resonant with a single quantum coherence, but coherence transfer results in new coherences with different frequencies. The new output frequency is observed with a monochromator that resolves it from the stronger peak at the original excitation frequency. This technique spectrally resolves pathways that include coherence transfer, discriminates against spectral features created solely by radiative transitions, and temporally resolves modulations created by interference between different coherence transfer pathways. Redfield theory simulates the temporal modulations in the impulsive limit, but it is also clear that coherence transfer violates the secular approximation invoked in most Redfield theories. Instead, it requires non-Markovian and bath memory effects. RDC may provide a simple model for the development of theories that incorporate these effects. PMID:18572931

  17. A high-efficiency spin-resolved photoemission spectrometer combining time-of-flight spectroscopy with exchange-scattering polarimetry

    SciTech Connect

    Jozwiak, Chris M.; Graff, Jeff; Lebedev, Gennadi; Andresen, Nord; Schmid, Andreas; Fedorov, Alexei; El Gabaly, Farid; Wan, Weishi; Lanzara, Alessandra; Hussain, Zahid

    2010-04-13

    We describe a spin-resolved electron spectrometer capable of uniquely efficient and high energy resolution measurements. Spin analysis is obtained through polarimetry based on low-energy exchange scattering from a ferromagnetic thin-film target. This approach can achieve a similar analyzing power (Sherman function) as state-of-the-art Mott scattering polarimeters, but with as much as 100 times improved efficiency due to increased reflectivity. Performance is further enhanced by integrating the polarimeter into a time-of-flight (TOF) based energy analysis scheme with a precise and flexible electrostatic lens system. The parallel acquisition of a range of electron kinetic energies afforded by the TOF approach results in an order of magnitude (or more) increase in efficiency compared to hemispherical analyzers. The lens system additionally features a 90 degrees bandpass filter, which by removing unwanted parts of the photoelectron distribution allows the TOF technique to be performed at low electron drift energy and high energy resolution within a wide range of experimental parameters. The spectrometer is ideally suited for high-resolution spin- and angle-resolved photoemission spectroscopy (spin-ARPES), and initial results are shown. The TOF approach makes the spectrometer especially ideal for time-resolved spin-ARPES experiments.

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

    PubMed

    Ogawa, Manami; Yamamoto, Susumu; Kousa, Yuka; Nakamura, Fumitaka; Yukawa, Ryu; Fukushima, Akiko; Harasawa, Ayumi; Kondoh, Hiroshi; Tanaka, Yoshihito; Kakizaki, Akito; Matsuda, Iwao

    2012-02-01

    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. PMID:22380081

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

    SciTech Connect

    Ogawa, Manami; Yamamoto, Susumu; Nakamura, Fumitaka; Yukawa, Ryu; Fukushima, Akiko; Harasawa, Ayumi; Kakizaki, Akito; Matsuda, Iwao; Kousa, Yuka; Kondoh, Hiroshi; Tanaka, Yoshihito

    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.

  20. Time-resolved spectroscopy of the Mercury 6 3P1 state

    NASA Technical Reports Server (NTRS)

    Halstead, J. A.; Reeves, R. R.

    1981-01-01

    The time-resolved fluorescence was observed from the Hg 6 3P1 state under the influence of the earth's magnetic field and with applied fields of up to 14 G. Modulation of the fluorescence decay signal was observed as a function of both time and space and can be interpreted in terms of a classical precession of the excited atom about the magnetic field or as quantum beats resulting from interference between coherently populated Zeeman sublevels. This modulation was studied for each of the five resolvable components of the hyperfine structure separately. The fluorescence from the even isotopes was determined to be almost completely modulated while the fluorescence from the odd isotopes was only partially modulated. The frequency of modulation of the fluorescence from the mercury-202 isotope was observed as a function of the applied magnetic field and a value for the Lande factor of 1.46 + or - 0.03 was obtained. This is within experimental error of the accepted value of 1.486. In addition, the frequency of modulation as a function of applied magnetic field was determined for each of the three resolvable components with more than one contributing isotopic hyperfine line. An investigation of the effect of radiation trapping on the degree modulation was also made.

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

    NASA Astrophysics Data System (ADS)

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

    2003-04-01

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

  2. Spectrally interleaved, comb-mode-resolved spectroscopy using swept dual terahertz combs

    PubMed Central

    Hsieh, Yi-Da; Iyonaga, Yuki; Sakaguchi, Yoshiyuki; Yokoyama, Shuko; Inaba, Hajime; Minoshima, Kaoru; Hindle, Francis; Araki, Tsutomu; Yasui, Takeshi

    2014-01-01

    Optical frequency combs are innovative tools for broadband spectroscopy because a series of comb modes can serve as frequency markers that are traceable to a microwave frequency standard. However, a mode distribution that is too discrete limits the spectral sampling interval to the mode frequency spacing even though individual mode linewidth is sufficiently narrow. Here, using a combination of a spectral interleaving and dual-comb spectroscopy in the terahertz (THz) region, we achieved a spectral sampling interval equal to the mode linewidth rather than the mode spacing. The spectrally interleaved THz comb was realized by sweeping the laser repetition frequency and interleaving additional frequency marks. In low-pressure gas spectroscopy, we achieved an improved spectral sampling density of 2.5 MHz and enhanced spectral accuracy of 8.39 × 10−7 in the THz region. The proposed method is a powerful tool for simultaneously achieving high resolution, high accuracy, and broad spectral coverage in THz spectroscopy. PMID:24448604

  3. Spatial resolved temperature measurement based on absorption spectroscopy using a single tunable diode laser

    NASA Astrophysics Data System (ADS)

    Yu, Xilong; Li, Fei; Chen, Lihong; Zhang, Xinyu

    2010-03-01

    A novel method based on wavelength-multiplexed line-of-sight absorption and profile fitting for non-uniform flow field measurement is reported. A wavelength scanning combing laser temperature and current modulation WMS scheme is used to implement the wavelength-multiplexed-profile fitting method. Second harmonic (2f) signal of eight H2O transitions features near 7,170 cm-1 are measured in one period using a single tunable diode laser. Spatial resolved temperature distribution upon a CH4/air premixed flat flame burner is obtained. The result validates the feasibility of strategy for non-uniform flow field diagnostics by means of WMS-2f TDLAS.

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    1995-11-01

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

  6. Development of time resolved x-ray spectroscopy in high intensity laser-plasma interactions

    SciTech Connect

    Notley, M. M.; Weber, R. L.; Fell, B.; Jeffries, J.; Freeman, R. R.; Mackinnon, A. J.; Dickson, R.; Hey, D.; Khattak, F.; Saiz, E. Garcia; Gregori, G.

    2006-10-15

    This article discusses the design of a novel time resolved von Hamos Bragg spectrometer to provide spectra in the region around the titanium K-{alpha} and He-{alpha} lines. The instrument consists of a highly oriented pyrolitic graphite mosaic crystal coupled to a picosecond x-ray streak camera. Measurements of the time dependent behavior from Ti foils illuminated with intense laser pulses can be used to improve the understanding of recombination dynamics, electron transport, and phase transitions in strongly coupled dense plasma. This is important for the modeling of the compression phase in inertial confinement fusion research and the study of astrophysical environments.

  7. Spatially resolved x-ray spectroscopy investigation of femtosecond laser irradiated Ar clusters.

    PubMed

    Junkel-Vives, G C; Abdallah, J; Auguste, T; D'Oliveira, P; Hulin, S; Monot, P; Dobosz, S; Faenov, A Ya; Magunov, A I; Pikuz, T A; Skobelev, I Yu; Boldarev, A S; Gasilov, V A

    2002-03-01

    High temperature plasmas have been created by irradiating Ar clusters with high intensity 60-fs laser pulses. Detailed spectroscopic analysis of spatially resolved, high resolution x-ray data near the He(alpha) line of Ar is consistent with a two-temperature collisional-radiative model incorporating the effects of highly energetic electrons. The results of the spectral analysis are compared with a theoretical hydrodynamic model of cluster production, as well as interferometric data. The plasma parameters are notably uniform over one Rayleigh length (600 microm). PMID:11909265

  8. Direct observation of the mass renormalization in SrVO3 by angle resolved photoemission spectroscopy

    SciTech Connect

    Yoshida, t.

    2010-05-03

    We have performed an angle-resolved photoemission study of the three-dimensional perovskite-type SrVO{sub 3}. Observed spectral weight distribution of the coherent part in the momentum space shows cylindrical Fermi surfaces consisting of the V 3d t{sub 2g} orbitals as predicted by local-density approximation (LDA) band-structure calculation. The observed energy dispersion shows a moderately enhanced effective mass compared to the LDA results, corresponding to the effective mass enhancement seen in the thermodynamic properties. Contributions from the bulk and surface electronic structures to the observed spectra are discussed based on model calculations.

  9. PHASE-RESOLVED INFRARED SPECTROSCOPY AND PHOTOMETRY OF V1500 CYGNI, AND A SEARCH FOR SIMILAR OLD CLASSICAL NOVAE

    SciTech Connect

    Harrison, Thomas E.; Campbell, Randy D.; Lyke, James E. E-mail: jlyke@keck.hawaii.edu

    2013-08-01

    We present phase-resolved near-infrared photometry and spectroscopy of the classical nova (CN) V1500 Cyg to explore whether cyclotron emission is present in this system. While the spectroscopy do not indicate the presence of discrete cyclotron harmonic emission, the light curves suggest that a sizable fraction of its near-infrared fluxes are due to this component. The light curves of V1500 Cyg appear to remain dominated by emission from the heated face of the secondary star in this system. We have used infrared spectroscopy and photometry to search for other potential magnetic systems among old CNe. We have found that the infrared light curves of V1974 Cyg superficially resemble those of V1500 Cyg, suggesting a highly irradiated companion. The old novae V446 Her and QV Vul have light curves with large amplitude variations like those seen in polars, suggesting they might have magnetic primaries. We extract photometry for 79 old novae from the Two Micron All Sky Survey Point Source Catalog and use those data to derive the mean, un-reddened infrared colors of quiescent novae. We also extract WISE data for these objects and find that 45 of them were detected. Surprisingly, a number of these systems were detected in the WISE 22 {mu}m band. While two of those objects produced significant dust shells (V705 Cas and V445 Pup), the others did not. It appears that line emission from their ionized ejected shells is the most likely explanation for those detections.

  10. TOF Electron Energy Analyzer for Spin and Angular Resolved Photoemission Spectroscopy

    SciTech Connect

    Lebedev, Gennadi; Jozwiak, Chris; Andresen, Nord; Lanzara, Alessandra; Hussain, Zahid

    2008-07-09

    Current pulsed laser and synchrotron x-ray sources provide new opportunities for Time-Of- Flight (TOF) based photoemission spectroscopy to increase photoelectron energy resolution and efficiency compared to current standard techniques. The principals of photoelectron timing front formation, temporal aberration minimization, and optimization of electron beam transmission are presented. We have developed these concepts into a high resolution Electron Optical Scheme (EOS) of a TOF Electron Energy Analyzer (TOF-EEA) for photoemission spectroscopy. The EOS of the analyzer includes an electrostatic objective lens, three columns of transport lenses and a 90 degree energy band pass filter (BPF). The analyzer has two modes of operation: Spectrometer Mode (SM) with straight passage of electrons through the EOS undeflected by the BPF, allowing the entire spectrum to be measured, and Monochromator Mode (MM) in which the BPF defines a certain energy window inside the scope of the electron energy spectrum.

  11. Spatially resolved optical and near-infrared spectroscopy of I Zw 18

    NASA Technical Reports Server (NTRS)

    Skillman, Evan D.; Kennicutt, Robert C., Jr.

    1993-01-01

    Long-slit optical and near-IR spectroscopy are presented for the bright NW and faint SE components of the oxygen-poor H II galaxy I Zw 18, yielding physical conditions and O, N, S, and He abundances for these components. All of the elemental abundances for the two components of I Zw 18 are equal (within errors), thereby placing constraints on evolutionary theories for this system.

  12. Spatially resolved Raman spectroscopy on indium-catalyzed core-shell germanium nanowires: size effects.

    PubMed

    Xiang, Y; Zardo, I; Cao, L Y; Garma, T; Heiss, M; Morante, J R; Arbiol, J; Brongersma, M L; Fontcuberta I Morral, A

    2010-03-12

    The structure of indium-catalyzed germanium nanowires is investigated by atomic force microscopy, scanning confocal Raman spectroscopy and transmission electron microscopy. The nanowires are formed by a crystalline core and an amorphous shell. We find that the diameter of the crystalline core varies along the nanowire, down to few nanometers. Phonon confinement effects are observed in the regions where the crystalline region is the thinnest. The results are consistent with the thermally insulating behavior of the core-shell nanowires. PMID:20154375

  13. Wavelength-resolved emission spectroscopy of the alkoxy and alkylthio radicals in a supersonic jet

    NASA Technical Reports Server (NTRS)

    Misra, Prabhakar; Zhu, Xinming; Hsueh, Ching-Yu; Kamal, Mohammed M.

    1993-01-01

    Wavelength-resolved emission spectra of methoxy (CH3O) and methylthio (CH3S) radicals have been obtained in a supersonic jet environment with a resolution of 0.3 nm by dispersing the total laser-induced fluorescence with a 0.6 m monochromator. A detailed analysis of the single vibronic level dispersed fluorescence spectra yields the following vibrational frequencies for CH3O in the X(2)E state; nu(sub 1 double prime) = 2953/cm, nu(sub 2 double prime) = 1375/cm, nu(sub 3 double prime) = 1062/cm, nu(sub 4 double prime) = 2869/cm, nu(sub 5 double prime) = 1528/cm and nu(sub 6 double prime) = 688/cm. A similar analysis of the wavelength-resolved emission spectra of CH3S provides the following ground state vibrational frequencies: nu(sub 2 double prime) = 1329/cm, nu(sub 3 double prime) = 739/cm and nu(sub 6 double prime) = 601/cm. An experimental uncertainty of 20/cm is estimated for the assigned frequencies.

  14. Time-resolved spectroscopy of endogenous NAD(P)H in Gluconobacter oxydans

    NASA Astrophysics Data System (ADS)

    Horilova, J.; Kromkova, K.; Bucko, M.; Illesova, A.; Vikartovska, A.; Stefuca, V.; Mateasik, A.; Chorvat, D.; Chorvatova, A.

    2013-02-01

    The genus Gluconobacter is frequently used for biotechnological and/or nanotechnological applications. We studied endogenous fluorescence of nicotinamide adenine dinucleotide (phosphate) (NAD(P)H), indicator of the oxidative metabolic state in mammalian cells, in Gluconobacter oxydans (G. oxydans). Time-resolved measurements (excitation by 375nm pulsed diode laser) were employed to record the bacterial fluorescence intensity, as well as its modifications by metabolic modulation. Results were gathered on fresh bacteria, on de-frozen ones, as well as on bacteria encapsulated in alginate beads. NAD(P)H fluorescence increased linearly with the concentration of bacteria. Freezing, which has little effect on the viability of bacteria or the concentration-dependent fluorescence rise, affected the temperature-dependence of NAD(P)H fluorescence. Sodium cyanide (10 mM) provoked significant rise in the NAD(P)H fluorescence, while dinitrophenol (200 μM) induced its decrease, confirming the bacterial NAD(P)H fluorescence sensitivity to modulators of electron transport chain. Gathered results demonstrate that endogenous NAD(P)H fluorescence can be successfully recorded in the bacterial strain G. oxydans using time-resolved measurements.

  15. Time-resolved and steady-state fluorescence spectroscopy from bacteria subjected to bactericidal agents

    NASA Astrophysics Data System (ADS)

    Katz, Alvin; Alimova, Alexandra; Siddique, Masood; Savage, Howard E.; Shah, Mahendra; Rosen, Richard; Alfano, Robert

    2004-03-01

    The time-resolved and steady-state changes in fluorescence were investigated from one spore-forming (Bacillus subtilis) and four non-spore forming (Escherichia coli, Staphylococcus aureus, Enterococcus faecalis, and Pseudomonas aeruginosa) bacteria subjected to different bactericidal agents. The bactericidal agents were sodium hypochlorite (bleach) hydrogen peroxide, formaldehyde, and UV light exposure. Application of sodium hypochlorite resulted in an almost total lose of fluorescence signal and large decrease in the optical density of the bacterial suspension. Addition of hydrogen peroxide resulted in a 35% decrease in emission intensity fom the Sa and an 85-95% decrease for the other bacteria. Ultraviolet light exposure resulted in a 5-35% decrease in the emission intensity of the tryptophan band. The addition of formaldehyde to the bacteria did not result in significant changes in the steady-state emission intensity, but did shift the tryptophan emission peak position to shorter wavelengths by 3 to 5 nm. Time-resolved fluorescence measurements showed that the fluorescence lifetime of tryptophan in the bacteria could not be described by a single exponential decay, and was similar to that of tryptophan in neutral aqueous solution. Upon addition of formaldehyde to the Gram positive bacteria (Bs and Sa) the strength of the short lifetime component increased dramatically, while for the Gram negative bacteria, a smaller increase was observed. These fluorescence changes reflect the different mechanisms of the bactericidal agents and may provide a useful tool to monitor the effectiveness of disinfectants.

  16. Spatially resolved high resolution x-ray spectroscopy for magnetically confined fusion plasmas (invited)

    SciTech Connect

    Ince-Cushman, A.; Rice, J. E.; Reinke, M. L.; Podpaly, Y.; Marmar, E. S.; Bitter, M.; Hill, K. W.; Scott, S.; Gu, M. F.; Eikenberry, E.; Broennimann, Ch.; Lee, S. G.

    2008-10-15

    The use of high resolution x-ray crystal spectrometers to diagnose fusion plasmas has been limited by the poor spatial localization associated with chord integrated measurements. Taking advantage of a new x-ray imaging spectrometer concept [M. Bitter et al., Rev. Sci. Instrum. 75, 3660 (2004)], and improvements in x-ray detector technology [Ch. Broennimann et al., J. Synchrotron Radiat. 13, 120 (2006)], a spatially resolving high resolution x-ray spectrometer has been built and installed on the Alcator C-Mod tokamak. This instrument utilizes a spherically bent quartz crystal and a set of two dimensional x-ray detectors arranged in the Johann configuration [H. H. Johann, Z. Phys. 69, 185 (1931)] to image the entire plasma cross section with a spatial resolution of about 1 cm. The spectrometer was designed to measure line emission from H-like and He-like argon in the wavelength range 3.7 and 4.0 A with a resolving power of approximately 10 000 at frame rates up to 200 Hz. Using spectral tomographic techniques [I. Condrea, Phys. Plasmas 11, 2427 (2004)] the line integrated spectra can be inverted to infer profiles of impurity emissivity, velocity, and temperature. From these quantities it is then possible to calculate impurity density and electron temperature profiles. An overview of the instrument, analysis techniques, and example profiles are presented.

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

    NASA Astrophysics Data System (ADS)

    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

  18. Time resolved optical biopsy spectroscopy of normal, benign and malignant tissues from NADH and FAD changes

    NASA Astrophysics Data System (ADS)

    Masilamani, V.; Das, B. B.; Secor, J.; AlSalhi, M.; Amer, S. B.; Farhat, K.; Rabah, D.; Alfano, R. R.

    2012-01-01

    Histo pathological examination is the gold standard to discriminate between benign and malignant growth of tissue. But this is invasive and stressful. Hence many non invasive imaging techniques, such as CT, MRI, PET, etc are employed, each having certain advantages and disadvantages. In this context optical biopsy is a newly emerging technique, since it employs non-ionizing radiation like light or laser, which could be shined directly or launched through optical fiber to reach any part of the body. This paper reports results of time resolved emission spectra of 24 excised tissue sample (normal control=12; benign=4; malignant=8) of breast and prostate, employing a 390nm, 100 fs, Ti-Sapphire laser pulses. The fluorescence decay times were measured using streak camera and fitted for single and bi- exponential decays with reliability of 97%. Our results show the distinct difference between normal, benign and malignant tissues attributed changes of NADH and FAD levels.

  19. Averaging picosecond streak camera for time resolved x-ray and XUV spectroscopy of ultrashort plasmas

    NASA Astrophysics Data System (ADS)

    Maksimchuk, A.; Nantel, M.; Workman, J.; Umstadter, D.; Mourou, G.; Pikuz, S.

    1996-11-01

    We have developed an averaging picosecond x-ray streak camera that uses a DC-biased semi-insulating GaAs photoconductive switch as a generator of a high-voltage ramp for the deflection plates of the streak camera. The streak camera is operated at a sweep speed of up to 8 ps/mm, with a shot-to-shot jitter of 1 ps. The streak camera driven by this switch is absolutely synhronized with the femtosecond laser pulse and allows the direct accumulation of the x-ray temporal signals at a 10 Hz repetition rate. The streak camera has been used for the investigation of temporal behavior of keV x-ray lines and spectrally resolved XUV emission from solid target at the laser intensity of 10^17 W/cm^2. This work is supported by NSF under Grant STC PHY 8920108.

  20. Time-resolved spectroscopy of self-assembly of CCMV protein capsids

    NASA Astrophysics Data System (ADS)

    Moore, Jelyn; Aronzon, Dina; Manoharan, V. N.

    2008-10-01

    In order to gain a deeper understanding of the process a virus undergoes to assemble; the purpose of this study to time resolve the self-assembly of a virus. Cowpea Chlorotic Mottle virus (CCMV), an icosahedral type virus, can assemble without its genetic code (RNA) depending on its chemical and physical surroundings. The surface plasmon resonance (SPR) of colloidal gold particles is known to display a shift when the gold interacts with the proteins of a virus. Surface plasmon resonance is the free electron oscillation occurring at the surface of the gold particle resulting in a characteristic peak location at maximal absorbance and peak width. The shift results from the change in the refractive index of the particles as induced by the presence of the proteins. We hope to detect this shift through total internal reflection microscopy (TIRM). The accomplishments of this research are the completion of the TIR setup and the purification of the virus and its proteins.

  1. Polarization-resolved spectroscopy imaging of grain boundaries and optical excitations in crystalline organic thin films

    PubMed Central

    Pan, Z.; Rawat, N.; Cour, I.; Manning, L.; Headrick, R. L.; Furis, M.

    2015-01-01

    Exploration of optical properties of organic crystalline semiconductors thin films is challenging due to submicron grain sizes and the presence of numerous structural defects, disorder and grain boundaries. Here we report on the results of combined linear dichroism (LD)/ polarization-resolved photoluminescence (PL) scanning microscopy experiments that simultaneously probe the excitonic radiative recombination and the molecular ordering in solution-processed metal-free phthalocyanine crystalline thin films with macroscopic grain sizes. LD/PL images reveal the relative orientation of the singlet exciton transition dipoles at the grain boundaries and the presence of a localized electronic state that acts like a barrier for exciton diffusion across the grain boundary. We also show how this energy barrier can be entirely eliminated through the optimization of deposition parameters that results in films with large grain sizes and small-angle boundaries. These studies open an avenue for exploring the influence of long-range order on exciton diffusion and carrier transport. PMID:26365682

  2. Orbital Rashba effect and its detection by circular dichroism angle-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Park, Jin-Hong; Kim, Choong H.; Rhim, Jun-Won; Han, Jung Hoon

    2012-05-01

    We show, by way of tight-binding and first-principles calculations, that a one-to-one correspondence between an electron's crystal momentum k and nonzero orbital angular momentum (OAM) is a generic feature of surface bands. The OAM forms a chiral structure in momentum space much as its spin counterpart in Rashba model does, as a consequence of the inherent inversion symmetry breaking at the surface but not of spin-orbit interaction. This is the orbital counterpart of conventional Rashba effect and may be called the “orbital Rashba effect.” The circular dichroism (CD) angle-resolved photoemission (ARPES) method is an efficient way to detect this new order, and we derive formulas explicitly relating the CD-ARPES signal to the existence of OAM in the band structure. The cases of degenerate p- and d-orbital bands are considered.

  3. Time-resolved positron annihilation spectroscopy study of relaxation dynamics of ion damage in fused quartz

    NASA Astrophysics Data System (ADS)

    Tsuchida, Hidetsugu; Mizuno, Shohei; Tsutsumi, Hironori; Kinomura, Atsushi; Suzuki, Ryoichi; Itoh, Akio

    2016-05-01

    Relaxation dynamics of ion damage in fused quartz is investigated by our newly developed pump–probe technique combining energetic ions (pump) with slow positrons (probe). This method enables determination of time-resolved positron lifetime. We study the time-dependent relaxation of ion damage, by analyzing the intensity variation in the ortho-positronium lifetime component associated with irradiation damage. For irradiation with 160 keV He ions in the temperature range of 300–573 K, the positron annihilation lifetime spectra are obtained as a function of time after ion irradiation. We observe that the relaxation time of ion damage is strongly influenced by specimen temperatures; the relaxation time constant is approximately 400 ms at room temperature (300 K) and becomes smaller with an increasing temperature. Analysis for the effect of temperature on damage accumulation reveals that the activation energy for thermal annealing of the observed damage is approximately 0.1 eV.

  4. Chandra Phase-Resolved X-Ray Spectroscopy of the Crab Pulsar

    NASA Technical Reports Server (NTRS)

    Weisskopf, Martin C.; ODell, Stephen L.; Paerels, Frits; Elsner, Ronald F.; Becker, Werner E.; Tennant, Allyn F.; Swartz, Douglas A.

    2003-01-01

    We present here the first phase-resolved study of the X-ray spectral properties of the Crab Pulsar that covers all pulse phases. The superb angular resolution of the Chandra X-ray Observatory enables distinguishing the pulsar from the surrounding nebulosity, even at pulse minimum. Analysis of the pulse-averaged spectrum measures interstellar photoelectric absorption and scattering by dust grains in the direction of the Crab Nebula. Analysis of the spectrum as a function of pulse phase measures the low-energy X-ray spectral index even at pulse minimum - albeit with large statistical uncertainty. The data are used to set a new upper limit to any thermal component.

  5. Drug/protein interactions studied by time-resolved fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Gustavsson, Thomas; Markovitsi, Dimitra; Vayá, Ignacio; Bonancía, Paula; Jiménez, M. C.; Miranda, Miguel A.

    2014-09-01

    We report here on a recent time-resolved fluorescence study [1] of the interaction between flurbiprofen (FBP), a chiral non-steroidal anti-inflammatory drug, and human serum albumin (HSA), the main transport protein in the human body. We compare the results obtained for the drug-protein complex with those of various covalently linked flurbiprofentryptophan dyads having well-defined geometries. In all cases stereoselective dynamic fluorescence quenching is observed, varying greatly from one system to another. In addition, the fluorescence anisotropy decays also display a clear stereoselectivity. For the drug-protein complexes, this can be interpreted in terms of the protein microenvironment playing a significant role in the conformational relaxation of FBP, which is more restricted in the case of the (R)- enantiomer.

  6. Theory of spatiotemporally resolved spectroscopy for phase-separation dynamics in electron-hole systems

    NASA Astrophysics Data System (ADS)

    Ishikawa, Akira

    2013-02-01

    Phase separation such as the formation of electron-hole droplets has been observed in semiconductor electron-hole systems. In such conventional experiments, the information averaged in real space was obtained. However, in recent years, optical-near-field techniques have enabled us to acquire spatial information. In this study, I propose a theoretical formulation of spatiotemporal dynamics and spatiotemporally resolved optical response of the gas-liquid phase separation in electron-hole systems. In addition, the nature of the nonequilibrium open system is an essential point in electron-hole systems. Therefore, I investigate the effect of the finite lifetime of electron-hole pairs on phase-separation dynamics. Contribution to the Topical Issue "Excitonic Processes in Condensed Matter, Nanostructured and Molecular Materials", edited by Maria Antonietta Loi, Jasper Knoester and Paul H. M. van Loosdrecht.

  7. Tunable vacuum ultraviolet laser based spectrometer for angle resolved photoemission spectroscopy

    SciTech Connect

    Jiang, Rui; Mou, Daixiang; Wu, Yun; Huang, Lunan; Kaminski, Adam; McMillen, Colin D.; Kolis, Joseph; Giesber, Henry G.; Egan, John J.

    2014-03-15

    We have developed an angle-resolved photoemission spectrometer with tunable vacuum ultraviolet laser as a photon source. The photon source is based on the fourth harmonic generation of a near IR beam from a Ti:sapphire laser pumped by a CW green laser and tunable between 5.3 eV and 7 eV. The most important part of the set-up is a compact, vacuum enclosed fourth harmonic generator based on potassium beryllium fluoroborate crystals, grown hydrothermally in the US. This source can deliver a photon flux of over 10{sup 14} photon/s. We demonstrate that this energy range is sufficient to measure the k{sub z} dispersion in an iron arsenic high temperature superconductor, which was previously only possible at synchrotron facilities.

  8. Vibrational Cooling in A Cold Ion Trap: Vibrationally Resolved Photoelectron Spectroscopy of Cold C60- Anions

    SciTech Connect

    Wang, Xue B.; Woo, Hin-koon; Wang, Lai S.

    2005-08-01

    We demonstrate vibrational cooling of anions via collisions with a background gas in an ion trap attached to a cryogenically controlled cold head (10 ? 400 K). Photoelectron spectra of vibrationally cold C60- anions, produced by electrospray ionization and cooled in the cold ion trap, have been obtained. Relative to spectra taken at room temperature, vibrational hot bands are completely eliminated, yielding well resolved vibrational structures and a more accurate electron affinity for neutral C60. The electron affinity of C60 is measured to be 2.683 ? 0.008 eV. The cold spectra reveal complicated vibrational structures for the transition to the C60 ground state due to the Jahn-Teller effect in the ground state of C60-. Vibrational excitations in the two Ag modes and eight Hg modes are observed, providing ideal data to assess the vibronic couplings in C60-.

  9. Time-resolved spectroscopy of Bi3+ centers in Y4Al2O9

    NASA Astrophysics Data System (ADS)

    Babin, V.; Lipińska, L.; Mihokova, E.; Nikl, M.; Shalapska, T.; Suchocki, A.; Zazubovich, S.; Zhydachevskii, Ya

    2015-08-01

    Steady-state and time-resolved emission and excitation spectra as well as luminescence decay kinetics are studied at 4.2-400 K under excitation in the 3-6 eV energy range for Bi3+ ions substituting for Y3+ ions in four inequivalent crystal lattice sites of Y4Al2O9:Bi ceramics. Luminescence characteristics of Bi3+ centers of all the four types are identified and are shown to arise from the radiative decay of the triplet relaxed excited state (RES) of Bi3+ ions. The parameters of the triplet RES, namely, probabilities of the radiative and nonradiative transitions from the metastable and emitting levels as well as the energy distance between these levels, are determined. The influence of the nearest surroundings of Bi3+ ions on the luminescence characteristics and the parameters of the triplet RES of Bi3+ centers is discussed.

  10. Rotationally-resolved excitation spectroscopy of the alkoxy and alkylthio radicals in a supersonic jet

    NASA Technical Reports Server (NTRS)

    Misra, Prabhakar; Zhu, Xinming; Bryant, Hosie L.; Kamal, Mohammed M.

    1993-01-01

    Rotationally-resolved laser excitation spectra have been obtained for the alkoxy radicals (CH3O, C2H5O, i-C3H7O) and the alkylthio radicals (CH3S, C2H5S, i-C3H7S) in a supersonic jet expansion. Low resolution (0.2/cm) excitation spectra have helped identify several vibronic bands belonging to the A-X electronic system for these jet-cooled free radicals. High resolution (0.07/cm) laser-induced fluorescence excitation spectra have aided the unraveling of the associated rotational structure and in certain cases (CH3O and CH3S, for example) enabled explicit rotational (J,K) assignments of the transitions.

  11. Phase-resolved Spectroscopy of the Intermediate Polars -- TV Col and V1223 Sgr

    NASA Astrophysics Data System (ADS)

    Long, K.

    The cataclysmic variables called intermediate polars are characterized by magnetic fields that rip material from an accretion disk and funnel it to a WD that is not phase-locked to the binary period of the system. This is a proposal to use FUSE to conduct a time-resolved spectroscopic study to dissect the emission of two long-period intermediate polars, V1223 Sgr and TV Col, with very different inclination angles. These, along with the short-period high-inclination IP EX Hya (already observed with FUSE), comprise the only IPs with accurate distances derived from HST astrometry. We will isolate emission from the photosphere of the WD, the magnetically dominated accretion curtain, and the accretion stream. Having characterized the emission sources, we will explore the physical conditions in these same regions, and develop an integrated picture of these two intermediate polars.

  12. Chromatic-free spatially resolved optical emission spectroscopy diagnostics for microplasma

    NASA Astrophysics Data System (ADS)

    Zhu, Li-Guo; Chen, Wen-Cong; Zhu, Xi-Ming; Pu, Yi-Kang; Li, Ze-Ren

    2009-02-01

    A chromatic-free spatially resolved diagnostic system for microplasma measurement is proposed and demonstrated, which consists of an optical chromatic-free microscope mirror system, an electron multiplying charge coupled device (EMCCD), and bandpass filters. The diagnostic system free of chromatic aberrations with a spatial resolution of about 6 μm is achieved. The factors that limit the resolution of this diagnostic system have been analyzed, which are optical diffraction, the pixel size of the EMCCD, and the thickness of the microplasma. In this paper, the optimal condition for achieving a maximum resolution power has been analyzed. With this diagnostic system, we revealed the spatial nonuniformity of a microwave atmospheric-pressure argon microplasma. Furthermore, the spatial distribution of the time-averaged effective electron temperature has been estimated from the intensity distributions of 750.4 and 415.8 nm emissions.

  13. Noninvasive diagnostics of skin microphysical parameters based on spatially resolved diffuse reflectance spectroscopy

    NASA Astrophysics Data System (ADS)

    Lisenko, S. A.; Kugeiko, M. M.

    2013-01-01

    The ability to determine noninvasively microphysical parameters (MPPs) of skin characteristic of malignant melanoma was demonstrated. The MPPs were the melanin content in dermis, saturation of tissue with blood vessels, and concentration and effective size of tissue scatterers. The proposed method was based on spatially resolved spectral measurements of skin diffuse reflectance and multiple regressions between linearly independent measurement components and skin MPPs. The regressions were established by modeling radiation transfer in skin with a wide variation of its MPPs. Errors in the determination of skin MPPs were estimated using fiber-optic measurements of its diffuse reflectance at wavelengths of commercially available semiconductor diode lasers (578, 625, 660, 760, and 806 nm) at source-detector separations of 0.23-1.38 mm.

  14. Angle resolved photoelectron spectroscopy of two-color XUV–NIR ionization with polarization control

    NASA Astrophysics Data System (ADS)

    Düsterer, S.; Hartmann, G.; Babies, F.; Beckmann, A.; Brenner, G.; Buck, J.; Costello, J.; Dammann, L.; De Fanis, A.; Geßler, P.; Glaser, L.; Ilchen, M.; Johnsson, P.; Kazansky, A. K.; Kelly, T. J.; Mazza, T.; Meyer, M.; Nosik, V. L.; Sazhina, I. P.; Scholz, F.; Seltmann, J.; Sotoudi, H.; Viefhaus, J.; Kabachnik, N. M.

    2016-08-01

    Electron emission caused by extreme ultraviolet (XUV) radiation in the presence of a strong near infrared (NIR) field leads to multiphoton interactions that depend on several parameters. Here, a comprehensive study of the influence of the angle between the polarization directions of the NIR and XUV fields on the two-color angle-resolved photoelectron spectra of He and Ne is presented. The resulting photoelectron angular distribution strongly depends on the orientation of the NIR polarization plane with respect to that of the XUV field. The prevailing influence of the intense NIR field over the angular emission characteristics for He(1s) and Ne(2p) ionization lines is shown. The underlying processes are modeled in the frame of the strong field approximation (SFA) which shows very consistent agreement with the experiment reaffirming the power of the SFA for multicolor-multiphoton ionization in this regime.

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

    NASA Astrophysics Data System (ADS)

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

    2005-06-01

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

  16. [Discrimination of Crude Oil Samples Using Laser-Induced Time-Resolved Fluorescence Spectroscopy].

    PubMed

    Han, Xiao-shuang; Liu, De-qing; Luan, Xiao-ning; Guo, Jin-jia; Liu, Yong-xin; Zheng, Rong-er

    2016-02-01

    The Laser-induced fluorescence spectra combined with pattern recognition method has been widely applied in discrimination of different spilled oil, such as diesel, gasoline, and crude oil. However, traditional three-dimension fluorescence analysis method, which is not adapted to requirement of field detection, is limited to laboratory investigatio ns. The development of oil identification method for field detection is significant to quick response and operation of oil spill. In this paper, a new method based on laser-induced time-resolved fluorescence combined with support vector machine (SVM) model was introduced to discriminate crude oil samples. In this method, time-resolved spectra data was descended into two dimensions with selecting appropriate range in time and wavelength domains respectively to form a SVM data base. It is found that the classification accurate rate increased with an appropriate selection. With a selected range from 54 to 74 ns in time domain, the classification accurate rate has been increased from 83.3% (without selection) to 88.1%. With a selected wavelength range of 387.00~608.87 nm, the classification accurate rate of suspect oil was improved from 84% (without selection) to 100%. Since the detection delay of fluorescence lidar fluctuates due to wave and platform swing, the identification method with optimizing in both time and wavelength domains could offer a better flexibility for field applications. It is hoped that the developed method could provide some useful reference with data reduction for classification of suspect crude oil in the future development. PMID:27209747

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-09-01

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

  19. Spatially resolved spectroscopy of AG Carinae, and direct evidence for stellar evolution: The central star of NGC 2392

    NASA Technical Reports Server (NTRS)

    Altner, Bruce; Shore, Steven N.

    1993-01-01

    We have performed spatially-resolved low dispersion long-slit spectroscopy for the circumstellar shell of the luminous blue variable AG Carinae with IUE between lambda lambda 1200 - 3200 A. At all positions a strong dust-scattered stellar continuum is detected. Only a few emission lines, FE II 2600 and O I (?) 1304, have been detected; the emission is stronger on the southern side of the shell. The UV surface brightness and derived dust properties are completely consistent with the groundbased and KAO FIR observations: the grains are large (0.1 - 1 micron), warm (45 - 100 K depending on composition), highly reflecting (C(sub sca)/C(sub abs) approximately equal to 1), and tie up about 10(exp -4) to 10(exp -3) solar mass of material. We also observe similarities of the results for HR Car and LBV's to those reported here.

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

    NASA Astrophysics Data System (ADS)

    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.

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

    PubMed

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

    2016-06-01

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

  2. Time-Resolved Photoluminescence Spectroscopy and Imaging: New Approaches to the Analysis of Cultural Heritage and Its Degradation

    PubMed Central

    Nevin, Austin; Cesaratto, Anna; Bellei, Sara; D'Andrea, Cosimo; Toniolo, Lucia; Valentini, Gianluca; Comelli, Daniela

    2014-01-01

    Applications of time-resolved photoluminescence spectroscopy (TRPL) and fluorescence lifetime imaging (FLIM) to the analysis of cultural heritage are presented. Examples range from historic wall paintings and stone sculptures to 20th century iconic design objects. A detailed description of the instrumentation developed and employed for analysis in the laboratory or in situ is given. Both instruments rely on a pulsed laser source coupled to a gated detection system, but differ in the type of information they provide. Applications of FLIM to the analysis of model samples and for the in-situ monitoring of works of art range from the analysis of organic materials and pigments in wall paintings, the detection of trace organic substances on stone sculptures, to the mapping of luminescence in late 19th century paintings. TRPL and FLIM are employed as sensors for the detection of the degradation of design objects made in plastic. Applications and avenues for future research are suggested. PMID:24699285

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

    SciTech Connect

    Xiao, Yang; Zhai, Zhao-Hui; Zhu, Li-Guo E-mail: huangwanxia@scu.edu.cn; Li, Jun; Peng, Qi-Xian; Li, Ze-Ren; Shi, Qi-Wu; Huang, Wan-Xia E-mail: huangwanxia@scu.edu.cn; Yue, Fang; Hu, Yan-Yan

    2015-07-20

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

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

    NASA Astrophysics Data System (ADS)

    Fjodorow, Peter; Fikri, Mustapha; Schulz, Christof; Hellmig, Ortwin; Baev, Valery M.

    2016-06-01

    In this paper, we demonstrate the first application of intracavity absorption spectroscopy (ICAS) for monitoring species concentration, total pressure, and temperature in shock-tube experiments. ICAS with a broadband Er3+-doped fiber laser is applied to time-resolved measurements of absorption spectra of shock-heated C2H2. The measurements are performed in a spectral range between 6512 and 6542 cm-1, including many absorption lines of C2H2, with a time resolution of 100 µs and an effective absorption path length of 15 m. Up to 18-times increase of the total pressure and a temperature rise of up to 1200 K have been monitored. Due to the ability of simultaneously recording many absorption lines in a broad spectral range, the presented technique can also be applied to multi-component analysis of transient single-shot processes in reactive gas mixtures in shock tubes, pulse detonation engines, or explosions.

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

    NASA Astrophysics Data System (ADS)

    Xiao, Yang; Zhai, Zhao-Hui; Shi, Qi-Wu; Zhu, Li-Guo; Li, Jun; Huang, Wan-Xia; Yue, Fang; Hu, Yan-Yan; Peng, Qi-Xian; Li, Ze-Ren

    2015-07-01

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

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

    PubMed

    Göries, D; Dicke, B; Roedig, P; Stübe, N; Meyer, J; Galler, A; Gawelda, W; Britz, A; Geßler, P; Sotoudi Namin, H; Beckmann, A; Schlie, M; Warmer, M; Naumova, M; Bressler, C; Rübhausen, M; Weckert, E; Meents, A

    2016-05-01

    We report about the development and implementation of a new setup for time-resolved X-ray absorption fine structure spectroscopy at beamline P11 utilizing the outstanding source properties of the low-emittance PETRA III synchrotron storage ring in Hamburg. Using a high intensity micrometer-sized X-ray beam in combination with two positional feedback systems, measurements were performed on the transition metal complex fac-Tris[2-phenylpyridinato-C2,N]iridium(III) also referred to as fac-Ir(ppy)3. This compound is a representative of the phosphorescent iridium(III) complexes, which play an important role in organic light emitting diode (OLED) technology. The experiment could directly prove the anticipated photoinduced charge transfer reaction. Our results further reveal that the temporal resolution of the experiment is limited by the PETRA III X-ray bunch length of ∼103 ps full width at half maximum (FWHM). PMID:27250401

  7. Characterization of the sorption of europium(III) on calcite by site-selective and time-resolved luminescence spectroscopy

    SciTech Connect

    Piriou, B.; Fedoroff, M.; Jeanjean, J.; Bercis, L.

    1997-10-15

    Sorption of europium(III) on calcite from aqueous solution was investigated by kinetics and sorption isotherms at 323 K and by site-selective and time-resolved luminescence spectroscopy at 15 K. Three sorption sites (A, B, C) were characterized by this last technique. B constitutes a major family which appears in all samples with sorbed Eu and is characterized by an environment involving water or hydroxyl ions. The C family is observed only for the highest Eu concentrations. In these sites, the environment is more hydrated than in sites B. Site A constitutes a minority but appears in all samples. It corresponds to the centrosymmetric structural Ca site of calcite in position 2b, thus demonstrating that sorbed Eu(III) can substitute for Ca in calcite.

  8. Temporally resolved characterization of shock-heated foam target with Al absorption spectroscopy for fast electron transport study

    SciTech Connect

    Yabuuchi, T.; Sawada, H.; Wei, M. S.; Beg, F. N.; Regan, S. P.; Anderson, K.; Betti, R.; Hund, J.; Paguio, R. R.; Saito, K. M.; Stephens, R. B.; Key, M. H.; Mackinnon, A. J.; McLean, H. S.; Patel, P. K.; Wilks, S. C.

    2012-09-15

    The CH foam plasma produced by a laser-driven shock wave has been characterized by a temporally resolved Al 1s-2p absorption spectroscopy technique. A 200 mg/cm{sup 3} foam target with Al dopant was developed for this experiment, which used an OMEGA EP [D. D. Meyerhofer et al., J. Phys.: Conf. Ser. 244, 032010 (2010)] long pulse beam with an energy of 1.2 kJ and 3.5 ns pulselength. The plasma temperatures were inferred with the accuracy of 5 eV from the fits to the measurements using an atomic physics code. The results show that the inferred temperature is sustained at 40-45 eV between 6 and 7 ns and decreases to 25 eV at 8 ns. 2-D radiation hydrodynamic simulations show a good agreement with the measurements. Application of the shock-heated foam plasma platform toward fast electron transport experiments is discussed.

  9. Substrate interactions with suspended and supported monolayer MoS2: Angle-resolved photoemission spectroscopy

    SciTech Connect

    Jin, Wencan; Yeh, Po -Chun; Zaki, Nader; Zhang, Datong; Liou, Jonathan T.; Dadap, Jerry I.; Barinov, Alexey; Yablonskikh, Mikhail; Sadowski, Jerzy T.; Sutter, Peter; Herman, Irving P.; Osgood, Jr., Richard M.

    2015-03-17

    We report the directly measured electronic structure of exfoliated monolayer molybdenum disulfide (MoS₂) using micrometer-scale angle-resolved photoemission spectroscopy. Measurements of both suspended and supported monolayer MoS₂ elucidate the effects of interaction with a substrate. Thus, a suggested relaxation of the in-plane lattice constant is found for both suspended and supported monolayer MoS₂ crystals. For suspended MoS₂, a careful investigation of the measured uppermost valence band gives an effective mass at Γ¯ and Κ¯ of 2.00m₀ and 0.43m₀, respectively. We also measure an increase in the band linewidth from the midpoint of Γ¯Κ¯ to the vicinity of Κ¯ and briefly discuss its possible origin.

  10. Modified diglycol-amides for actinide separation: solvent extraction and time-resolved laser fluorescence spectroscopy complexation studies

    SciTech Connect

    Wilden, A.; Modolo, G.; Lange, S.; Sadowski, F.; Bosbach, D.; Beele, B.B.; Panak, P.J.; Skerencak-Frech, A.; Geist, A.; Iqbal, M.; Verboom, W.

    2013-07-01

    In this work, the back-bone of the diglycolamide-structure of the TODGA extractant was modified by adding one or two methyl groups to the central methylene carbon-atoms. The influence of these structural modifications on the extraction behavior of trivalent actinides and lanthanides and other fission products was studied in solvent extraction experiments. The addition of methyl groups to the central methylene carbon atoms leads to reduced distribution ratios, also for Sr(II). This reduced extraction efficiency for Sr(II) is beneficial for process applications, as the co-extraction of Sr(II) can be avoided, resulting in an easier process design. The use of these modified diglycol-amides in solvent extraction processes is discussed. Furthermore, the complexation of Cm(III) and Eu(III) to the ligands was studied using Time-Resolved-Laser-Fluorescence-Spectroscopy (TRLFS). The complexes were characterized by slope analysis and conditional stability constants were determined.

  11. Space-resolved analysis of trace elements in fresh vegetables using ultraviolet nanosecond laser-induced breakdown spectroscopy

    NASA Astrophysics Data System (ADS)

    Juvé, Vincent; Portelli, Richard; Boueri, Myriam; Baudelet, Matthieu; Yu, Jin

    2008-10-01

    Laser-induced breakdown spectroscopy (LIBS) has been applied to analyze trace elements contained in fresh vegetables. A quadrupled Nd:YAG laser is used in the experiments for ablation. Analyzed samples come from local markets and represent frequently consumed vegetables. For a typical root vegetable, such as potato, spectral analysis of the plasma emission reveals more than 400 lines emitted by 27 elements and 2 molecules, C 2 and CN. Among these species, one can find trace as well as ultra-trace elements. A space-resolved analysis of several trace elements with strong emissions is then applied to typical root, stem and fruit vegetables. The results from this study demonstrate the potential of an interesting tool for botanical and agricultural studies as well for food quality/safety and environment pollution assessment and control.

  12. Phenomenological study of the normal state angle resolved photoelectron spectroscopy line shapes of high temperature superconducting cuprates

    NASA Astrophysics Data System (ADS)

    Matsuyama, Kazue; Dilip, Rohit; Gweon, G.-H.

    2015-03-01

    Understanding the normal state properties of high temperature (high-Tc) superconducting cuprates remains a central mystery in the high-Tc problem. Standing out among those mysterious properties are the anomalous angle resolved photoelectron spectroscopy (ARPES) line shapes. The extremely correlated Fermi liquid (ECFL) theory recently introduced by Shastry has renewed interest in quantitatively understanding ARPES line shapes. In this talk, we combine certain phenomenological considerations with the ECFL framework in order to describe the ARPES data. Our phenomenological models have the property of preserving the universal property of the original ECFL theory, while introducing phenomenological changes in a non-universal property. Our models describe, with unprecedented fidelity, the key aspects of the dichotomy between momentum distribution curves (MDCs) and energy distribution curves (EDCs) of high-Tc ARPES data. Therefore, our study goes well beyond the prevailing studies that discuss only MDCs and EDCs.

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Angle-resolved Photoemission Spectroscopy Study on the Surface States of the Correlated Topological Insulator YbB6

    PubMed Central

    Xia, M.; Jiang, J.; Ye, Z. R.; Wang, Y. H.; Zhang, Y.; Chen, S. D.; Niu, X. H.; Xu, D. F.; Chen, F.; Chen, X. H.; Xie, B. P.; Zhang, T.; Feng, D. L.

    2014-01-01

    YbB6 is recently predicted to be a moderately correlated topological insulator, which provides a playground to explore the interplay between correlation and topological properties. With angle-resolved photoemission spectroscopy, we directly observed almost linearly dispersive bands around the time-reversal invariant momenta and with negligible kz dependence, consistent with odd number of surface states crossing the Fermi level in a Z2 topological insulator. Circular dichroism photoemission spectra suggest that these in-gap states possess chirality of orbital angular momentum, which is related to the chiral spin texture, further indicative of their topological nature. The observed insulating gap of YbB6 is about 100 meV, larger than that found by theoretical calculations. Our results present strong evidence that YbB6 is a correlated topological insulator and provide a foundation for further studies of this promising material. PMID:25102781

  15. Radiative lifetime measurements of some Tm I and Tm II levels by time-resolved laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Tian, Yanshan; Wang, Xinghao; Yu, Qi; Li, Yongfan; Gao, Yang; Dai, Zhenwen

    2016-04-01

    Radiative lifetimes of 88 levels of Tm I in the energy range 22 791.176-48 547.98 cm-1 and 29 levels of Tm II in the range 27 294.79-65 612.85 cm-1 were measured by time-resolved laser-induced fluorescence spectroscopy in laser-ablation plasma. The lifetime values obtained are in the range from 15.4 to 7900 ns for Tm I and from 36.5 to 1000 ns for Tm II. To the best of our knowledge, 77 lifetimes of Tm I and 22 lifetimes of Tm II are reported for the first time. Good agreements between the present results and the previous experimental values were achieved for both Tm I and Tm II.

  16. Phase-resolved two-dimensional terahertz spectroscopy including off-resonant interactions beyond the χ(3) limit

    NASA Astrophysics Data System (ADS)

    Somma, Carmine; Folpini, Giulia; Reimann, Klaus; Woerner, Michael; Elsaesser, Thomas

    2016-05-01

    We present the first two-dimensional (2D) terahertz (THz) experiment with three phase-locked THz pulses and a fully phase-resolved detection of the nonlinearly emitted field by electrooptic sampling. In a prototype experiment we study the ultrafast dynamics of nonlinear two-phonon and two-photon interband coherences in the narrow-gap semiconductor InSb. Due to the extraordinarily large optical interband dipole of InSb the experiments were performed in the strongly nonperturbative regime of light-matter interaction allowing for impulsive off-resonant excitation of both two-phonon coherences and two-photon interband coherences, the ultrafast dynamics of which is experimentally observed as a function of the waiting time in the three-pulse 2D experiment. Our novel three-pulse 2D THz spectroscopy paves the way for the detailed investigation of nonlinear quantum coherences in solids and holds potential for an extension to other systems.

  17. Reduced photoconductivity observed by time-resolved terahertz spectroscopy in metal nanofilms with and without adhesion layers

    NASA Astrophysics Data System (ADS)

    Alberding, Brian G.; Kushto, Gary P.; Lane, Paul A.; Heilweil, Edwin J.

    2016-05-01

    Non-contact, optical time-resolved terahertz spectroscopy has been used to study the transient photoconductivity of nanometer-scale metallic films deposited on the fused quartz substrates. Samples of 8 nm thick gold or titanium show an instrument-limited (ca. 0.5 ps) decrease in conductivity following photoexcitation due to electron-phonon coupling and subsequent increased lattice temperatures which increases charge carrier scattering. In contrast, for samples of 8 nm gold with a 4 nm adhesion layer of titanium or chromium, a ca. 70 ps rise time for the lattice temperature increase is observed. These results establish the increased transient terahertz transmission sign change of metallic compared to semiconductor materials. The results also suggest nanoscale gold films that utilize an adhesion material do not consist of distinct layers.

  18. Direct Observation of Localized Spin Antiferromagnetic Transition in PdCrO2 by Angle-Resolved Photoemission Spectroscopy

    PubMed Central

    Noh, Han-Jin; Jeong, Jinwon; Chang, Bin; Jeong, Dahee; Moon, Hyun Sook; Cho, En-Jin; Ok, Jong Mok; Kim, Jun Sung; Kim, Kyoo; Min, B. I.; Lee, Han-Koo; Kim, Jae-Young; Park, Byeong-Gyu; Kim, Hyeong-Do; Lee, Seongsu

    2014-01-01

    We report the first case of the successful measurements of a localized spin antiferromagnetic transition in delafossite-type PdCrO2 by angle-resolved photoemission spectroscopy (ARPES). This demonstrates how to circumvent the shortcomings of ARPES for investigation of magnetism involved with localized spins in limited size of two-dimensional crystals or multi-layer thin films that neutron scattering can hardly study due to lack of bulk compared to surface. Also, our observations give direct evidence for the spin ordering pattern of Cr3+ ions in PdCrO2 suggested by neutron diffraction and quantum oscillation measurements, and provide a strong constraint that has to be satisfied by a microscopic mechanism for the unconventional anomalous Hall effect recently reported in this system. PMID:24419488

  19. Temperature measurements in reacting flows by time-resolved femtosecond coherent anti-Stokes Raman scattering (fs-CARS) spectroscopy

    NASA Astrophysics Data System (ADS)

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

    2008-01-01

    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. The initial frequency-spread dephasing rate of the Raman coherence induced by the ultrafast (∼85 fs) Stokes and pump beams is used as a measure of gas-phase temperature. This initial frequency-spread dephasing rate of the Raman coherence is completely independent of collisions and depends only on the frequency spread of the Raman transitions at different temperatures. A simple theoretical model based on the assumption of impulsive excitation of Raman coherence is used to extract temperatures from time-resolved fs-CARS experimental signals. The extracted temperatures from fs-CARS signals are in excellent agreement with the theoretical temperatures calculated from an adiabatic equilibrium calculation. The estimated absolute accuracy and the precision of the measurement technique are found to be ±40 K and ±50 K, respectively, over the temperature range 1500-2500 K.

  20. The study of polyplex formation and stability by time-resolved fluorescence spectroscopy of SYBR Green I-stained DNA.

    PubMed

    D'Andrea, Cosimo; Pezzoli, Daniele; Malloggi, Chiara; Candeo, Alessia; Capelli, Giulio; Bassi, Andrea; Volonterio, Alessandro; Taroni, Paola; Candiani, Gabriele

    2014-12-01

    Polyplexes are nanoparticles formed by the self-assembly of DNA/RNA and cationic polymers specifically designed to deliver exogenous genetic material to cells by a process called transfection. There is a general consensus that a subtle balance between sufficient extracellular protection and intracellular release of nucleic acids is a key factor for successful gene delivery. Therefore, there is a strong need to develop suitable tools and techniques for enabling the monitoring of the stability of polyplexes in the biological environment they face during transfection. In this work we propose time-resolved fluorescence spectroscopy in combination with SYBR Green I-DNA dye as a reliable tool for the in-depth characterization of the DNA/vector complexation state. As a proof of concept, we provide essential information on the assembly and disassembly of complexes formed between DNA and each of three cationic polymers, namely a novel promising chitosan-graft-branched polyethylenimine copolymer (Chi-g-bPEI), one of its building block 2 kDa bPEI and the gold standard transfectant 25 kDa bPEI. Our results highlight the higher information content provided by the time-resolved studies of SYBR Green I/DNA, as compared to conventional steady state measurements of ethidium bromide/DNA that enabled us to draw relationships among fluorescence lifetime, polyplex structural changes and transfection efficiency. PMID:25308511

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

    NASA Astrophysics Data System (ADS)

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

    2013-05-01

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

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

    NASA Technical Reports Server (NTRS)

    Nickolaisen, Scott L.; Cartland, Harry E.

    1993-01-01

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

  3. Resolving Losses at the Negative Electrode in All-Vanadium Redox Flow Batteries Using Electrochemical Impedance Spectroscopy

    SciTech Connect

    Sun, Che Nan; Delnick, Frank M; Aaron, D; Mench, Matthew M; Zawodzinski, Thomas A

    2014-01-01

    We present an in situ electrochemical technique for the quantitative measurement and resolution of the ohmic, charge transfer and diffusion overvoltages at the negative electrode of an all-vanadium redox flow battery (VRFB) using electrochemical impedance spectroscopy (EIS). The mathematics describing the complex impedance of the V+2/V+3 redox reaction is derived and matches the experimental data. The voltage losses contributed by each process have been resolved and quantified at various flow rates and electrode thicknesses as a function of current density during anodic and cathodic polarization. The diffusion overvoltage was affected strongly by flow rate while the charge transfer and ohmic losses were invariant. On the other hand, adopting a thicker electrode significantly changed both the charge transfer and diffusion losses due to increased surface area. Furthermore, the Tafel plot obtained from the impedance resolved charge transfer overvoltage yielded the geometric exchange current density, anodic and cathodic Tafel slopes (135 5 and 121 5 mV/decade respectively) and corresponding transfer coefficients = 0.45 0.02 and = 0.50 0.02 in an operating cell.

  4. Elucidating low-frequency vibrational dynamics in calcite and water with time-resolved third-harmonic generation spectroscopy.

    PubMed

    Wang, Liang; Liu, Weimin; Fang, Chong

    2015-07-14

    Low-frequency vibrations are foundational for material properties including thermal conductivity and chemical reactivity. To resolve the intrinsic molecular conformational dynamics in condensed phase, we implement time-resolved third-harmonic generation (TRTHG) spectroscopy to unravel collective skeletal motions in calcite, water, and aqueous salt solution in situ. The lifetime of three Raman-active modes in polycrystalline calcite at 155, 282 and 703 cm(-1) is found to be ca. 1.6 ps, 1.3 ps and 250 fs, respectively. The lifetime difference is due to crystallographic defects and anharmonic effects. By incorporating a home-built wire-guided liquid jet, we apply TRTHG to investigate pure water and ZnCl2 aqueous solution, revealing ultrafast dynamics of water intermolecular stretching and librational bands below 500 cm(-1) and a characteristic 280 cm(-1) vibrational mode in the ZnCl4(H2O)2(2-) complex. TRTHG proves to be a compact and versatile technique that directly uses the 800 nm fundamental laser pulse output to capture ultrafast low-frequency vibrational motion snapshots in condensed-phase materials including the omnipresent water, which provides the important time dimension to spectral characterization of molecular structure-function relationships. PMID:26062639

  5. Monitoring the folding kinetics of a β-hairpin by time-resolved IR spectroscopy in silico.

    PubMed

    Daidone, Isabella; Thukral, Lipi; Smith, Jeremy C; Amadei, Andrea

    2015-04-01

    Protein folding is one of the most fundamental problems in modern biochemistry. Time-resolved infrared (IR) spectroscopy in the amide I region is commonly used to monitor folding kinetics. However, associated atomic detail information on the folding mechanism requires simulations. In atomistic simulations structural order parameters are typically used to follow the folding process along the simulated trajectories. However, a rigorous test of the reliability of the mechanisms found in the simulations requires calculation of the time-dependent experimental observable, i.e., in the present case the IR signal in the amide I region. Here, we combine molecular dynamics simulation with a mixed quantum mechanics/molecular mechanics theoretical methodology, the Perturbed Matrix Method, in order to characterize the folding of a β-hairpin peptide, through modeling the time-dependence of the amide I IR signal. The kinetic and thermodynamic data (folding and unfolding rate constants, and equilibrium folded- and unfolded-state probabilities) obtained from the fit of the calculated signal are in good agreement with the available experimental data [Xu et al. J. Am. Chem. Soc. 2003, 125, 15388-15394]. To the best of our knowledge, this is the first report of the simulation of the time-resolved IR signal of a complex process occurring on a long (microsecond) time scale. PMID:25777154

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

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

  7. Effects of Cosmetic Therapy on Cognitive Function in Elderly Women Evaluated by Time-Resolved Spectroscopy Study.

    PubMed

    Machida, A; Shirato, M; Tanida, M; Kanemaru, C; Nagai, S; Sakatani, K

    2016-01-01

    With the rapid increase in dementia in developed countries, it is important to establish methods for maintaining or improving cognitive function in elderly people. To resolve such problems, we have been developing a cosmetic therapy (CT) program for elderly women. However, the mechanism and limitations of CT are not yet clear. In order to clarify these issues, we employed time-resolved spectroscopy (TRS) to evaluate the effect of CT on prefrontal cortex (PFC) activity in elderly females with various levels of cognitive impairment. Based on the Mini-Mental State Examination (MMSE) score, the subjects were classified into mild (mean MMSE score: 24.1±3.8) and moderate (mean MMSE score: 10.3±5.8) cognitive impairment (CI) groups (p<0.0001). The mild CI group exhibited significantly larger baseline concentrations of oxy-Hb and t-Hb than the moderate CI group. CT significantly increased the baseline concentrations of oxy-Hb (p<0.002) and t-Hb (p<0.0013) in the left PFC in the mild CI group. In contrast, CT did not change the concentrations of oxy-Hb and t-Hb in the moderate CI group (p>0.05). These results suggest that CT affects cognitive function by altering PFC activity in elderly women with mild CI, but not moderate CI. PMID:26782224

  8. Depth-resolved confocal micro-Raman spectroscopy for characterizing GaN-based light emitting diode structures

    SciTech Connect

    Chen, Wei-Liang; Lee, Yu-Yang; Chang, Yu-Ming; Chang, Chiao-Yun; Huang, Huei-Min; Lu, Tien-Chang

    2013-11-15

    In this work, we demonstrate that depth-resolved confocal micro-Raman spectroscopy can be used to characterize the active layer of GaN-based LEDs. By taking the depth compression effect due to refraction index mismatch into account, the axial profiles of Raman peak intensities from the GaN capping layer toward the sapphire substrate can correctly match the LED structural dimension and allow the identification of unique Raman feature originated from the 0.3 μm thick active layer of the studied LED. The strain variation in different sample depths can also be quantified by measuring the Raman shift of GaN A{sub 1}(LO) and E{sub 2}(high) phonon peaks. The capability of identifying the phonon structure of buried LED active layer and depth-resolving the strain distribution of LED structure makes this technique a potential optical and remote tool for in operando investigation of the electronic and structural properties of nitride-based LEDs.

  9. Time-resolved Fourier transform infrared spectroscopy of chemical reactions in solution using a focal plane array detector.

    PubMed

    Kaun, N; Vellekoop, M J; Lendl, B

    2006-11-01

    A Fourier transform infrared (FT-IR) microscope equipped with a single as well as a 64 x 64 element focal plane array MCT detector was used to measure chemical reaction taking place in a microstructured flow cell designed for time-resolved FT-IR spectroscopy. The flow cell allows transmission measurements through aqueous solutions and incorporates a microstructured mixing unit. This unit achieves lamination of the two input streams with a cross-section of 300 x 5 microm each, resulting in fast diffusion-controlled mixing of the two input streams. Microscopic measurement at defined positions along the outlet channel allows time-resolved information of the reaction taking place in the flow cell to be obtained. In this paper we show experimental results on the model reaction between formaldehyde and sulfite. Using the single-point MCT detector, high-quality FT-IR spectra could be obtained from a spot size of 80 x 200 microm whereas the FPA detector allowed recording light from an area of 260 x 260 microm focused on its 64 x 64 detector elements. Therefore, more closely spaced features could be discerned at the expense of a significantly lower signal-to-noise (S/N) ratio per spectrum. Multivariate curve resolution-alternating least squares was used to extract concentration profiles of the reacting species along the outlet channel axis. PMID:17132444

  10. Reaction mechanism of adenylyltransferase DrrA from Legionella pneumophila elucidated by time-resolved fourier transform infrared spectroscopy.

    PubMed

    Gavriljuk, Konstantin; Schartner, Jonas; Itzen, Aymelt; Goody, Roger S; Gerwert, Klaus; Kötting, Carsten

    2014-07-01

    Modulation of the function of small GTPases that regulate vesicular trafficking is a strategy employed by several human pathogens. Legionella pneumophila infects lung macrophages and injects a plethora of different proteins into its host cell. Among these is DrrA/SidM, which catalyzes stable adenylylation of Rab1b, a regulator of endoplasmatic reticulum to Golgi trafficking, and thereby alters the function and interactions of this small GTPase. We employed time-resolved FTIR-spectroscopy to monitor the DrrA-catalyzed AMP-transfer to Tyr77 of Rab1b. A transient complex between DrrA, adenylylated Rab1b, and the pyrophosphate byproduct was resolved, allowing us to analyze the interactions at the active site. Combination of isotopic labeling and site-directed mutagenesis allowed us to derive the catalytic mechanism of DrrA from the FTIR difference spectra. DrrA shares crucial residues in the ATP-binding pocket with similar AMP-transferring enzymes such as glutamine synthetase adenylyltransferase or kanamycin nucleotidyltransferase, but provides the complete active site on a single subunit. We determined that Asp112 of DrrA functions as the catalytic base for deprotonation of Tyr77 of Rab1b to enable nucleophilic attack on the ATP. The study provides detailed understanding of the Legionella pneumophila protein DrrA and of AMP-transfer reactions in general. PMID:24950229

  11. Discrimination of human coronary artery atherosclerotic lipid-rich lesions by time-resolved laser-induced fluorescence spectroscopy.

    PubMed

    Marcu, L; Fishbein, M C; Maarek, J M; Grundfest, W S

    2001-07-01

    Lesion composition plays a significant role in atherosclerotic lesion instability and rupture. Current clinical techniques cannot fully characterize lesion composition or accurately identify unstable lesions. This study investigates the use of time-resolved fluorescence spectroscopy for unstable atherosclerotic lesion diagnosis. The fluorescence of human coronary artery samples was induced with nitrogen laser and detected in the 360- to 510-nm wavelength range. The samples were sorted into 7 groups according to the AHA classification: normal wall and types I, II(a) (fatty streaks), III (preatheroma), IV (atheroma), V(a) (fibrous), and V(b) (calcified) lesions. Spectral intensities and time-dependent parameters [average lifetime tau(f); decay constants: tau(1) (fast-term), tau(2) (slow-term), A(1) (fast-term amplitude contribution)] derived from the time-resolved spectra of coronary samples were used for tissue characterization. We determined that a few intensity values at longer wavelengths (>430 nm) and time-dependent parameters at peak emission region (390 nm) discriminate between all types of arterial samples except between normal wall and type I lesions. The lipid-rich lesions (more unstable) can be discriminated from fibrous lesions (more stable) on the basis of time-dependent parameters (lifetime and fast-term decay). We inferred that features of lipid fluorescence are reflected on lipid-rich lesion emission. Our results demonstrate that analysis of the time-resolved spectra may be used to enhance the discrimination between different grades of atherosclerotic lesions and provide a means of discrimination between lipid-rich and fibrous lesions. PMID:11451759

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

    NASA Astrophysics Data System (ADS)

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

    2007-09-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  14. Time-resolved and steady-state fluorescence spectroscopy for the assessment of skin photoaging process

    NASA Astrophysics Data System (ADS)

    D´Almeida, Camila de Paula; Campos, Carolina; Saito Nogueira, Marcelo; Pratavieira, Sebastião.; Kurachi, Cristina

    2015-06-01

    pathology. The optical properties of these intrinsic fluorophores respond to the microenvironment and the metabolic status, thus making fluorescence spectroscopy a valuable tool to study the conditions of biological tissues. The purpose of this study is to investigate the hairless mice skin metabolic changes during the photoaging process through lifetime and fluorescence measurements targeting NADH and FAD. Two lasers centered at 378 nm and 445 nm, respectively, perform excitation of NADH and FAD. The fluorescence acquisition is carried out at mice dorsal and ventral regions throughout the photoaging protocol and aging process. Differences in fluorescence and lifetime data between young and photoaged mice measurements were observed. The endogenous fluorescence spectrum of photoaged dorsal skin showed an increase compared to young and aged skin. Lifetime of bound NADH and free FAD presented an increase in the first week that continued until the end of the protocol. Aging process is being investigated to complement the information obtained from fluorescence data and lifetime of photoaging process.

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

    PubMed

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

    2005-01-21

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

  16. Time-resolved spectroscopy measurements of hydrogen-alpha, -beta, and -gamma emissions

    SciTech Connect

    Parigger, Christian G.; Dackman, Matthew; Hornkohl, James O

    2008-11-01

    Hydrogen emission spectroscopy results are reported following laser-induced optical breakdown with infrared Nd:YAG laser radiation focused into a pulsed methane flow. Measurements of Stark-broadened atomic hydrogen-alpha, -beta, and -gamma lines show electron number densities of 0.3 to 4x10{sup 17} cm{sup -3} for time delays of 2.1 to 0.4 {mu}s after laser-induced optical breakdown. In methane flow, recombination molecular spectra of the {delta}{nu}=+2 progression of the C2 Swan system are discernable in the H{beta} and H{gamma} plasma emissions within the first few microseconds. The recorded atomic spectra indicate the occurrence of hydrogen self-absorption for pulsed CH4 flow pressures of 2.7x10{sup 5} Pa (25 psig) and 6.5x10{sup 5} Pa (80 psig)

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

    PubMed

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

    2016-05-27

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

  18. Time-resolved spectroscopy measurements of hydrogen-alpha, -beta, and -gamma emissions.

    PubMed

    Parigger, Christian G; Dackman, Matthew; Hornkohl, James O

    2008-11-01

    Hydrogen emission spectroscopy results are reported following laser-induced optical breakdown with infrared Nd:YAG laser radiation focused into a pulsed methane flow. Measurements of Stark-broadened atomic hydrogen-alpha, -beta, and -gamma lines show electron number densities of 0.3 to 4x10(17) cm(-3) for time delays of 2.1 to 0.4 micros after laser-induced optical breakdown. In methane flow, recombination molecular spectra of the Delta nu = +2 progression of the C(2) Swan system are discernable in the H(beta) and H(gamma) plasma emissions within the first few microseconds. The recorded atomic spectra indicate the occurrence of hydrogen self-absorption for pulsed CH(4) flow pressures of 2.7x10(5) Pa (25 psig) and 6.5x10(5) Pa (80 psig). PMID:19122690

  19. Development of Multi-Color Time-Resolved Spectroscopy Methods for Investigating Molecular Systems

    NASA Astrophysics Data System (ADS)

    Larsen, Kirk; Champenois, Elio; Wright, Travis; Cryan, James; Shivaram, Niranjan; Ray, Dipanwita; Troy, Tyler; Bandyopadhyay, Biswajit; Kostko, Oleg; Rude, Bruce; Ahmed, Musa; Belkacem, Ali; Slaughter, Dan

    2016-05-01

    Ultrafast transient absorption spectroscopy facilitates the study of a system's electronic excited state dynamics. Employing a multi-color technique, the time evolution of excited states of a given target can be investigated in great detail. We have developed methods for performing multi-color experiments using a femtosecond UV (266nm) pulse obtained from a frequency tripled IR (800nm) pulse, in conjunction with soft x-rays from the synchrotron at the Advanced Light Source (ALS). We are additionally working towards developing similar techniques with multi-color, multi-pulse schemes using extreme ultraviolet light from a high harmonic generation (HHG) source as a probe. We also present reflectivity measurements of different mirror coatings, that allow us to select relevant energies from the HHG source. Work supported by Chemical Sciences, Geosciences and Biosciences division of BES/DOE.

  20. SPATIALLY RESOLVED HST GRISM SPECTROSCOPY OF A LENSED EMISSION LINE GALAXY AT z {approx} 1

    SciTech Connect

    Frye, Brenda L.; Hurley, Mairead; Bowen, David V.; Meurer, Gerhardt; Sharon, Keren; Straughn, Amber; Coe, Dan; Broadhurst, Tom; Guhathakurta, Puragra

    2012-07-20

    We take advantage of gravitational lensing amplification by A1689 (z 0.187) to undertake the first space-based census of emission line galaxies (ELGs) in the field of a massive lensing cluster. Forty-three ELGs are identified to a flux of i{sub 775} = 27.3 via slitless grism spectroscopy. One ELG (at z = 0.7895) is very bright owing to lensing magnification by a factor of Almost-Equal-To 4.5. Several Balmer emission lines (ELs) detected from ground-based follow-up spectroscopy signal the onset of a major starburst for this low-mass galaxy (M{sub *} Almost-Equal-To 2 Multiplication-Sign 10{sup 9} M{sub Sun }) with a high specific star formation rate ( Almost-Equal-To 20 Gyr{sup -1}). From the blue ELs we measure a gas-phase oxygen abundance consistent with solar (12+log(O/H) = 8.8 {+-} 0.2). We break the continuous line-emitting region of this giant arc into seven {approx}1 kpc bins (intrinsic size) and measure a variety of metallicity-dependent line ratios. A weak trend of increasing metal fraction is seen toward the dynamical center of the galaxy. Interestingly, the metal line ratios in a region offset from the center by {approx}1 kpc have a placement on the blue H II region excitation diagram with f ([O III])/f (H{beta}) and f ([Ne III])/f (H{beta}) that can be fitted by an active galactic nucleus (AGN). This asymmetrical AGN-like behavior is interpreted as a product of shocks in the direction of the galaxy's extended tail, possibly instigated by a recent galaxy interaction.

  1. Fourier resolved spectroscopy of 4U 1543-47 during the 2002 outburst

    NASA Technical Reports Server (NTRS)

    Reig, P.; Papadakis, I. E.; Shrader, C. R.; Kazanas, D.

    2006-01-01

    We have obtained Fourier-resolved spectra of the black-hole binary 4U 1543-47 in the canonical states (high/soft, very high, intermediate and low/hard) observed in this source during the decay of an outburst that took place in 2002. Our objective is to investigate the variability of the spectral components generally used to describe the energy spectra of black-hole systems, namely a disk component, a power-law component attributed to Comptonization by a hot corona and the contribution of the iron line due to reprocessing of the high energy (E greater than or approx, equal to 7 keV) radiation. We find that i) the disk component is not variable on time scales shorter than approx. 100 seconds, ii) the reprocessing emission as manifest by the variability of the Fe K(alpha) line responds to the primary radiation variations down to time scales of approx. 70 ms in the high and very-high states, but longer than 2 s in the low state, iii) the low-frequency QPOs are associated with variations of the X-ray power law spectral component and not to the disk component and iv) the spectra corresponding to the highest Fourier frequency are the hardest (show the flatter spectra) at a given spectral state. These results questions the models that explain the observed power spectra as due to modulations of the accretion rate only.

  2. Time-resolved infrared spectroscopy of the lowest triplet state of thymine and thymidine

    NASA Astrophysics Data System (ADS)

    Hare, Patrick M.; Middleton, Chris T.; Mertel, Kristin I.; Herbert, John M.; Kohler, Bern

    2008-05-01

    Vibrational spectra of the lowest energy triplet states of thymine and its 2'-deoxyribonucleoside, thymidine, are reported for the first time. Time-resolved infrared (TRIR) difference spectra were recorded over seven decades of time from 300 fs to 3 μs using femtosecond and nanosecond pump-probe techniques. The carbonyl stretch bands in the triplet state are seen at 1603 and ˜1700 cm -1 in room-temperature acetonitrile- d3 solution. These bands and additional ones observed between 1300 and 1450 cm -1 are quenched by dissolved oxygen on a nanosecond time scale. Density-functional calculations accurately predict the difference spectrum between triplet and singlet IR absorption cross sections, confirming the peak assignments and elucidating the nature of the vibrational modes. In the triplet state, the C4 dbnd O carbonyl exhibits substantial single-bond character, explaining the large (˜70 cm -1) red shift in this vibration, relative to the singlet ground state. Femtosecond TRIR measurements unambiguously demonstrate that the triplet state is fully formed within the first 10 ps after excitation, ruling out a relaxed 1nπ ∗ state as the triplet precursor.

  3. Time resolved laser absorption spectroscopy in a self-pulsed microplasma.

    NASA Astrophysics Data System (ADS)

    Aubert, X.; Rousseau, A.; Lagrange, J. F.; Sadeghi, N.

    2006-10-01

    It was recently shown that microplasmas of the microhollow cathode type geometry may operate in a self-pulsing regime for intermediate current (0.1-1 mA) [1]. At lower current (< 0.1 mA) the plasma is stable and located inside the hole; at higher current (> 1 mA) , the plasma is also stable but expands outside the hole on the cathode backside region. The self pulsing was attributed to the breakdown of the gas, outside the micro-hole, on the cathode backside. However, the mechanisms of the plasma ignition on the cathode backside are not understood and metastable atoms may play a major role. In the present work, time resolved diode laser absorption measurements have been performed through the micro-hole in the self-pulsing regime; the plasma hole ranges is in the range of 100 μm and the gas pressure ranges from 50 to 300 Torr; the feed gas is argon and the transition studied is 772.376 nm (Paschen notation 1s5-2p7). The objective is i) to measure the time evolution of the 1s5 metastable density, ii) deduce the gas temperature and plasma density from the absorption line profile. Similar results are performed in 3 electrodes configuration [1] A. Rousseau and X. Aubert J. Phys.D : Appl. Phys. 39 (2006) 1619--1622.

  4. Time-resolved spectroscopy and photometry of the eclipsing AM Herculis binary EXO 033319 - 2554. 2

    SciTech Connect

    Allen, R.G.; Berriman, G.; Smith, P.S.; Schmidt, G.D. )

    1989-12-01

    Time-resolved optical observations of the eclipsing AM Herculis binary EXO 033319 - 2554.2 are presented. High-speed photometry of an eclipse is presented and used to derive a new ephemeris for the system and to estimate the size of the region responsible for the cyclotron emission. Optical spectra that span the orbital cycle are presented, the cyclotron emission in these spectra is discussed, and the flux and radial velocity variations of H-beta, H-gamma, and He II 4686 A are examined. Models of the flux and radial velocity variations of the emission lines indicate that about half the line emission comes from low-velocity material that is about 1.4 x 10 to the 10th cm from the white dwarf. The rest comes from high-velocity material that is about 10 to the 10th cm from the white dwarf and is moving toward it at about 600 km/s. 13 refs.

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

  6. Microstructure Imaging Using Frequency Spectrum Spatially Resolved Acoustic Spectroscopy F-Sras

    NASA Astrophysics Data System (ADS)

    Sharples, S. D.; Li, W.; Clark, M.; Somekh, M. G.

    2010-02-01

    Material microstructure can have a profound effect on the mechanical properties of a component, such as strength and resistance to creep and fatigue. SRAS—spatially resolved acoustic spectroscopy—is a laser ultrasonic technique which can image microstructure using highly localized surface acoustic wave (SAW) velocity as a contrast mechanism, as this is sensitive to crystallographic orientation. The technique is noncontact, nondestructive, rapid, can be used on large components, and is highly tolerant of acoustic aberrations. Previously, the SRAS technique has been demonstrated using a fixed frequency excitation laser and a variable grating period (к-vector) to determine the most efficiently generated SAWs, and hence the velocity. Here, we demonstrate an implementation which uses a fixed grating period with a broadband laser excitation source. The velocity is determined by analyzing the measured frequency spectrum. Experimental results using this "frequency spectrum SRAS" (f-SRAS) method are presented. Images of microstructure on an industrially relevant material are compared to those obtained using the previous SRAS method ("k-SRAS"), excellent agreement is observed. Moreover, f-SRAS is much simpler and potentially much more rapid than k-SRAS as the velocity can be determined at each sample point in one single laser shot, rather than scanning the grating period.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  8. Spatially Resolved Spectroscopy of Europa: The Distinct Spectrum of Large-scale Chaos

    NASA Astrophysics Data System (ADS)

    Fischer, P. D.; Brown, M. E.; Hand, K. P.

    2015-11-01

    We present a comprehensive analysis of spatially resolved moderate spectral resolution near-infrared spectra obtained with the adaptive optics system at the Keck Observatory. We identify three compositionally distinct end member regions: the trailing hemisphere bullseye, the leading hemisphere upper latitudes, and a third component associated with leading hemisphere chaos units. We interpret the composition of the three end member regions to be dominated by irradiation products, water ice, and evaporite deposits or salt brines, respectively. The third component is associated with geological features and distinct from the geography of irradiation, suggesting an endogenous identity. Identifying the endogenous composition is of particular interest for revealing the subsurface composition. However, its spectrum is not consistent with linear mixtures of the salt minerals previously considered relevant to Europa. The spectrum of this component is distinguished by distorted hydration features rather than distinct spectral features, indicating hydrated minerals but making unique identification difficult. In particular, it lacks features common to hydrated sulfate minerals, challenging the traditional view of an endogenous salty component dominated by Mg-sulfates. Chloride evaporite deposits are one possible alternative.

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

    NASA Astrophysics Data System (ADS)

    Kaiser, U.; Jimenez de Aberasturi, D.; Malinowski, R.; Amin, F.; Parak, W. J.; Heimbrodt, W.

    2014-01-01

    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.

  10. Channel-resolved photo- and Auger-electron spectroscopy of halogenated hydrocarbons

    NASA Astrophysics Data System (ADS)

    Ablikim, Utuq; Kaderiya, B.; Kumarapan, V.; Kushawaha, R.; Rudenko, A.; Rolles, D.; Xiong, H.; Berrah, N.; Bomme, C.; Savelyev, E.; Kilcoyne, D.

    2016-05-01

    Inner-shell photoelectron and Auger electron spectra of polyatomic molecules such as halogenated hydrocarbons are typically hard to interpret and assign due to many overlapping states that form broad bands even in high-resolution measurements. With the help of electron-ion-ion coincidence measurements performed using the velocity map imaging technique, we are able to detect high-energy (<= 150 eV) photo- and Auger electrons in coincidence with two- or many-body ionic fragmentation channels. Such channel-resolved measurements allow disentangling the overlapping electronic structures and help assigning individual components of the electron spectra to specific potential surfaces and final states. In this work, we present measurements on CH3 I, CH2 IBr, and CH2 ICl molecules in the gas-phase using soft x-ray light provided by the Advanced Light Source at LBNL. This project is supported by the DOE, Office of Science, BES, Division of Chemical, Geological and Biological Sciences under Award Number DE-FG02-86ER13491 (U.A., B.K., V.K., A.R., D.R.) and Award Number DE-SC0012376 (H.X., N.B.).

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

    SciTech Connect

    Kaiser, U.; Jimenez de Aberasturi, D.; Malinowski, R.; Amin, F.; Parak, W. J.; Heimbrodt, W.

    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.

  12. Spatially resolved spectroscopy of an impulse plasma for thin film deposition

    NASA Astrophysics Data System (ADS)

    Kułakowska-Pawlak, Barbara

    2009-08-01

    Radially resolved emission measurements have been employed for a better understanding of plasma generated in a pulsed coaxial accelerator operating in a mixture of propane and butane under conditions which enable diamond-like layer deposition. The measurements were taken at two positions along the axis of symmetry of the discharge. Assuming the Boltzmann and Saha equilibrium, the emission from the plasma has been quantified. Abel-transformed radial profiles of the spectral lines of C I, C II and C III have been used to study radial changes in the concentration of excited neutral, singly and doubly ionized carbon, in the excitation temperature, in the ionization temperature and in the electron number density. Values of excitation and ionization temperatures and their radial profiles for a given axial position did not differ significantly. On the axis of symmetry of the discharge, the excitation temperature of C II and the electron density were found to reach values of about 29 000 K and 5 × 1017 cm-3, respectively. In addition, the relative densities of the C, C+ and C2+ species were evaluated, and hence the spatial inhomogeneous plasma structure with respect to the distribution of neutral and ionized fractions of carbon has been revealed and discussed in terms of deposition conditions.

  13. Transit spectroscopy of exoplanets from space: how to optimize the wavelength coverage and spectral resolving power

    NASA Astrophysics Data System (ADS)

    Encrenaz, T.; Tinetti, G.; Tessenyi, M.; Drossart, P.; Hartogh, P.; Coustenis, A.

    2015-12-01

    The study of exoplanets is an exploding field in astronomy. Recent discoveries have made possible the development of a new research field, the spectroscopic characterization of the exoplanetary atmospheres, using both primary and eclipse transits. A dedicated space mission will make possible the characterization of many classes of exoplanets, from the hot Jupiters to the temperate super-Earths. In this paper, we discuss how the spectral range and the spectral resolving power can be optimized for identifying a maximum number of candidate atmospheric species. Spectral modeling shows that the simultaneous observation of the whole spectral range, from 0.55 to 16 μm is ideal for (1) capturing all types of planets at different temperatures, (2) detecting the variety of chemical atmospheric compounds with some redundancy, and (3) enabling an optimal retrieval of the chemical abundances and thermal profile. Limiting the spectral interval to 11 μm would make the retrieval more difficult in the case of cold exoplanets. In the visible range, the extension down to 0.4 s at different temperatures, (2) detecting the variety of chemical atmospheric compounds with some redundancy, and (3) enabling an optimal retrieval of the chemical abundances andst candidate molecules.

  14. Single-shot time-resolved THz spectroscopy using non-collinear electro-optic imaging

    NASA Astrophysics Data System (ADS)

    Wang, Zhenyou; Su, Fuhai; Hegmann, Frank A.

    2010-03-01

    We demonstrate a technique for rapid substance identification via single-shot, coherent THz imaging using non-collinear electro-optic sampling. A THz probe pulse generated in ZnTe is transmitted through the sample then focused on a (110) ZnTe detection crystal. An 800nm, 100fs optical pulse employed as a sampling beam passes through the ZnTe detection crystal at an angle of 7^o relative to the THz beam.footnotetextT. Yasuda et al., Opt. Commun. 267, 128 (2006) The THz field induced birefringence is resolved as a variation of the intensity of the sampling pulse transmitted through a crossed polarizer. The modified sampling beam spot is imaged using a CCD camera. Because of the non-collinear geometry, the spatial overlap between the THz field and the optical pulse depends on the temporal position within the THz waveform. Consequently, we obtain high-resolution 2D images of the THz waveform without scanning the relative path length. The resolution of the absorption spectra extracted from wet paper and lactose using the single-shot imaging approach is comparable to the resolution obtained through conventional scanning lock-in measurements. Possible applications for substance detection are discussed.

  15. Determination of Iron in Water Solution by Time-Resolved Femtosecond Laser-Induced Breakdown Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sergey, S. Golik; Alexey, A. Ilyin; Michael, Yu. Babiy; Yulia, S. Biryukova; Vladimir, V. Lisitsa; Oleg, A. Bukin

    2015-11-01

    The influence of the energy of femtosecond laser pulses on the intensity of Fe I (371.99 nm) emission line and the continuous spectrum of the plasma generated on the surface of Fe3+ water solution by a Ti: sapphire laser radiation with pulse duration < 45 fs and energies up to 7 mJ is determined. A calibration curve was obtained for Fe3+ concentration range from 0.5 g/L to the limit of detection in water solution, and its saturation was detected for concentrations above 0.25 g/L, which is ascribed to self-absorption. The 3σ- limit of detection obtained for Fe in water solution is 2.6 mg/L in the case of 7 mJ laser pulse energy. It is found that an increase of laser pulse energy insignificantly affects on LOD in the time-resolved LIBS and leads to a slight improvement of the limit of detection. supported by the Russian Science Foundation (agreement #14-50-00034) (measurements of limit of detection), Russian Foundation for Basic Research (NK 15-32-20878/15) obtained in the frame of “Organization of Scientific Research” in the Far Eastern Federal University supported by Ministry of Education and Science of Russian Federation

  16. Dual analyzer system for surface analysis dedicated for angle-resolved photoelectron spectroscopy at liquid surfaces and interfaces.

    PubMed

    Niedermaier, Inga; Kolbeck, Claudia; Steinrück, Hans-Peter; Maier, Florian

    2016-04-01

    The investigation of liquid surfaces and interfaces with the powerful toolbox of ultra-high vacuum (UHV)-based surface science techniques generally has to overcome the issue of liquid evaporation within the vacuum system. In the last decade, however, new classes of liquids with negligible vapor pressure at room temperature-in particular, ionic liquids (ILs)-have emerged for surface science studies. It has been demonstrated that particularly angle-resolved X-ray Photoelectron Spectroscopy (ARXPS) allows for investigating phenomena that occur at gas-liquid and liquid-solid interfaces on the molecular level. The results are not only relevant for IL systems but also for liquids in general. In all of these previous ARXPS studies, the sample holder had to be tilted in order to change the polar detection angle of emitted photoelectrons, which restricted the liquid systems to very thin viscous IL films coating a flat solid support. We now report on the concept and realization of a new and unique laboratory "Dual Analyzer System for Surface Analysis (DASSA)" which enables fast ARXPS, UV photoelectron spectroscopy, imaging XPS, and low-energy ion scattering at the horizontal surface plane of macroscopically thick non-volatile liquid samples. It comprises a UHV chamber equipped with two electron analyzers mounted for simultaneous measurements in 0° and 80° emission relative to the surface normal. The performance of DASSA on a first macroscopic liquid system will be demonstrated. PMID:27131705

  17. Dual analyzer system for surface analysis dedicated for angle-resolved photoelectron spectroscopy at liquid surfaces and interfaces

    NASA Astrophysics Data System (ADS)

    Niedermaier, Inga; Kolbeck, Claudia; Steinrück, Hans-Peter; Maier, Florian

    2016-04-01

    The investigation of liquid surfaces and interfaces with the powerful toolbox of ultra-high vacuum (UHV)-based surface science techniques generally has to overcome the issue of liquid evaporation within the vacuum system. In the last decade, however, new classes of liquids with negligible vapor pressure at room temperature—in particular, ionic liquids (ILs)—have emerged for surface science studies. It has been demonstrated that particularly angle-resolved X-ray Photoelectron Spectroscopy (ARXPS) allows for investigating phenomena that occur at gas-liquid and liquid-solid interfaces on the molecular level. The results are not only relevant for IL systems but also for liquids in general. In all of these previous ARXPS studies, the sample holder had to be tilted in order to change the polar detection angle of emitted photoelectrons, which restricted the liquid systems to very thin viscous IL films coating a flat solid support. We now report on the concept and realization of a new and unique laboratory "Dual Analyzer System for Surface Analysis (DASSA)" which enables fast ARXPS, UV photoelectron spectroscopy, imaging XPS, and low-energy ion scattering at the horizontal surface plane of macroscopically thick non-volatile liquid samples. It comprises a UHV chamber equipped with two electron analyzers mounted for simultaneous measurements in 0° and 80° emission relative to the surface normal. The performance of DASSA on a first macroscopic liquid system will be demonstrated.

  18. Multi-Object Spectroscopy with the James Webb Space Telescope’s Near Infrared Spectrograph: Observing Resolved Stellar Populations

    NASA Astrophysics Data System (ADS)

    Gilbert, Karoline; Karakla, Diane M.; Beck, Tracy

    2015-08-01

    The James Webb Space Telescope’s (JWST) Near Infrared Spectrograph (NIRSpec) will provide a multi-object spectroscopy mode through the four Micro-Shutter Arrays (MSAs). Each MSA is a grid of contiguous shutters that can be configured to form slits on more than 100 astronomical targets simultaneously. The combination of JWST’s sensitivity and superb resolution in the infrared and NIRSpec’s full wavelength coverage from 0.6 to 5 μm will open new parameter space for studies of galaxies and resolved stellar populations alike. We describe a NIRSpec MSA observing scenario for obtaining spectroscopy of individual stars in an external galaxy, and investigate the technical challenges posed by this scenario. We examine the multiplexing capability of the MSA as a function of the possible MSA configuration design choices, and investigate the primary sources of error in velocity measurements and the prospects for minimizing them. We give examples of how this and other use cases are guiding development of the NIRSpec user interfaces, including proposal planning and pipeline calibrations.

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

    PubMed

    Beard, P C; Mills, T N

    1997-01-01

    Time-resolved photoacoustic spectroscopy has been used to characterize post mortem arterial tissue for the purpose of discriminating between normal and atheromatous areas of tissue. Ultrasonic thermoelastic waves were generated in post mortem human aorta by the absorption of nanosecond laser pulses at 436, 461 and 532 nm produced by a frequency doubled Q-switched Nd:YAG laser in conjunction with a gas filled Raman cell. A PVDF membrane hydrophone was used to detect the thermoelastic waves. At 436 nm, differences in the photoacoustic signatures of normal tissue and atherorma were found to be highly variable. At 461 nm, there was a clear and reproducible difference between the photacoustic response of atheroma and normal tissue as a result of increased optical attenuation in atheroma. At 532 nm, the generation of subsurface thermoelastic waves provided a means of determining the structure and thickness of the tissue sample. It is suggested that pulsed photoacoustic spectroscopy at 461 and 532 nm may find application in characterizing arterial tissue in situ by providing information about both the composition and thickness of the vessel wall. PMID:9015817

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

    SciTech Connect

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

    2009-04-24

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

  1. A field programmable gate array-based time-resolved scaler for collinear laser spectroscopy with bunched radioactive potassium beams

    SciTech Connect

    Rossi, D. M. Davis, M.; Ringle, R.; Rodriguez, J. A.; Ryder, C. A.; Schwarz, S.; Sumithrarachchi, C.; Zhao, S.; Minamisono, K. Barquest, B. R.; Bollen, G.; Hughes, M.; Strum, R.; Tarazona, D.; Cooper, K.; Hammerton, K.; Mantica, P. F.; Morrissey, D. J.

    2014-09-15

    A new data acquisition system including a Field Programmable Gate Array (FPGA) based time-resolved scaler was developed for laser-induced fluorescence and beam bunch coincidence measurements. The FPGA scaler was tested in a collinear laser-spectroscopy experiment on radioactive {sup 37}K at the BEam COoler and LAser spectroscopy (BECOLA) facility at the National Superconducting Cyclotron Laboratory at Michigan State University. A 1.29 μs bunch width from the buncher and a bunch repetition rate of 2.5 Hz led to a background suppression factor of 3.1 × 10{sup 5} in resonant photon detection measurements. The hyperfine structure of {sup 37}K and its isotope shift relative to the stable {sup 39}K were determined using 5 × 10{sup 4} s{sup −1} {sup 37}K ions injected into the BECOLA beam line. The obtained hyperfine coupling constants A({sup 2}S{sub 1/2}) = 120.3(1.4) MHz, A({sup 2}P{sub 1/2}) = 15.2(1.1) MHz, and A({sup 2}P{sub 3/2}) = 1.4(8) MHz, and the isotope shift δν{sup 39,} {sup 37} = −264(3) MHz are consistent with the previously determined values, where available.

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

    PubMed

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

    2009-06-01

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

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

    SciTech Connect

    Williams, Kurtis A.; Howell, Steve B.; Bellini, Andrea; Rubin, Kate H. R.; Bolte, Michael E-mail: steve.b.howell@nasa.gov E-mail: psmith@as.arizona.edu E-mail: rubin@mpia.de

    2013-05-15

    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{sub WD} {>=} 0.68 M{sub Sun} with M{sub WD} Almost-Equal-To 0.83 M{sub Sun} 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{sub Sun }.

  4. Detection of cancer cells in prostate tissue with time-resolved fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Gerich, C. E.; Opitz, J.; Toma, M.; Sergon, M.; Füssel, S.; Nanke, R.; Fehre, J.; Wirth, M.; Baretton, G.; Schreiber, J.

    2011-03-01

    Goals: Improving cancer diagnosis is one of the important challenges at this time. The precise differentiation between benign and malignant tissue is in the oncology and oncologic surgery of the utmost significance. A new diagnostic system, that facilitates the decision which tissue has to be removed, would be appreciated. In previous studies many attempts were made to use tissue fluorescence for cancer recognition. However, no clear correlation was found between tissue type and fluorescence parameters like time and wavelength dependent fluorescence intensity I(t, λ). The present study is focused on cooperative behaviour of cells in benign or malignant prostates tissue reflecting differences in their metabolism. Material and Methods: 50 prostate specimens were obtained directly after radical prostatectomy and from each specimen 6 punch biopsies were taken. Time-resolved fluorescence spectra were recorded for 4 different measurement points for each biopsy. The pathologist evaluated each measurement point separately. An algorithm was developed to determine a relevant parameter of the time dependent fluorescence data (fractal dimension DF ). The results of the finding and the DF -value were correlated for each point and then analysed with statistical methods. Results: A total of 1200 measurements points were analysed. The optimal algorithm and conditions for discrimination between malignant and non-malignant tissue areas were found. The correct classification could be stated in 93.4% of analysed points. The ROC-curve (AUC = 0.94) confirms the chosen statistical method as well as it informs about the specificity (0.94) and sensitivity (0.90). Conclusion: The new method seems to offer a very helpful diagnostic tool for pathologists as well as for surgery.

  5. Infrared absorption of CH3OSO detected with time-resolved Fourier-transform spectroscopy.

    PubMed

    Chen, Jin-Dah; Lee, Yuan-Pern

    2011-03-01

    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). PMID:21384966

  6. Infrared absorption of CH3OSO detected with time-resolved Fourier-transform spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Jin-Dah; Lee, Yuan-Pern

    2011-03-01

    A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to detect temporally resolved infrared absorption spectra of CH3OSO produced upon irradiation of a flowing gaseous mixture of CH3OS(O)Cl in N2 or CO2 at 248 nm. Two intense transient features with origins near 1152 and 994 cm-1 are assigned to syn-CH3OSO; the former is attributed to overlapping bands at 1154 ± 3 and 1151 ± 3 cm-1, assigned to the S=O stretching mixed with CH3 rocking (ν8) and the S=O stretching mixed with CH3 wagging (ν9) modes, respectively, and the latter to the C-O stretching (ν10) mode at 994 ± 6 cm-1. Two weak bands at 2991 ± 6 and 2956 ± 3 cm-1 are assigned as the CH3 antisymmetric stretching (ν2) and symmetric stretching (ν3) 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-CH3OSO 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 CH3OSO and yields a second-order rate coefficient k = (4 ± 2)×10-10 cm3 molecule-1 s-1.

  7. Resolved spectroscopy of Mercury in the near-IR with SpeX/IRTF

    NASA Astrophysics Data System (ADS)

    Vernazza, P.; DeMeo, F.; Nedelcu, D. A.; Birlan, M.; Doressoundiram, A.; Erard, S.; Volquardsen, E.

    2010-09-01

    We present resolved near-infrared spectra of Mercury scanning 70% of the surface in latitude and longitude from three separate observations, allowing us to perform a compositional investigation of its surface. By scanning the surface we find that all spectra in our sample are remarkably similar suggesting overall compositional homogeneity. We do, however, observe a slope difference between the spectra. These slope changes are most likely due to differences in the emission angle over different parts of the surface. We confirm the presence of a 1.1 μm feature that had been previously detected (Warell, J. et al. [2006]. Icarus 180, 281-291) and attributed to Ca-rich clinopyroxene. Finally, we investigated Mercury's surface composition by comparing its spectrum with ground-based lunar spectra, lunar soil spectra collected in the laboratory, and analysis with a simple linear mixing model using various minerals as end-members. The result of this compositional investigation reveals that Mercury's surface composition is likely to be quite different from the Moon's. While low-Ca iron-rich pyroxenes are main surface components on the Moon (abundance varying from ˜5% to ˜35%), their abundance on Mercury may not exceed 5%. We also find that a Ca-rich clinopyroxene (in the hedenbergite-diopside series) is likely to be a main component of Mercury's surface whereas this mineral is almost absent on the Moon. Our analysis also suggests the possible presence of olivine. We find that Mercury's slope is less red than that of the Moon, in agreement with results from MESSENGER (McClintock, W.E., and 12 colleagues [2008]. Science 321, 62-65), and composition rather than variation of space weathering is likely the cause of this difference.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

    Ultrafast photoelectron studies of surface dynamics are often limited by low repetition rates. At Stony Brook we have built a cavity-enhanced high-harmonic generation XUV source that delivers ultrafast pulses to a surface science apparatus for photoelectron spectroscopy. We begin with a Ytterbium fiber laser at a repetition rate of 78 MHz and up to 90 W of average power. After compression the pulses have μJ's of energy with < 180 fs pulse width. We then use an enhancement cavity with a finesse of a few hundred to build up to the peak intensity required for high harmonic generation. The enhancement cavity is a six mirror double folded bow-tie geometry with a focus of 15 μm at a Krypton gas jet, followed by a Sapphire crystal at Brewster's angle for the fundamental to allow outcoupling of the harmonics. A single harmonic is selected using a time-preserving monochromator to maintain the short pulses, and is sent to an ultra high vacuum chamber with sample preparation and diagnostic tools as well as an electron energy spectrometer. This allows us to study the electronic dynamics of semiconductor surfaces and their interfaces with adsorbed molecules which enable various charge transfer effects. Supported by AFOSR.

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

    NASA Astrophysics Data System (ADS)

    Heberle, Joachim

    2013-03-01

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

  10. Spectral watermarking in femtosecond stimulated Raman spectroscopy: resolving the nature of the carotenoid S* state.

    PubMed

    Kloz, Miroslav; Weißenborn, Jörn; Polívka, Tomáš; Frank, Harry A; Kennis, John T M

    2016-05-25

    A new method for recording femtosecond stimulated Raman spectra was developed that dramatically improves and automatizes baseline problems. Instead of using a narrowband Raman source, the experiment is performed using shaping of a broadband source. This allows locking the signal into carefully crafted watermarks that can be recovered from measured data with high fidelity. The approach uses unique properties of Raman scattering, thus allowing a direct recording of stimulated Raman signals with robust rejection of baselines and fixed-pattern-noise. Low cost technology for generating required pulse-shapes was developed and demonstrated. The methodology is applicable to any Raman experiment but primarily targets Femtosecond Stimulated Raman spectroscopy (FSRS) where a lack of robust methods for parasitic signal rejection has been a major obstacle in the practical development of the field in the last decade. The delivered improvement in FSRS experiments was demonstrated by recording evidence that the so-called S* state of carotenoids in solution corresponds to the optically forbidden S1 state of a sparsely populated carotenoid conformation. PMID:27180633

  11. Spatially resolved localized vibrational mode spectroscopy of carbon in liquid encapsulated Czochralski grown gallium arsenide wafers

    SciTech Connect

    Yau, Waifan.

    1988-04-01

    Substitutional carbon on an arsenic lattice site is the shallowest and one of the most dominant acceptors in semi-insulating Liquid Encapsulated Czochralski (LEC) GaAs. However, the role of this acceptor in determining the well known W'' shape spatial variation of neutral EL2 concentration along the diameter of a LEC wafer is not known. In this thesis, we attempt to clarify the issue of the carbon acceptor's effect on this W'' shaped variation by measuring spatial profiles of this acceptor along the radius of three different as-grown LEC GaAs wafers. With localized vibrational mode absorption spectroscopy, we find that the profile of the carbon acceptor is relatively constant along the radius of each wafer. Average values of concentration are 8 {times} 10E15 cm{sup -3}, 1.1 {times} 10E15 cm{sup -3}, and 2.2 {times} 10E15 cm{sup -3}, respectively. In addition, these carbon acceptor LVM measurements indicate that a residual donor with concentration comparable to carbon exists in these wafers and it is a good candidate for the observed neutral EL2 concentration variation. 22 refs., 39 figs.

  12. Spatially resolved integral field spectroscopy of the ionized gas in IZw18

    NASA Astrophysics Data System (ADS)

    Kehrig, C.; Vílchez, J. M.; Pérez-Montero, E.; Iglesias-Páramo, J.; Hernández-Fernández, J. D.; Duarte Puertas, S.; Brinchmann, J.; Durret, F.; Kunth, D.

    2016-07-01

    We present a detailed 2D study of the ionized ionized interstellar medium (ISM) of IZw18 using new Potsdam Multi-Aperture Spectrophotometer-integral field unit (PMAS-IFU) optical observations. IZw18 is a high-ionization galaxy which is among the most metal-poor starbursts in the local Universe. This makes IZw18 a local benchmark for understanding the properties most closely resembling those prevailing at distant starbursts. Our IFU aperture (˜1.4 × 1.4 kpc2) samples the entire IZw18 main body and an extended region of its ionized gas. Maps of relevant emission lines and emission line ratios show that higher-excitation gas is preferentially located close to the north-west knot and thereabouts. We detect a Wolf-Rayet feature near the north-west knot. We derive spatially resolved and integrated physical-chemical properties for the ionized gas in IZw18. We find no dependence between the metallicity indicator R23 and the ionization parameter (as traced by [O III]/[O II]) across IZw18. Over ˜0.30 kpc2, using the [O III] λ4363 line, we compute Te[O III] values (˜15 000-25 000 K), and oxygen abundances are derived from the direct determinations of Te[O III]. More than 70 per cent of the higher-Te[O III] (≳22 000 K) spaxels are He IIλ4686-emitting spaxels too. From a statistical analysis, we study the presence of variations in the ISM physical-chemical properties. A galaxy-wide homogeneity, across hundreds of parsecs, is seen in O/H. Based on spaxel-by-spaxel measurements, the error-weighted mean of 12 + log(O/H) = 7.11 ± 0.01 is taken as the representative O/H for IZw18. Aperture effects on the derivation of O/H are discussed. Using our IFU data we obtain, for the first time, the IZw18 integrated spectrum.

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

    NASA Technical Reports Server (NTRS)

    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.

  14. Information processing in parallel through directionally resolved molecular polarization components in coherent multidimensional spectroscopy

    NASA Astrophysics Data System (ADS)

    Yan, Tian-Min; Fresch, Barbara; Levine, R. D.; Remacle, F.

    2015-08-01

    We propose that information processing can be implemented by measuring the directional components of the macroscopic polarization of an ensemble of molecules subject to a sequence of laser pulses. We describe the logic operation theoretically and demonstrate it by simulations. The measurement of integrated stimulated emission in different phase matching spatial directions provides a logic decomposition of a function that is the discrete analog of an integral transform. The logic operation is reversible and all the possible outputs are computed in parallel for all sets of possible multivalued inputs. The number of logic variables of the function is the number of laser pulses used in sequence. The logic function that is computed depends on the chosen chromophoric molecular complex and on its interactions with the solvent and on the two time intervals between the three pulses and the pulse strengths and polarizations. The outputs are the homodyne detected values of the polarization components that are measured in the allowed phase matching macroscopic directions, kl, k l = ∑ i l i k i where ki is the propagation direction of the ith pulse and {li} is a set of integers that encodes the multivalued inputs. Parallelism is inherently implemented because all the partial polarizations that define the outputs are processed simultaneously. The outputs, which are read directly on the macroscopic level, can be multivalued because the high dynamical range of partial polarization measurements by nonlinear coherent spectroscopy allows for fine binning of the signals. The outputs are uniquely related to the inputs so that the logic is reversible.

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

    SciTech Connect

    France, Kevin; Froning, Cynthia S.; Linsky, Jeffrey L.; Tian, Feng; Roberge, Aki

    2012-05-10

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

  16. Resolving the coronal line region of NGC 1068 with near-infrared integral field spectroscopy

    NASA Astrophysics Data System (ADS)

    Mazzalay, X.; Rodríguez-Ardila, A.; Komossa, S.; McGregor, Peter J.

    2013-04-01

    We present adaptive optics-assisted J- and K-band integral field spectroscopy of the inner 300 × 300 pc of the Seyfert 2 galaxy NGC 1068. The data were obtained with the Gemini Near-infrared Integral-Field Spectrograph integral field unit spectrometer, which provided us with high-spatial and high-spectral resolution sampling. The wavelength range covered by the observations allowed us to study the [Ca VIII], [Si VI], [Si VII], [Al IX] and [S IX] coronal line (CL) emission, covering ionization potentials up to 328 eV. The observations reveal very rich and complex structures, both in terms of velocity fields and emission-line ratios. The CL emission is elongated along the NE-SW direction, with the stronger emission preferentially localized to the NE of the nucleus. CLs are emitted by gas covering a wide range of velocities, with maximum blueshifts/redshifts of ˜ -1600/1000 km s-1. There is a trend for the gas located on the NE side of the nucleus to be blueshifted while the gas located towards the SW is redshifted. The morphology and the kinematics of the near-infrared CLs are in very good agreement with the ones displayed by low-ionization lines and optical CLs, suggesting a common origin. The line flux distributions, velocity maps, ionization structure (traced by the [Si VII]/[Si VI] emission-line ratio) and low-ionization emission-line ratios (i.e. [Fe II]/Paβ and [Fe II]/[P II]) suggest that the radio jet plays an important role in the structure of the CL region of this object, and possibly in its kinematics.

  17. Absolute calibration method for nanosecond-resolved, time-streaked, fiber optic light collection, spectroscopy systems

    SciTech Connect

    Johnston, Mark D.; Oliver, Bryan V.; Droemer, Darryl W.; Frogget, Brent; Crain, Marlon D.; Maron, Yitzhak

    2012-08-15

    This paper describes a convenient and accurate method to calibrate fast (<1 ns resolution) streaked, fiber optic light collection, spectroscopy systems. Such systems are inherently difficult to calibrate due to the lack of sufficiently intense, calibrated light sources. Such a system is used to collect spectral data on plasmas generated in electron beam diodes fielded on the RITS-6 accelerator (8-12MV, 140-200kA) at Sandia National Laboratories. On RITS, plasma light is collected through a small diameter (200 {mu}m) optical fiber and recorded on a fast streak camera at the output of a 1 meter Czerny-Turner monochromator. For this paper, a 300 W xenon short arc lamp (Oriel Model 6258) was used as the calibration source. Since the radiance of the xenon arc varies from cathode to anode, just the area around the tip of the cathode ('hotspot') was imaged onto the fiber, to produce the highest intensity output. To compensate for chromatic aberrations, the signal was optimized at each wavelength measured. Output power was measured using 10 nm bandpass interference filters and a calibrated photodetector. These measurements give power at discrete wavelengths across the spectrum, and when linearly interpolated, provide a calibration curve for the lamp. The shape of the spectrum is determined by the collective response of the optics, monochromator, and streak tube across the spectral region of interest. The ratio of the spectral curve to the measured bandpass filter curve at each wavelength produces a correction factor (Q) curve. This curve is then applied to the experimental data and the resultant spectra are given in absolute intensity units (photons/sec/cm{sup 2}/steradian/nm). Error analysis shows this method to be accurate to within +/- 20%, which represents a high level of accuracy for this type of measurement.

  18. Absolute calibration method for nanosecond-resolved, time-streaked, fiber optic light collection, spectroscopy systems

    NASA Astrophysics Data System (ADS)

    Johnston, Mark D.; Oliver, Bryan V.; Droemer, Darryl W.; Frogget, Brent; Crain, Marlon D.; Maron, Yitzhak

    2012-08-01

    This paper describes a convenient and accurate method to calibrate fast (<1 ns resolution) streaked, fiber optic light collection, spectroscopy systems. Such systems are inherently difficult to calibrate due to the lack of sufficiently intense, calibrated light sources. Such a system is used to collect spectral data on plasmas generated in electron beam diodes fielded on the RITS-6 accelerator (8-12MV, 140-200kA) at Sandia National Laboratories. On RITS, plasma light is collected through a small diameter (200 μm) optical fiber and recorded on a fast streak camera at the output of a 1 meter Czerny-Turner monochromator. For this paper, a 300 W xenon short arc lamp (Oriel Model 6258) was used as the calibration source. Since the radiance of the xenon arc varies from cathode to anode, just the area around the tip of the cathode ("hotspot") was imaged onto the fiber, to produce the highest intensity output. To compensate for chromatic aberrations, the signal was optimized at each wavelength measured. Output power was measured using 10 nm bandpass interference filters and a calibrated photodetector. These measurements give power at discrete wavelengths across the spectrum, and when linearly interpolated, provide a calibration curve for the lamp. The shape of the spectrum is determined by the collective response of the optics, monochromator, and streak tube across the spectral region of interest. The ratio of the spectral curve to the measured bandpass filter curve at each wavelength produces a correction factor (Q) curve. This curve is then applied to the experimental data and the resultant spectra are given in absolute intensity units (photons/sec/cm2/steradian/nm). Error analysis shows this method to be accurate to within +/- 20%, which represents a high level of accuracy for this type of measurement.

  19. Near-infrared spatially resolved spectroscopy of (136108) Haumea's multiple system

    NASA Astrophysics Data System (ADS)

    Gourgeot, F.; Carry, B.; Dumas, C.; Vachier, F.; Merlin, F.; Lacerda, P.; Barucci, M. A.; Berthier, J.

    2016-08-01

    Context. The transneptunian region of the solar system is populated by a wide variety of icy bodies showing great diversity in orbital behavior, size, surface color, and composition. Aims: The dwarf planet (136108) Haumea is among the largest transneptunian objects (TNOs) and is a very fast rotator (~3.9 h). This dwarf planet displays a highly elongated shape and hosts two small moons that are covered with crystalline water ice, similar to their central body. A particular region of interest is the Dark Red Spot (DRS) identified on the surface of Haumea from multiband light-curve analysis (Lacerda et al. 2008). Haumea is also known to be the largest member of the sole TNO family known to date, and an outcome of a catastrophic collision that is likely responsible for the unique characteristics of Haumea. Methods: We report here on the analysis of a new set of near-infrared Laser Guide Star assisted observations of Haumea obtained with the Integral Field Unit (IFU) Spectrograph for INtegral Field Observations in the Near Infrared (SINFONI) at the European Southern Observatory (ESO) Very Large Telescope (VLT) Observatory. Combined with previous data published by Dumas et al. (2011), and using light-curve measurements in the optical and far infrared to associate each spectrum with its corresponding rotational phase, we were able to carry out a rotationally resolved spectroscopic study of the surface of Haumea. Results: We describe the physical characteristics of the crystalline water ice present on the surface of Haumea for both regions, in and out of the DRS, and analyze the differences obtained for each individual spectrum. The presence of crystalline water ice is confirmed over more than half of the surface of Haumea. Our measurements of the average spectral slope (1.45 ± 0.82% by 100 nm) confirm the redder characteristic of the spot region. Detailed analysis of the crystalline water-ice absorption bands do not show significant differences between the DRS and the

  20. Rotationally resolved spectroscopy of a librational fundamental band of hydrogen fluoride tetramer

    SciTech Connect

    Blake, Thomas A.; Sharpe, Steven W.; Xantheas, Sotiris S.

    2000-07-08

    The rotationally resolved spectrum of a fundamental band of hydrogen fluoride tetramer has been recorded using a pulsed slit-jet, diode laser spectrometer. The band has a parallel rotational structure and is assigned as the H-F out-of-plane libration fundamental with A{sub u} symmetry. Ninety-five ground state combination differences were fit to a symmetric top Hamiltonian to give the following ground state rotational constants: B{sup ''}=0.132 081(7) cm{sup -1}, D{sub J}{sup ''}=7.1(7)x10{sup -7} cm{sup -1}, D{sub JK}{sup ''}=-9(2)x10{sup -7} cm{sup -1}, H{sub JJJ}{sup ''}=6(2)x10{sup -10} cm{sup -1}, H{sub JJK}{sup ''}=9(7)x10{sup -10} cm{sup -1}, H{sub JKK}{sup ''}=-1.3(8)x10{sup -10} cm{sup -1}. A total of 190 transitions were fit to determine the upper state spectroscopic constants: v{sub 4}=714.7849(1) cm{sup -1}, B{sup '}=0.129 634(5) cm{sup -1}, {delta}(C-B)=0.001 344 cm{sup -1}, D{sub J}{sup '}=6.4(5)x10{sup -7} cm{sup -1}, D{sub JK}{sup '}=-4.5(6)x10{sup -7} cm{sup -1}, {delta}D{sub K}=2.92(8)x10{sup -6} cm{sup -1}, H{sub JJJ}{sup '}=3(1)x10{sup -10} cm{sup -1}, H{sub JKK}{sup '}=-1.55(6)x10{sup -8} cm{sup -1}; {delta}H{sub KKK}=-4.65(6)x10{sup -8} cm{sup -1}. Furthermore, a perpendicular band centered at 752.7 cm{sup -1} was observed. The band has a rotational line spacing that gives an approximate B{sup ''} value of 0.132 cm{sup -1}; it has been assigned as the E{sub u} symmetry, H-F in-plane libration fundamental of the HF tetramer. Finally, a parallel band was observed at 741.0 cm{sup -1} with B{sup ''}=0.076 cm{sup -1} and has been assigned as the A{sup ''} symmetry, H-F out-of-plane libration fundamental of the HF pentamer. Structural parameters and harmonic vibrational frequencies are estimated from first-principles, correlated MP2 and CCSD(T) calculations. These are the largest calculations performed to date for this system with respect to both orbital basis set and level of electron correlation. The CCSD(T) harmonic frequencies are, in particular

  1. Holographic Spectroscopy for Rapid Electron Bunch Analysis: Development of an Instrument with THZ Resolved Optical Gating

    SciTech Connect

    Sievers, Albert

    2011-10-28

    The main thrust of our project was to apply the concepts of holographic spectroscopy, developed earlier in the visible and near IR spectral regions for satellite mapping, to the THz region in order to measure the spectral signature of the coherent radiation emanating from a relativistic electron bunch to obtain the bunch length itself. There were four major discoveries. (1) In the course of this ground-breaking work we developed and built the first static THz interferometer suitable for the realization of such a holographic Fourier transform spectrometer. Experimental tests and analysis of the observed results have provided the necessary foundation for future development of THz detector arrays optimized for spectroscopic applications. (2) Since such detectors do not exist at the present time our next effort was to find an alternative approach. We explored the electro-optic (EO) detection of the THz pulse using the short pulse of a visible diode laser synchronized to the bunch with the long-term goal aimed at single bunch measurement capability. The main hurdle was found to be the parasitic scattering of the diode radiation in the EO medium. By using the optical Fourier transform of the THz interference pattern the effects of this background were suppressed enough to obtain the spectrum using multiple shot acquisition. During our experiments at the FLASH facility at DESY we determined that for single bunch measurement capability the diode laser has to be able to produce sub 100 ps pulses with peak power of at least 1 W. Since these parameters are quite feasible at the current stage of diode laser science this combination of techniques can be used for single shot measurement of a short electron bunch. (3) In carrying out the above effort a simpler measurement possibility was uncovered involving the visible/nearIR pulse of incoherent radiation produced by the same bunch. This observation made possible the cross-correlation of the THz coherent and visible incoherent

  2. Excited state non-adiabatic dynamics of pyrrole: A time-resolved photoelectron spectroscopy and quantum dynamics study

    SciTech Connect

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

    2015-02-21

    The dynamics of pyrrole excited at wavelengths in the range 242-217 nm are studied using a combination of time-resolved photoelectron spectroscopy and wavepacket propagations performed using the multi-configurational time-dependent Hartree method. Excitation close to the origin of pyrrole’s electronic spectrum, at 242 and 236 nm, is found to result in an ultrafast decay of the system from the ionization window on a single timescale of less than 20 fs. This behaviour is explained fully by assuming the system to be excited to the A{sub 2}(πσ{sup ∗}) state, in accord with previous experimental and theoretical studies. Excitation at shorter wavelengths has previously been assumed to result predominantly in population of the bright A{sub 1}(ππ{sup ∗}) and B{sub 2}(ππ{sup ∗}) states. We here present time-resolved photoelectron spectra at a pump wavelength of 217 nm alongside detailed quantum dynamics calculations that, together with a recent reinterpretation of pyrrole’s electronic spectrum [S. P. Neville and G. A. Worth, J. Chem. Phys. 140, 034317 (2014)], suggest that population of the B{sub 1}(πσ{sup ∗}) state (hitherto assumed to be optically dark) may occur directly when pyrrole is excited at energies in the near UV part of its electronic spectrum. The B{sub 1}(πσ{sup ∗}) state is found to decay on a timescale of less than 20 fs by both N-H dissociation and internal conversion to the A{sub 2}(πσ{sup ∗}) state.

  3. Nanosecond time-resolved microscopic spectroscopy for diagnostics of an atmospheric-pressure discharge plasma formed in aqueous solution

    NASA Astrophysics Data System (ADS)

    Banno, Motohiro; Kanno, Kenta; Someya, Yuu; Yui, Hiroharu

    2015-06-01

    Glow discharge plasma formed in solution under atmospheric pressure has been expected to provide reaction fields with characteristic physical and chemical properties owing to the frequent collisions and reactions of reactive particles inside and the rapid quenching of the products by the surrounding cold solutions. In particular, when an aqueous solution is utilized as the surrounding solution, the atmospheric-pressure in-solution glow (ASG) plasma contains hydrogen and hydroxyl radicals showing large activities for reduction and oxidation, respectively. In addition, because the ASG plasma is formed under atmospheric pressure, the collision frequencies between the particles contained in the plasma are higher than those in other plasmas ordinarily formed under low pressure. This feature should result in rapid energy redistribution among particles contained in the plasma. In the present study, time-resolved optical emission spectroscopy with nanosecond time resolution was applied for the diagnostics of the ASG plasma with chemical species selectivity. The time-resolved measurements revealed that the temporal evolutions of the temperatures of blackbody, hydrogen radical, and hydroxyl radical contained in the ASG plasma consist of two stages: initial rise within 0.15 µs (rising stage) and fluctuation around certain values for about 1 µs (fluctuating stage). In the time region corresponding to the rising stage, the electron number density is about ten times larger than the value temporally averaged during the plasma emission. The initial rise should result from frequent collisions between charged particles accelerated by the applied voltage and unexcited particles. In the fluctuating stage, the electron number density strongly correlates with the increase in the radical temperatures. It is concluded that the electron number density, rather than the electron temperature, is a key parameter determining the temperatures of reactive species in the ASG plasma.

  4. Characterization of a hybrid diffuse correlation spectroscopy and time-resolved near-infrared spectroscopy system for real-time monitoring of cerebral blood flow and oxygenation

    NASA Astrophysics Data System (ADS)

    Verdecchia, K.; Diop, M.; Lee, A.; St. Lawrence, K.

    2015-03-01

    The combination of near-infrared spectroscopy (NIRS) and diffuse correlation spectroscopy (DCS) offers the ability to provide real-time monitoring of cerebral oxygenation, blood flow and oxygen consumption. However, measuring these parameters accurately requires depth-sensitive techniques that can remove the effects of signal contamination from extracerebral tissues. Towards this goal, we developed and characterized a hybrid DCS/time-resolved (TR)-NIRS system. Both systems acquire data at three source-detector distances (SDD: 7, 20 and 30 mm) to provide depth sensitivity. The TR-NIRS system uses three pulsed lasers (760, 810, and 830 nm) to quantify tissue optical properties, and DCS uses one continuous-wave, long coherence length (>5 m) laser (785 nm) for blood flow monitoring. The stability of the TR-NIRS system was characterized by continuously measuring the instrument response function (IRF) for four hours, and a warmup period of two hours was required to reduce the coefficient of variation of the extracted optical properties to < 2%. The errors in the measured optical properties were <10% at SDDs of 20 and 30 mm; however, the error at 7 mm was greater due to the effects of the IRF. The number of DCS detectors at each SDD and the minimum count-rate (20 kHz per detector resulting in <10% uncertainty in the extracted blood flow index) were optimized using a homogenous phantom. The depth sensitivity was assessed using a two-layer phantom, with the flow rate in the bottom layer altered to mimic cerebral blood flow.

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

    NASA Astrophysics Data System (ADS)

    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.

  6. Influence of cutaneous and muscular circulation on spatially resolved versus standard Beer-Lambert near-infrared spectroscopy.

    PubMed

    Messere, Alessandro; Roatta, Silvestro

    2013-12-01

    The potential interference of cutaneous circulation on muscle blood volume and oxygenation monitoring by near-infrared spectroscopy (NIRS) remains an important limitation of this technique. Spatially resolved spectroscopy (SRS) was reported to minimize the contribution of superficial tissue layers in cerebral monitoring but this characteristic has never been documented in muscle tissue monitoring. This study aims to compare SRS with the standard Beer-Lambert (BL) technique in detecting blood volume changes selectively induced in muscle and skin. In 16 healthy subjects, the biceps brachii was investigated during isometric elbow flexion at 70% of the maximum voluntary contractions lasting 10 sec, performed before and after exposure of the upper arm to warm air flow. From probes applied over the muscle belly the following variables were recorded: total hemoglobin index (THI, SRS-based), total hemoglobin concentration (tHb, BL-based), tissue oxygenation index (TOI, SRS-based), and skin blood flow (SBF), using laser Doppler flowmetry. Blood volume indices exhibited similar changes during muscle contraction but only tHb significantly increased during warming (+5.2 ± 0.7 μmol/L·cm, an effect comparable to the increase occurring in postcontraction hyperemia), accompanying a 10-fold increase in SBF. Contraction-induced changes in tHb and THI were not substantially affected by warming, although the tHb tracing was shifted upward by (5.2 ± 3.5 μmol/L·cm, P < 0.01). TOI was not affected by cutaneous warming. In conclusion, SRS appears to effectively reject interference by SBF in both muscle blood volume and oxygenation monitoring. Instead, BL-based parameters should be interpreted with caution, whenever changes in cutaneous perfusion cannot be excluded. PMID:24744858

  7. Single water solvation dynamics in the 4-aminobenzonitrile-water cluster cation revealed by picosecond time-resolved infrared spectroscopy.

    PubMed

    Miyazaki, Mitsuhiko; Nakamura, Takashi; Wohlgemuth, Matthias; Mitrić, Roland; Dopfer, Otto; Fujii, Masaaki

    2015-11-28

    The dynamics of a solvent is important for many chemical and biological processes. Here, the migration dynamics of a single water molecule is triggered by the photoionization of the 4-aminobenzonitrile-water (4ABN-W) cluster and monitored in real time by picosecond time-resolved IR (ps TRIR) spectroscopy. In the neutral cluster, water is hydrogen-bonded to the CN group. When this CN-bound cluster is selectively ionized with an excess energy of 1238 cm(-1), water migrates with a lifetime of τ = 17 ps from the CN to the NH2 group, forming a more stable 4ABN(+)-W(NH) isomer with a yield of unity. By decreasing the ionization excess energy, the yield of the CN → NH2 reaction is reduced. The relatively slow migration in comparison to the ionization-induced solvent dynamics in the related acetanilide-water cluster cation (τ = 5 ps) is discussed in terms of the internal excess energy after photoionization and the shape of the potential energy surface. PMID:26490096

  8. Spatially resolved optical absorption spectroscopy of single- and few-layer MoS2 by hyperspectral imaging

    NASA Astrophysics Data System (ADS)

    Castellanos-Gomez, Andres; Quereda, Jorge; van der Meulen, Herko P.; Agraït, Nicolás; Rubio-Bollinger, Gabino

    2016-03-01

    The possibility of spatially resolving the optical properties of atomically thin materials is especially appealing as they can be modulated at the micro- and nanoscale by reducing their thickness, changing the doping level or applying a mechanical deformation. Therefore, optical spectroscopy techniques with high spatial resolution are necessary to get a deeper insight into the properties of two-dimensional (2D) materials. Here we study the optical absorption of single- and few-layer molybdenum disulfide (MoS2) in the spectral range from 1.24 eV to 3.22 eV (385 nm to 1000 nm) by developing a hyperspectral imaging technique that allows one to probe the optical properties with diffraction limited spatial resolution. We find hyperspectral imaging very suited to study indirect bandgap semiconductors, unlike photoluminescence which only provides high luminescence yield for direct gap semiconductors. Moreover, this work opens the door to study the spatial variation of the optical properties of other 2D systems, including non-semiconducting materials where scanning photoluminescence cannot be employed.

  9. Communication: Vibrationally resolved photoelectron spectroscopy of the tetracyanoquinodimethane (TCNQ) anion and accurate determination of the electron affinity of TCNQ

    NASA Astrophysics Data System (ADS)

    Zhu, Guo-Zhu; Wang, Lai-Sheng

    2015-12-01

    Tetracyanoquinodimethane (TCNQ) is widely used as an electron acceptor to form highly conducting organic charge-transfer solids. Surprisingly, the electron affinity (EA) of TCNQ is not well known and has never been directly measured. Here, we report vibrationally resolved photoelectron spectroscopy (PES) of the TCNQ- anion produced using electrospray and cooled in a cryogenic ion trap. Photoelectron spectrum taken at 354.7 nm represents the detachment transition from the ground state of TCNQ- to that of neutral TCNQ with a short vibrational progression. The EA of TCNQ is measured accurately to be 3.383 ± 0.001 eV (27 289 ± 8 cm-1), compared to the 2.8 ± 0.1 eV value known in the literature and measured previously using collisional ionization technique. In addition, six vibrational peaks are observed in the photoelectron spectrum, yielding vibrational frequencies for three totally symmetric modes of TCNQ. Two-photon PES via a bound electronic excited state of TCNQ- at 3.100 eV yields a broad low kinetic energy peak due to fast internal conversion to vibrationally excited levels of the anion ground electronic state. The high EA measured for TCNQ underlies its ability as a good electron acceptor.

  10. Characterization of direct-drive-implosion core conditions on OMEGA with time-resolved Ar K-shell spectroscopy

    NASA Astrophysics Data System (ADS)

    Regan, S. P.; Delettrez, J. A.; Epstein, R.; Jaanimagi, P. A.; Yaakobi, B.; Smalyuk, V. A.; Marshall, F. J.; Meyerhofer, D. D.; Seka, W.; Haynes, D. A.; Golovkin, I. E.; Hooper, C. F.

    2002-04-01

    Direct-drive-implosion core conditions have been characterized on the 60-beam OMEGA [T. R. Boehly et al., Opt. Commun. 133, 495 (1997)] laser system with time-resolved Ar K-shell spectroscopy. Plastic shells with an Ar-doped deuterium fill gas were driven with a 23 kJ, 1 ns square laser pulse smoothed with 1 THz smoothing by spectral dispersion (SSD) and polarization smoothing (PS) using birefringent wedges. The targets are predicted to have a convergence ratio of ˜15. The emissivity-averaged core electron temperature (Te) and density (ne) were inferred from the measured time-dependent Ar K-shell spectral line shapes. As the imploding shell decelerates the observed Te and ne increase to 2.0 (±0.2) keV and 2.5 (±0.5)×1024cm-3 at peak neutron production, which is assumed to occur at the time of the peak emissivity-averaged Te. At peak compression the ne increases to 3.1 (±0.6)×1024cm-3 and the Te decreases to 1.7 (±0.17) keV. The observed core conditions are close to those predicted by a one-dimensional hydrodynamics code.

  11. Determination of the Fermi surface in high-T{sub c} superconductors by angle-resolved photoemission spectroscopy

    SciTech Connect

    Mesot, J.; Randeria, M.; Norman, M. R.; Kaminski, A.; Fretwell, H. M.; Campuzano, J. C.; Ding, H.; Takeuchi, T.; Sato, T.; Yokoya, T.

    2001-06-01

    We study the normal-state electronic excitations probed by angle-resolved photoemission spectroscopy (ARPES) in Bi{sub 1.6}Pb{sub 0.4}Sr{sub 2}CuO{sub 6} (Bi2201) and Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+{delta}} (Bi2212). Our main goal is to establish explicit criteria for determining the Fermi surface from ARPES data on strongly interacting systems where sharply defined quasiparticles do not exist and the dispersion is very weak in parts of the Brillouin zone. Additional complications arise from strong matrix element variations within the zone. We present detailed results as a function of incident photon energy, and show simple experimental tests to distinguish between an intensity drop due to matrix element effects and spectral weight loss due to a Fermi crossing. We reiterate the use of polarization selection rules in disentangling the effect of umklapps due to the BiO superlattice in Bi2212. We conclude that, despite all the complications, the Fermi surface can be determined unambiguously; it is a single large hole barrel centered about ({pi},{pi}) in both materials.

  12. Direct Observation of Localized Spin Antiferromagnetic Transition in PdCrO2 by Angle-Resolved Photoemission Spectroscopy

    NASA Astrophysics Data System (ADS)

    Noh, Han-Jin; Jeong, Jinwon; Chang, Bin; Jeong, Dahee; Moon, Hyun Sook; Cho, En-Jin; Ok, Jong Mok; Kim, Jun Sung; Kim, Kyoo; Min, B. I.; Lee, Han-Koo; Kim, Jae-Young; Park, Byeong-Gyu; Kim, Hyeong-Do; Lee, Seongsu

    2014-03-01

    We report the first case of the successful measurements of a localized spin antiferromagnetic transition in delafossite-type PdCrO2 by angle-resolved photoemission spectroscopy (ARPES). This demonstrates how to circumvent the shortcomings of ARPES for investigation of magnetism involved with localized spins in limited size of two-dimensional crystals or multi-layer thin films that neutron scattering can hardly study due to lack of bulk compared to surface. Also, our observations give direct evidence for the spin ordering pattern of Cr3+ ions in PdCrO2 suggested by neutron diffraction and quantum oscillation measurements, and provide a strong constraint that has to be satisfied by a microscopic mechanism for the unconventional anomalous Hall effect recently reported in this system. This work was supported by the National Research Foundation (NRF) of Korea Grant funded by the Korean Government (MEST) (Nos. 2010-0010771 and 2012M2B2A4029607). K.K. and B.I.M. acknowledge the support of NRF (Nos. 2009-0079947 and 2011-0025237) and KISTI.

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

    SciTech Connect

    Plogmaker, S. E-mail: Joachim.Terschluesen@physics.uu.se Terschlüsen, J. A. E-mail: Joachim.Terschluesen@physics.uu.se Krebs, N.; Svanqvist, M.; Forsberg, J.; Cappel, U. B.; Rubensson, J.-E.; Siegbahn, H.; Söderström, J. E-mail: Joachim.Terschluesen@physics.uu.se

    2015-12-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-03-01

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

  15. Pump laser-induced space-charge effects in HHG-driven time- and angle-resolved photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Oloff, L.-P.; Hanff, K.; Stange, A.; Rohde, G.; Diekmann, F.; Bauer, M.; Rossnagel, K.

    2016-06-01

    With the advent of ultrashort-pulsed extreme ultraviolet sources, such as free-electron lasers or high-harmonic-generation (HHG) sources, a new research field for photoelectron spectroscopy has opened up in terms of femtosecond time-resolved pump-probe experiments. The impact of the high peak brilliance of these novel sources on photoemission spectra, so-called vacuum space-charge effects caused by the Coulomb interaction among the photoemitted probe electrons, has been studied extensively. However, possible distortions of the energy and momentum distributions of the probe photoelectrons caused by the low photon energy pump pulse due to the nonlinear emission of electrons have not been studied in detail yet. Here, we systematically investigate these pump laser-induced space-charge effects in a HHG-based experiment for the test case of highly oriented pyrolytic graphite. Specifically, we determine how the key parameters of the pump pulse—the excitation density, wavelength, spot size, and emitted electron energy distribution—affect the measured time-dependent energy and momentum distributions of the probe photoelectrons. The results are well reproduced by a simple mean-field model, which could open a path for the correction of pump laser-induced space-charge effects and thus toward probing ultrafast electron dynamics in strongly excited materials.

  16. Anisotropy of chemical bonding in semifluorinated graphite C2F revealed with angle-resolved X-ray absorption spectroscopy.

    PubMed

    Okotrub, Alexander V; Yudanov, Nikolay F; Asanov, Igor P; Vyalikh, Denis V; Bulusheva, Lyubov G

    2013-01-22

    Highly oriented pyrolytic graphite characterized by a low misorientation of crystallites is fluorinated using a gaseous mixture of BrF(3) with Br(2) at room temperature. The golden-colored product, easily delaminating into micrometer-size transparent flakes, is an intercalation compound where Br(2) molecules are hosted between fluorinated graphene layers of approximate C(2)F composition. To unravel the chemical bonding in semifluorinated graphite, we apply angle-resolved near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and quantum-chemical modeling. The strong angular dependence of the CK and FK edge NEXAFS spectra on the incident radiation indicates that room-temperature-produced graphite fluoride is a highly anisotropic material, where half of the carbon atoms are covalently bonded with fluorine, while the rest of the carbon atoms preserve π electrons. Comparison of the experimental CK edge spectrum with theoretical spectra plotted for C(2)F models reveals that fluorine atoms are more likely to form chains. This conclusion agrees with the atomic force microscopy observation of a chain-like pattern on the surface of graphite fluoride layers. PMID:23214423

  17. Two-photon resonances in femtosecond time-resolved four-wave mixing spectroscopy: {beta}-carotene

    SciTech Connect

    Namboodiri, V.; Namboodiri, M.; Flachenecker, G.; Materny, A.

    2010-08-07

    Femtosecond time-resolved pump-degenerate four-wave mixing (pump-DFWM) spectroscopy has been used to study the ultrafast dynamics of {beta}-carotene involving several electronic and vibrational states. An initial pump pulse, resonant with the S{sub 0}-to-S{sub 2} transition, excites the molecular system and a DFWM process, resonant with the S{sub 1}-to-S{sub n} transition, is used to probe the relaxation pathways. The transient shows a peculiar decay behavior, which is due to the contributions of resonant DFWM signal of the excited S{sub 1} state, nonresonant DFWM signal of the ground S{sub 0} state and vibrational hot S{sub 0}{sup *} state, and the two-photon resonant DFWM signal of the ground S{sub 0} state. We have used a kinetic model including all the signal contributions to successfully fit the transient. The time constants extracted are in very good agreement with the known values for {beta}-carotene. For comparison, a two-pulse pump-probe experiment was performed measuring the transient absorption at the wavelength of the DFWM experiment.

  18. Communication: Vibrationally resolved photoelectron spectroscopy of the tetracyanoquinodimethane (TCNQ) anion and accurate determination of the electron affinity of TCNQ

    SciTech Connect

    Zhu, Guo-Zhu; Wang, Lai-Sheng

    2015-12-14

    Tetracyanoquinodimethane (TCNQ) is widely used as an electron acceptor to form highly conducting organic charge-transfer solids. Surprisingly, the electron affinity (EA) of TCNQ is not well known and has never been directly measured. Here, we report vibrationally resolved photoelectron spectroscopy (PES) of the TCNQ{sup −} anion produced using electrospray and cooled in a cryogenic ion trap. Photoelectron spectrum taken at 354.7 nm represents the detachment transition from the ground state of TCNQ{sup −} to that of neutral TCNQ with a short vibrational progression. The EA of TCNQ is measured accurately to be 3.383 ± 0.001 eV (27 289 ± 8 cm{sup −1}), compared to the 2.8 ± 0.1 eV value known in the literature and measured previously using collisional ionization technique. In addition, six vibrational peaks are observed in the photoelectron spectrum, yielding vibrational frequencies for three totally symmetric modes of TCNQ. Two-photon PES via a bound electronic excited state of TCNQ{sup −} at 3.100 eV yields a broad low kinetic energy peak due to fast internal conversion to vibrationally excited levels of the anion ground electronic state. The high EA measured for TCNQ underlies its ability as a good electron acceptor.

  19. Method for depth-resolved quantitation of optical properties in layered media using spatially modulated quantitative spectroscopy

    PubMed Central

    Saager, Rolf B.; Truong, Alex; Cuccia, David J.; Durkin, Anthony J.

    2011-01-01

    We have demonstrated that spatially modulated quantitative spectroscopy (SMoQS) is capable of extracting absolute optical properties from homogeneous tissue simulating phantoms that span both the visible and near-infrared wavelength regimes. However, biological tissue, such as skin, is highly structured, presenting challenges to quantitative spectroscopic techniques based on homogeneous models. In order to more accurately address the challenges associated with skin, we present a method for depth-resolved optical property quantitation based on a two layer model. Layered Monte Carlo simulations and layered tissue simulating phantoms are used to determine the efficacy and accuracy of SMoQS to quantify layer specific optical properties of layered media. Initial results from both the simulation and experiment show that this empirical method is capable of determining top layer thickness within tens of microns across a physiological range for skin. Layer specific chromophore concentration can be determined to <±10% the actual values, on average, whereas bulk quantitation in either visible or near infrared spectroscopic regimes significantly underestimates the layer specific chromophore concentration and can be confounded by top layer thickness. PMID:21806282

  20. Communication: Ultrafast time-resolved ion photofragmentation spectroscopy of photoionization-induced proton transfer in phenol-ammonia complex

    SciTech Connect

    Shen, Ching-Chi; Tsai, Tsung-Ting; Ho, Jr-Wei; Chen, Yi-Wei; Cheng, Po-Yuan

    2014-11-07

    Photoionization-induced proton transfer (PT) in phenol-ammonia (PhOH-NH{sub 3}) complex has been studied using ultrafast time-resolved ion photofragmentation spectroscopy. Neutral PhOH-NH{sub 3} complexes prepared in a free jet are photoionized by femtosecond [1+1] resonance-enhanced multiphoton ionization via the S{sub 1} state, and the subsequent dynamics occurring in the cations is probed by delayed pulses that result in ion fragmentation. The observed temporal evolutions of the photofragmentation spectra are consistent with an intracomplex PT reaction. The experiments revealed that PT in [PhOH-NH{sub 3}]{sup +} cation proceeds in two distinct steps: an initial impulsive wave-packet motion in ∼70 fs followed by a slower relaxation of about 1 ps that stabilizes the system into the final PT configuration. These results indicate that for a barrierless PT system, even though the initial PT motions are impulsive and ultrafast, the reaction may take a much longer time scale to complete.

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

    NASA Astrophysics Data System (ADS)

    Sabau, A.; Pipon, Y.; Toulhoat, N.; Lomenech, C.; Jordan, N.; Moncoffre, N.; Barkleit, A.; Marmier, N.; Brendler, V.; Surblé, S.; Giffaut, E.

    2014-08-01

    This study aims at elucidating the mechanisms regulating the interaction of Eu and Ni with calcite (CaCO3). Calcite powders or single crystals (some mm sized) were put into contact with Eu or Ni solutions at concentrations ranging from 10-3 to 10-5 mol L-1 for Eu and 10-3 mol L-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.

  2. Angle-resolved photoelectron spectroscopy study of initial stage of thermal oxidation on 4H-SiC(0001)

    NASA Astrophysics Data System (ADS)

    Arai, Hitoshi; Nohira, Hiroshi

    2016-04-01

    A key to improving the performance of SiC MOSFETs is to clarify the SiO2/SiC interface structure formed by thermal oxidation. We have investigated the initial stage of thermal oxidation on 4H-SiC(0001) by angle-resolved photoelectron spectroscopy. From the changes in the Si 2p3/2 and C 1s photoelectron spectra, the changes in the chemical bonding state of the SiO2/SiC structure with the progress of thermal oxidation were observed. We also found that the intensity of C-O bonds in the case of 4H-SiC(0001) was smaller than that in the case of 4H-SiC(000\\bar{1}) with the same oxide thickness and that the oxidation rate of 4H-SiC(0001) is already slower than that of 4H-SiC(000\\bar{1}) in the early stage of oxidation.

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

    PubMed

    Plogmaker, S; Terschlüsen, J A; Krebs, N; Svanqvist, M; Forsberg, J; Cappel, U B; Rubensson, J-E; Siegbahn, H; Söderström, J

    2015-12-01

    In this paper, we present the HELIOS (High Energy Laser Induced Overtone Source) laboratory, an in-house high-order harmonic generation facility which generates extreme ultraviolet (XUV) photon pulses in the range of 15-70 eV with monochromatized XUV pulse lengths below 35 fs. HELIOS is a source for time-resolved pump-probe/two-color spectroscopy in the sub-50 fs range, which can be operated at 5 kHz or 10 kHz. An optical parametric amplifier is available for pump-probe experiments with wavelengths ranging from 240 nm to 20,000 nm. The produced XUV radiation is monochromatized by a grating in the so-called off-plane mount. Together with overall design parameters, first monochromatized spectra are shown with an intensity of 2 ⋅ 10(10) photons/s (at 5 kHz) in the 29th harmonic, after the monochromator. The XUV pulse duration is measured to be <25 fs after monochromatization. PMID:26724006

  4. The structure of 4-methylphenol and its water cluster revealed by rotationally resolved UV spectroscopy using a genetic algorithm approach

    NASA Astrophysics Data System (ADS)

    Myszkiewicz, Grzegorz; Meerts, W. Leo; Ratzer, Christian; Schmitt, Michael

    2005-07-01

    The structure of 4-methylphenol (p-cresol) and its binary water cluster have been elucidated by rotationally resolved laser-induced fluorescence spectroscopy. The electronic origins of the monomer and the cluster are split into four sub-bands by the internal rotation of the methyl group and of the hydroxy group in case of the monomer, and the water moiety in case of the cluster. From the rotational constants of the monomer the structure in the S1 state could be determined to be distorted quinoidally. The structure of the p-cresol-water cluster is determined to be trans linear, with a O-O hydrogen bond length of 290pm in the electronic ground state and of 285pm in the electronically excited state. The S1-state lifetime of p-cresol, p-cresol-d1, and the binary water cluster have been determined to be 1.6, 9.7, and 3.8ns, respectively.

  5. Phase-resolved two-dimensional terahertz spectroscopy including off-resonant interactions beyond the χ((3)) limit.

    PubMed

    Somma, Carmine; Folpini, Giulia; Reimann, Klaus; Woerner, Michael; Elsaesser, Thomas

    2016-05-14

    We present the first two-dimensional (2D) terahertz (THz) experiment with three phase-locked THz pulses and a fully phase-resolved detection of the nonlinearly emitted field by electrooptic sampling. In a prototype experiment we study the ultrafast dynamics of nonlinear two-phonon and two-photon interband coherences in the narrow-gap semiconductor InSb. Due to the extraordinarily large optical interband dipole of InSb the experiments were performed in the strongly nonperturbative regime of light-matter interaction allowing for impulsive off-resonant excitation of both two-phonon coherences and two-photon interband coherences, the ultrafast dynamics of which is experimentally observed as a function of the waiting time in the three-pulse 2D experiment. Our novel three-pulse 2D THz spectroscopy paves the way for the detailed investigation of nonlinear quantum coherences in solids and holds potential for an extension to other systems. PMID:27179477

  6. Spatially resolved optical absorption spectroscopy of single- and few-layer MoS₂ by hyperspectral imaging.

    PubMed

    Castellanos-Gomez, Andres; Quereda, Jorge; van der Meulen, Herko P; Agraït, Nicolás; Rubio-Bollinger, Gabino

    2016-03-18

    The possibility of spatially resolving the optical properties of atomically thin materials is especially appealing as they can be modulated at the micro- and nanoscale by reducing their thickness, changing the doping level or applying a mechanical deformation. Therefore, optical spectroscopy techniques with high spatial resolution are necessary to get a deeper insight into the properties of two-dimensional (2D) materials. Here we study the optical absorption of single- and few-layer molybdenum disulfide (MoS2) in the spectral range from 1.24 eV to 3.22 eV (385 nm to 1000 nm) by developing a hyperspectral imaging technique that allows one to probe the optical properties with diffraction limited spatial resolution. We find hyperspectral imaging very suited to study indirect bandgap semiconductors, unlike photoluminescence which only provides high luminescence yield for direct gap semiconductors. Moreover, this work opens the door to study the spatial variation of the optical properties of other 2D systems, including non-semiconducting materials where scanning photoluminescence cannot be employed. PMID:26876671

  7. Relation between the OH stretching frequency and the OO distance in time-resolved infrared spectroscopy of hydrogen bonding

    NASA Astrophysics Data System (ADS)

    Bratos, Savo; Leicknam, Jean-Claude; Pommeret, Stanislas

    2009-05-01

    A non-empirical theory is presented to study the relation between the OH stretching frequency and the OO distance in ultrafast laser spectra of water. Diluted solutions HDO/DO rather than pure HO were considered to switch off resonant vibrational interactions between water molecules; the local structure of water as well as the OO distribution functions remain unchanged in this substitution. Only times superior to 100-200fs are considered to avoid perturbations generated by collisions between water molecules. It is then shown that the Novak-Mikenda type relations between the OH stretching frequency and the OO distance largely survive when going from equilibrium to laser perturbed non-equilibrium systems. It is also shown that temporally varying infrared pump-probe profiles of OH stretching bands in HDO/DO closely parallel the oxygen-oxygen distribution functions of these solutions. Infrared pump-probe spectroscopy can thus replace time-resolved X-ray diffraction in this particular case.

  8. Testing the Physical Mechanisms of Gamma-Ray Bursts with Multi-Instrument Time-Resolved Spectroscopy

    NASA Technical Reports Server (NTRS)

    Briggs, Michael S.; Preece, Robert E.

    2001-01-01

    We have continued the project of time-resolved spectral analyses of gamma-ray bursts observed jointly by the BATSE and the Wide-Field Camera on board BeppoSAX. We are making progress understanding the systematic differences between the two data sets. These data comprise the most important joint analysis set for our project. In several meetings, we have reported on metal efforts to understand the blackbody portion of the time series of spectra from GRB970111. Clearly, a fading thermal component can provide a 'seed' spectrum for Compton upscattering. It is very likely the X-ray excess that has been observed previously in BATSE data alone continues into the X-ray band observed by the WFC. We have also made progress in joint fitting of BATSE Large Area Detector and Spectroscopy Detector data with that of the Total Absorption Scintillation Calorimeter (TASC) of the EGRET experiment on CGRO. The TASC data are important to understanding the high-energy response of the BATSE data. We have produced time-sequences of spectra for two important GRB with data from both instruments. The Summer workshop on GRBs at the Aspen Center for Physics provided an opportunity for in-depth discussion of our on-going work. To aid our effort, we continue to make improvements in our spectral analysis software, RMFIT (rewritten from WINGSPAN).

  9. Cy3 in AOT reverse micelles I. Dimer formation revealed through steady-state and time-resolved spectroscopy.

    PubMed

    McPhee, Jeffrey T; Scott, Eric; Levinger, Nancy E; Van Orden, Alan

    2011-08-11

    Cyanine-3 (Cy3) fluorescent dye molecules confined in sodium di-2-ethylhexyl sulfosuccinate (AOT) reverse micelles were examined using steady-state absorption and emission as well as time-resolved fluorescence spectroscopy to understand the effect of confinement on the spectroscopic properties of the dye. This study explored a wide range of reverse micelle sizes, with hydrodynamic radii ranging from ∼1.7 to ∼5 nm. The relative concentrations of Cy3 and AOT reverse micelles were such that, on average, one dye molecule was present for every 2 × 10(4) to 9 × 10(5) reverse micelles. In the smallest reverse micelles examined, observed changes in the absorption and emission spectra and fluorescence lifetime of the dye molecules indicated H-aggregation of Cy3 into side-by-side dimers. It is hypothesized that this dimerization is governed by the high local concentrations that result from the confinement of the Cy3 in the reverse micelles. What is notable about this study is that this dimer occurs even at overall dye concentrations in the nanomolar range. Such concentrations are too low for aggregation to occur in bulk solution. Hence, the reverse micelles serve as nanocatalysts for this aggregation process. PMID:21761942

  10. Study of Heat Transfer Dynamics from Gold Nanorods to the Environment via Time-Resolved Infrared Spectroscopy.

    PubMed

    Nguyen, Son C; Zhang, Qiao; Manthiram, Karthish; Ye, Xingchen; Lomont, Justin P; Harris, Charles B; Weller, Horst; Alivisatos, A Paul

    2016-02-23

    Studying the local solvent surrounding nanoparticles is important to understanding the energy exchange dynamics between the particles and their environment, and there is a need for spectroscopic methods that can dynamically probe the solvent region that is in nearby contact with the nanoparticles. In this work, we demonstrate the use of time-resolved infrared spectroscopy to track changes in a vibrational mode of local water on the time scale of hundreds of picoseconds, revealing the dynamics of heat transfer from gold nanorods to the local water environment. We applied this probe to a prototypical plasmonic photothermal system consisting of organic CTAB bilayer capped gold nanorods, as well as gold nanorods coated with varying thicknesses of inorganic mesoporous-silica. The heat transfer time constant of CTAB capped gold nanorods is about 350 ps and becomes faster with higher laser excitation power, eventually generating bubbles due to superheating in the local solvent. Silica coating of the nanorods slows down the heat transfer and suppresses the formation of superheated bubbles. PMID:26840805

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  12. Progress in (e, 2e) electron momentum spectroscopy: from the static to the time-resolved regime

    NASA Astrophysics Data System (ADS)

    Takahashi, Masahiko

    2015-09-01

    Electron momentum spectroscopy (EMS) is a kinematically-complete electron-impact ionization experiment performed under the high-energy Bethe ridge conditions, where the collision kinematics can be described by electron Compton scattering that most nearly corresponds to the collision of two free electrons with the residual ion acting as a spectator. The remarkable feature of this technique is its ability to measure momentum distributions of each electron bound in matter or to look at molecular orbitals in momentum space. We have been exploring atomic and molecular science using EMS, such as 3D orbital imaging for a stable gaseous molecule [Takahashi et al., PRL 2005], observation of the giant resonance phenomenon in the 2nd order projectile-target interactions [Takahashi et al., PRL 2007], and determination of spatial orientation of the constituent atomic orbitals in molecular orbitals [Watanabe et al., PRL 2012]. Recently, we have started to direct our efforts also towards expanding frontiers of EMS, through development of time-resolved EMS (TR-EMS) that employs ultrashort laser (120 fs) and electron (1 ps) pulses in a pump-probe scheme [Yamazaki et al., RSI 2013]. In spite of the low data statistics as well as of the limited time-resolution due to velocity mismatch, our experimental results on the deuterated acetone molecule in its second excited singlet state with a lifetime of 13.5 ps [Yamazaki et al., PRL 2015] have represented the first time that EMS measurements of short lived transient species are feasible, opening the door to time-resolved orbital imaging in momentum space. With further technical development, TR-EMS could eventually enable one to take a series of snapshots of molecular orbitals changing rapidly during chemical reaction, thereby making it possible to exploit a new area for studies of ultrafast molecular dynamics as well as the nature of molecular excited states; it is electrons that bind atoms into molecules, and chemical reactions are all

  13. Revealing the nature of the QPO and its harmonic in GX 339-4 using frequency-resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Axelsson, Magnus; Done, Chris

    2016-05-01

    We use frequency-resolved spectroscopy to examine the energy spectra of the prominent low-frequency quasi-periodic oscillation (QPO) and its harmonic in GX 339-4. We track the evolution of these spectra as the source makes a transition from a bright low/hard to hard intermediate state. In the hard/intermediate states, the QPO and time-averaged spectra are similar and the harmonic is either undetected or similar to the QPO. By contrast, in the softer states, the harmonic is dramatically softer than the QPO spectrum and the time-averaged spectrum, and the QPO spectrum is dramatically harder than the time-averaged spectrum. Clearly, the existence of these very different spectral shaped components mean that the time-averaged spectra are complex, as also seen by the fact that the softer spectra cannot be well described by a disc, Comptonization and its reflection. We use the frequency-resolved spectra to better constrain the model components, and find that the data are consistent with a time-averaged spectrum which has an additional low-temperature, optically thick Comptonization component. The harmonic can be described by this additional component alone, while the QPO spectrum is similar to that of the hard Comptonization and its reflection. Neither QPO nor harmonic shows signs of the disc component even when it is strong in the time-averaged spectrum. This adds to the growing evidence for inhomogeneous Comptonization in black hole binaries. While the similarity between the harmonic and QPO spectra in the intermediate state can be produced from the angular dependence of Compton scattering in a single region, this cannot explain the dramatic differences seen in the soft state. Instead, we propose that the soft Compton region is located predominantly above the disc while the hard Compton is from the hotter inner flow. Our results therefore point to multiple possible mechanisms for producing harmonic features in the power spectrum. The dominant mechanism in a given

  14. Development and demonstration of table-top synchronized fast-scan femtosecond time-resolved spectroscopy system by single-shot scan photo detector array

    NASA Astrophysics Data System (ADS)

    Yabushita, Atsushi; Kao, Chih-Hsien; Lee, Yu-Hsien; Kobayashi, Takayoshi

    2015-07-01

    Ultrafast dynamics is generally studied by pump-probe method with laser pulse, which scans optical delay by motorized stage step by step. Using ultrashort laser pulse shorter than typical molecular vibration periods, the pump-probe measurement can study both of electronic dynamics and vibration dynamics simultaneously. The probe wavelength dependence of the ultrafast electronic and vibration dynamics (UEVD) helps us to distinguish the signal contributions from the dynamics of the electronic ground state and that of the electronic excited states, which elucidates primary reaction mechanism after photoexcitation. Meanwhile, the measurement time of UEVD spectroscopy takes too long time to be used in realistic application. In our previous work, we have developed multi-channel lock-in amplifying (MLA) detectors to study UEVD at all probe wavelengths simultaneously, and synchronized it with laser and fast-scan delay stage to scan the data in five seconds. It enabled us to study UEVD spectroscopy even for photo-fragile materials. However, the home-made MLA detectors required for the measurement is expensive and massive in size and weight, thus not suitable for general researchers in the field of ultrafast time-resolved spectroscopy. In the present work, we have developed a table-top synchronized fast-scan femtosecond time-resolved spectroscopy system using single shot scan line CCD. This system measures time-resolved trace at all probe wavelengths simultaneously in five seconds. The CCD-based fast-scan time-resolved spectroscopy system enables us to study ultrafast dynamics of various materials even biomaterials, which have been thought to be hard or even impossible to be studied in previous methods.

  15. Co-localized confocal Raman spectroscopy and optical coherence tomography (CRS-OCT) for depth-resolved analyte detection in tissue

    PubMed Central

    Maher, Jason R.; Chuchuen, Oranat; Henderson, Marcus H.; Kim, Sanghoon; Rinehart, Matthew T.; Kashuba, Angela D. M.; Wax, Adam; Katz, David F.

    2015-01-01

    We report the development of a combined confocal Raman spectroscopy (CRS) and optical coherence tomography (OCT) instrument (CRS-OCT) capable of measuring analytes in targeted biological tissues with sub-100-micron spatial resolution. The OCT subsystem was used to measure depth-resolved tissue morphology and guide the acquisition of chemically-specific Raman spectra. To demonstrate its utility, the instrument was used to accurately measure depth-resolved, physiologically-relevant concentrations of Tenofovir, a microbicide drug used to prevent the sexual transmission of HIV, in ex vivo tissue samples. PMID:26114026

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

    SciTech Connect

    Yukawa, R.; Yamamoto, S.; Ogawa, M.; Yamamoto, Sh.; Fujikawa, K.; Hobara, R.; Matsuda, I.; Ozawa, K.; Emori, M.; Sakama, H.; Kitagawa, S.; Daimon, H.

    2014-10-13

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

  17. Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy

    PubMed Central

    Wang, Y. F.; Singh, Shashi B.; Limaye, Mukta V.; Shao, Y. C.; Hsieh, S. H.; Chen, L. Y.; Hsueh, H. C.; Wang, H. T.; Chiou, J. W.; Yeh, Y. C.; Chen, C. W.; Chen, C. H.; Ray, Sekhar C.; Wang, J.; Pong, W. F.; Takagi, Y.; Ohigashi, T.; Yokoyama, T.; Kosugi, N.

    2015-01-01

    This investigation studies the various magnetic behaviors of graphene oxide (GO) and reduced graphene oxides (rGOs) and elucidates the relationship between the chemical states that involve defects therein and their magnetic behaviors in GO sheets. Magnetic hysteresis loop reveals that the GO is ferromagnetic whereas photo-thermal moderately reduced graphene oxide (M-rGO) and heavily reduced graphene oxide (H-rGO) gradually become paramagnetic behavior at room temperature. Scanning transmission X-ray microscopy and corresponding X-ray absorption near-edge structure spectroscopy were utilized to investigate thoroughly the variation of the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups, as well as the C 2p(σ*)-derived states in flat and wrinkle regions to clarify the relationship between the spatially-resolved chemical states and the magnetism of GO, M-rGO and H-rGO. The results of X-ray magnetic circular dichroism further support the finding that C 2p(σ*)-derived states are the main origin of the magnetism of GO. Based on experimental results and first-principles calculations, the variation in magnetic behavior from GO to M-rGO and to H-rGO is interpreted, and the origin of ferromagnetism is identified as the C 2p(σ*)-derived states that involve defects/vacancies rather than the C 2p(π*) states that are bound with oxygen-containing and hydroxyl groups on GO sheets. PMID:26481557

  18. Development of spatially resolved high resolution x-ray spectroscopy for fusion and light-source research

    NASA Astrophysics Data System (ADS)

    Lu, J.; Hill, K. W.; Bitter, M.; Delgado-Aparicio, L.; Pablant, N. A.; Efthimion, P.; Beiersdorfer, P.; Chen, H.; Widmann, K.; Sanchez del Rio, M.

    2014-09-01

    One dimensional spatially resolved high resolution x-ray spectroscopy with spherically bent crystals and 2D pixelated detectors is an established technique on magnetic confinement fusion (MCF) experiments world wide for Doppler measurements of spatial profiles of plasma ion temperature and flow velocity. This technique is being further developed for diagnosis of High Energy Density Physics (HEDP) plasmas at laser-plasma facilities and synchrotron/x-ray free electron laser (XFEL) facilities. Useful spatial resolution (micron scale) of such small-scale plasma sources requires magnification, because of the finite pixel size of x-ray CCD detectors (13.5 μm). A von-Hamos like spectrometer using spherical crystals is capable of magnification, as well as uniform sagittal focusing across the full x-ray spectrum, and is being tested in laboratory experiments using a tungsten-target microfocus (5-10 μm) x-ray tube and 13-μm pixel x-ray CCD. A spatial resolution better than 10 μm has been demonstrated. Good spectral resolution is indicated by small differences (0.02 - 0.1 eV) of measured line widths with best available published natural line widths. Progress and status of HEDP measurements and the physics basis for these diagnostics are presented. A new type of x-ray crystal spectrometer with a convex spherically bent crystal is also reported. The status of testing of a 2D imaging microscope using matched pairs of spherical crystals with x rays will also be presented. The use of computational x-ray optics codes in development of these instrumental concepts is addressed.

  19. Temporally and spatially resolved plasma spectroscopy in pulsed laser deposition of ultra-thin boron nitride films

    NASA Astrophysics Data System (ADS)

    Glavin, Nicholas R.; Muratore, Christopher; Jespersen, Michael L.; Hu, Jianjun; Fisher, Timothy S.; Voevodin, Andrey A.

    2015-04-01

    Physical vapor deposition (PVD) has recently been investigated as a viable, alternative growth technique for two-dimensional materials with multiple benefits over other vapor deposition synthesis methods. The high kinetic energies and chemical reactivities of the condensing species formed from PVD processes can facilitate growth over large areas and at reduced substrate temperatures. In this study, chemistry, kinetic energies, time of flight data, and spatial distributions within a PVD plasma plume ablated from a boron nitride (BN) target by a KrF laser at different pressures of nitrogen gas were investigated. Time resolved spectroscopy and wavelength specific imaging were used to identify and track atomic neutral and ionized species including B+, B*, N+, N*, and molecular species including N2*, N2+, and BN. Formation and decay of these species formed both from ablation of the target and from interactions with the background gas were investigated and provided insights into fundamental growth mechanisms of continuous, amorphous boron nitride thin films. The correlation of the plasma diagnostic results with film chemical composition and thickness uniformity studies helped to identify that a predominant mechanism for BN film formation is condensation surface recombination of boron ions and neutral atomic nitrogen species. These species arrive nearly simultaneously to the substrate location, and BN formation occurs microseconds before arrival of majority of N+ ions generated by plume collisions with background molecular nitrogen. The energetic nature and extended dwelling time of incident N+ ions at the substrate location was found to negatively impact resulting BN film stoichiometry and thickness. Growth of stoichiometric films was optimized at enriched concentrations of ionized boron and neutral atomic nitrogen in plasma near the condensation surface, providing few nanometer thick films with 1:1 BN stoichiometry and good thicknesses uniformity over macroscopic areas.

  20. Temporally and spatially resolved plasma spectroscopy in pulsed laser deposition of ultra-thin boron nitride films

    SciTech Connect

    Glavin, Nicholas R. E-mail: andrey.voevodin@us.af.mil; Muratore, Christopher; Jespersen, Michael L.; Hu, Jianjun; Fisher, Timothy S.; Voevodin, Andrey A. E-mail: andrey.voevodin@us.af.mil

    2015-04-28

    Physical vapor deposition (PVD) has recently been investigated as a viable, alternative growth technique for two-dimensional materials with multiple benefits over other vapor deposition synthesis methods. The high kinetic energies and chemical reactivities of the condensing species formed from PVD processes can facilitate growth over large areas and at reduced substrate temperatures. In this study, chemistry, kinetic energies, time of flight data, and spatial distributions within a PVD plasma plume ablated from a boron nitride (BN) target by a KrF laser at different pressures of nitrogen gas were investigated. Time resolved spectroscopy and wavelength specific imaging were used to identify and track atomic neutral and ionized species including B{sup +}, B*, N{sup +}, N*, and molecular species including N{sub 2}*, N{sub 2}{sup +}, and BN. Formation and decay of these species formed both from ablation of the target and from interactions with the background gas were investigated and provided insights into fundamental growth mechanisms of continuous, amorphous boron nitride thin films. The correlation of the plasma diagnostic results with film chemical composition and thickness uniformity studies helped to identify that a predominant mechanism for BN film formation is condensation surface recombination of boron ions and neutral atomic nitrogen species. These species arrive nearly simultaneously to the substrate location, and BN formation occurs microseconds before arrival of majority of N{sup +} ions generated by plume collisions with background molecular nitrogen. The energetic nature and extended dwelling time of incident N{sup +} ions at the substrate location was found to negatively impact resulting BN film stoichiometry and thickness. Growth of stoichiometric films was optimized at enriched concentrations of ionized boron and neutral atomic nitrogen in plasma near the condensation surface, providing few nanometer thick films with 1:1 BN stoichiometry and good

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  2. Coherent photon interference elimination and spectral correction in femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy

    NASA Astrophysics Data System (ADS)

    Dang, Wei; Mao, Pengcheng; Weng, Yuxiang

    2013-07-01

    We report an improved setup of femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectroscopy (FNOPAS) with a 210 fs temporal response. The system employs a Cassegrain objective to collect and focus fluorescence photons, which eliminates the interference from the coherent photons in the fluorescence amplification by temporal separation of the coherent photons and the fluorescence photons. The gain factor of the Cassegrain objective-assisted FNOPAS is characterized as 1.24 × 105 for Rhodamine 6G. Spectral corrections have been performed on the transient fluorescence spectra of Rhodamine 6G and Rhodamine 640 in ethanol by using an intrinsic calibration curve derived from the spectrum of superfluorescence, which is generated from the amplification of the vacuum quantum noise. The validity of spectral correction is illustrated by comparisons of spectral shape and peak wavelength between the corrected transient fluorescence spectra of these two dyes acquired by FNOPAS and their corresponding standard reference spectra collected by the commercial streak camera. The transient fluorescence spectra of the Rhodamine 6G were acquired in an optimized phase match condition, which gives a deviation in the peak wavelength between the retrieved spectrum and the reference spectrum of 1.0 nm, while those of Rhodamine 640 were collected in a non-optimized phase match condition, leading to a deviation in a range of 1.0-3.0 nm. Our results indicate that the improved FNOPAS can be a reliable tool in the measurement of transient fluorescence spectrum for its high temporal resolution and faithfully corrected spectrum.

  3. Angle resolved x-ray photoelectron spectroscopy (ARXPS) analysis of lanthanum oxide for micro-flexography printing

    NASA Astrophysics Data System (ADS)

    Hassan, S.; Yusof, M. S.; Embong, Z.; Maksud, M. I.

    2016-01-01

    Micro-flexography printing was developed in patterning technique from micron to nano scale range to be used for graphic, electronic and bio-medical device on variable substrates. In this work, lanthanum oxide (La2O3) has been used as a rare earth metal candidate as depositing agent. This metal deposit was embedded on Carbon (C) and Silica (Si) wafer substrate using Magnetron Sputtering technique. The choose of Lanthanum as a target is due to its wide application in producing electronic devices such as thin film battery and printed circuit board. The La2O3 deposited on the surface of Si wafer substrate was then analyzed using Angle Resolve X-Ray Photoelectron Spectroscopy (ARXPS). The position for each synthetic component in the narrow scan of Lanthanum (La) 3d and O 1s are referred to the electron binding energy (eV). The La 3d narrow scan revealed that the oxide species of this particular metal is mainly contributed by La2O3 and La(OH)3. The information of oxygen species, O2- component from O 1s narrow scan indicated that there are four types of species which are contributed from the bulk (O2-), two chemisorb component (La2O3) and La(OH)3 and physisorp component (OH). Here, it is proposed that from the adhesive and surface chemical properties of La, it is suitable as an alternative medium for micro-flexography printing technique in printing multiple fine solid lines at nano scale. Hence, this paper will describe the capability of this particular metal as rare earth metal for use in of micro-flexography printing practice. The review of other parameters contributing to print fine lines will also be described later.

  4. Ultrafast excited-state dynamics in photochromic N-salicylideneaniline studied by femtosecond time-resolved REMPI spectroscopy

    SciTech Connect

    Okabe, Chie; Nakabayashi, Takakazu; Inokuchi, Yoshiya; Nishi, Nobuyuki; Sekiya, Hiroshi

    2004-11-15

    Ultrafast processes in photoexcited N-salicylideneaniline have been investigated with femtosecond time-resolved resonance-enhanced multiphoton ionization spectroscopy. The ion signals via the S{sub 1}(n,{pi}*) state of the enol form as well as the proton-transferred cis-keto form emerge within a few hundred femtoseconds after photoexcitation to the first S{sub 1}({pi},{pi}*) state of the enol form. This reveals that two ultrafast processes, excited-state intramolecular proton transfer (ESIPT) reaction and an internal conversion (IC) to the S{sub 1}(n,{pi}*) state, occur on a time scale less than a few hundred femtoseconds from the S{sub 1}({pi},{pi}*) state of the enol form. The rise time of the transient corresponding to the production of the proton-transferred cis-keto form is within 750 fs when near the red edge of the absorption is excited, indicating that the ESIPT reaction occurs within 750 fs. The decay time of the S{sub 1}({pi},{pi}*) state of the cis-keto form is 8.9 ps by exciting the enol form at 370 nm, but it dramatically decreases to be 1.5-1.6 ps for the excitation at 365-320 nm. The decrease in the decay time has been attributed to the opening of an efficient nonradiative channel; an IC from S{sub 1}({pi},{pi}*) to S{sub 1}(n,{pi}*) of the cis-keto form promotes the production of the trans-keto form as the final photochromic products. The two IC processes may provide opposite effect on the quantum yield of photochromic products: IC in the enol form may substantially reduce the quantum yield, but IC in the cis-keto form increase it.

  5. SPATIALLY RESOLVED SPECTROSCOPY AND CHEMICAL HISTORY OF STAR-FORMING GALAXIES IN THE HERCULES CLUSTER: THE EFFECTS OF THE ENVIRONMENT

    SciTech Connect

    Petropoulou, V.; Vilchez, J.; Iglesias-Paramo, J.; Cedres, B.; Papaderos, P.; Magrini, L.; Reverte, D.

    2011-06-10

    Spatially resolved spectroscopy has been obtained for a sample of 27 star-forming (SF) galaxies selected from our deep H{alpha} survey of the Hercules cluster. We have applied spectral synthesis models to all emission-line spectra of this sample using the population synthesis code STARLIGHT and have obtained fundamental parameters of stellar components such as mean metallicity and age. The emission-line spectra were corrected for underlying stellar absorption using these spectral synthesis models. Line fluxes were measured and O/H and N/O gas chemical abundances were obtained using the latest empirical calibrations. We have derived the masses and total luminosities of the galaxies using available Sloan Digital Sky Survey broadband photometry. The effects of cluster environment on the chemical evolution of galaxies and on their mass-metallicity (MZ) and luminosity-metallicity (LZ) relations were studied by combining the derived gas metallicities, the mean stellar metallicities and ages, the masses and luminosities of the galaxies, and their existing H I data. Our Hercules SF galaxies are divided into three main subgroups: (1) chemically evolved spirals with truncated ionized-gas disks and nearly flat oxygen gradients, demonstrating the effect of ram-pressure stripping; (2) chemically evolved dwarfs/irregulars populating the highest local densities, possible products of tidal interactions in preprocessing events; and (3) less metallic dwarf galaxies that appear to be 'newcomers' to the cluster and are experiencing pressure-triggered star formation. Most Hercules SF galaxies follow well-defined MZ and LZ sequences (for both O/H and N/O), though the dwarf/irregular galaxies located at the densest regions appear to be outliers to these global relations, suggesting a physical reason for the dispersion in these fundamental relations. The Hercules cluster appears to be currently assembling via the merger of smaller substructures, providing an ideal laboratory where the

  6. Spatially Resolved Spectroscopy and Chemical History of Star-forming Galaxies in the Hercules Cluster: The Effects of the Environment

    NASA Astrophysics Data System (ADS)

    Petropoulou, V.; Vílchez, J.; Iglesias-Páramo, J.; Papaderos, P.; Magrini, L.; Cedrés, B.; Reverte, D.

    2011-06-01

    Spatially resolved spectroscopy has been obtained for a sample of 27 star-forming (SF) galaxies selected from our deep Hα survey of the Hercules cluster. We have applied spectral synthesis models to all emission-line spectra of this sample using the population synthesis code STARLIGHT and have obtained fundamental parameters of stellar components such as mean metallicity and age. The emission-line spectra were corrected for underlying stellar absorption using these spectral synthesis models. Line fluxes were measured and O/H and N/O gas chemical abundances were obtained using the latest empirical calibrations. We have derived the masses and total luminosities of the galaxies using available Sloan Digital Sky Survey broadband photometry. The effects of cluster environment on the chemical evolution of galaxies and on their mass-metallicity (MZ) and luminosity-metallicity (LZ) relations were studied by combining the derived gas metallicities, the mean stellar metallicities and ages, the masses and luminosities of the galaxies, and their existing H I data. Our Hercules SF galaxies are divided into three main subgroups: (1) chemically evolved spirals with truncated ionized-gas disks and nearly flat oxygen gradients, demonstrating the effect of ram-pressure stripping; (2) chemically evolved dwarfs/irregulars populating the highest local densities, possible products of tidal interactions in preprocessing events; and (3) less metallic dwarf galaxies that appear to be "newcomers" to the cluster and are experiencing pressure-triggered star formation. Most Hercules SF galaxies follow well-defined MZ and LZ sequences (for both O/H and N/O), though the dwarf/irregular galaxies located at the densest regions appear to be outliers to these global relations, suggesting a physical reason for the dispersion in these fundamental relations. The Hercules cluster appears to be currently assembling via the merger of smaller substructures, providing an ideal laboratory where the local

  7. Reduction of O2 slow component by priming exercise: novel mechanistic insights from time-resolved near-infrared spectroscopy

    PubMed Central

    Fukuoka, Yoshiyuki; Poole, David C; Barstow, Thomas J; Kondo, Narihiko; Nishiwaki, Masato; Okushima, Dai; Koga, Shunsaku

    2015-01-01

    Novel time-resolved near-infrared spectroscopy (TR-NIRS), with adipose tissue thickness correction, was used to test the hypotheses that heavy priming exercise reduces the V̇O2 slow component (V̇O2SC) (1) by elevating microvascular [Hb] volume at multiple sites within the quadriceps femoris (2) rather than reducing the heterogeneity of muscle deoxygenation kinetics. Twelve subjects completed two 6-min bouts of heavy work rate exercise, separated by 6 min of unloaded cycling. Priming exercise induced faster overall V̇O2 kinetics consequent to a substantial reduction in the V̇O2SC (0.27 ± 0.12 vs. 0.11 ± 0.09 L·min−1, P < 0.05) with an unchanged primary V̇O2 time constant. An increased baseline for the primed bout [total (Hb + Mb)] (197.5 ± 21.6 vs. 210.7 ± 22.5 μmol L−1, P < 0.01), reflecting increased microvascular [Hb] volume, correlated significantly with the V̇O2SC reduction. At multiple sites within the quadriceps femoris, priming exercise reduced the baseline and slowed the increase in [deoxy (Hb + Mb)]. Changes in the intersite coefficient of variation in the time delay and time constant of [deoxy (Hb + Mb)] during the second bout were not correlated with the V̇O2SC reduction. These results support a mechanistic link between priming exercise-induced increase in muscle [Hb] volume and the reduced V̇O2SC that serves to speed overall V̇O2 kinetics. However, reduction in the heterogeneity of muscle deoxygenation kinetics does not appear to be an obligatory feature of the priming response. PMID:26109190

  8. 6-GHz, Kerr-lens mode-locked Yb:Lu2O3 ceramic laser for comb-resolved broadband spectroscopy.

    PubMed

    Endo, Mamoru; Ozawa, Akira; Kobayashi, Yohei

    2013-11-01

    A laser diode (LD)-pumped, 6-GHz repetition rate, ytterbium (Yb)-doped Lu2O3 ceramic Kerr-lens mode-locked laser is described. A bow-tie ring cavity enabled the generation of femtosecond pulses centered at a wavelength of 1076 nm with an average power of 10 mW. The pulse duration after an amplifier was 161 fs whereas the transform-limited pulse duration directly from the oscillator was 148 fs. The repetition frequency was sufficiently high for each longitudinal mode to be spectrally resolved by a commercially available optical spectrum analyzer. The developed laser was successfully applied to the absorption spectroscopy of metastable helium4 and demonstrated the suitability of the system as a source for comb-resolved broadband spectroscopy. PMID:24177130

  9. Angle-resolved environmental X-ray photoelectron spectroscopy: A new laboratory setup for photoemission studies at pressures up to 0.4 Torr

    SciTech Connect

    Mangolini, F.; Wabiszewski, G. E.; Egberts, P.; Ahlund, J.; Backlund, K.; Karlsson, P. G.; Adiga, V. P.; Streller, F.; Wannberg, B.; Carpick, R. W.

    2012-09-15

    The paper presents the development and demonstrates the capabilities of a new laboratory-based environmental X-ray photoelectron spectroscopy system incorporating an electrostatic lens and able to acquire spectra up to 0.4 Torr. The incorporation of a two-dimensional detector provides imaging capabilities and allows the acquisition of angle-resolved data in parallel mode over an angular range of 14 Degree-Sign without tilting the sample. The sensitivity and energy resolution of the spectrometer have been investigated by analyzing a standard Ag foil both under high vacuum (10{sup -8} Torr) conditions and at elevated pressures of N{sub 2} (0.4 Torr). The possibility of acquiring angle-resolved data at different pressures has been demonstrated by analyzing a silicon/silicon dioxide (Si/SiO{sub 2}) sample. The collected angle-resolved spectra could be effectively used for the determination of the thickness of the native silicon oxide layer.

  10. Evidence for Anionic Excess Electrons in a Quasi-Two-Dimensional Ca2N Electride by Angle-Resolved Photoemission Spectroscopy.

    PubMed

    Oh, Ji Seop; Kang, Chang-Jong; Kim, Ye Ji; Sinn, Soobin; Han, Moonsup; Chang, Young Jun; Park, Byeong-Gyu; Kim, Sung Wng; Min, Byung Il; Kim, Hyeong-Do; Noh, Tae Won

    2016-03-01

    Angle-resolved photoemission spectroscopy (ARPES) study of a layered electride Ca2N was carried out to reveal its quasi-two-dimensional electronic structure. The band dispersions and the Fermi-surface map are consistent with the density functional theory results except for a chemical potential shift that may originate from the high reactivity of surface excess electrons. Thus, the existence of anionic excess electrons in the interlayer region of Ca2N is strongly supported by ARPES. PMID:26840946

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

    NASA Astrophysics Data System (ADS)

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

    2003-11-01

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

  12. Effect of ouabain on metabolic oxidative state in living cardiomyocytes evaluated by time-resolved spectroscopy of endogenous NAD(P)H fluorescence

    NASA Astrophysics Data System (ADS)

    Chorvatova, Alzbeta; Elzwiei, Fathia; Mateasik, Anton; Chorvat, Dusan

    2012-10-01

    Time-resolved spectrometry of endogenous nicotinamide dinucleotide phosphate [NAD(P)H] fluorescence is a useful method to evaluate metabolic oxidative state in living cells. Ouabain is a well-known pharmaceutical drug used in the treatment of cardiovascular disease, the effects of which on myocardial metabolism were recently demonstrated. Mechanisms implicated in these actions are still poorly understood. We investigate the effect of ouabain on the metabolic oxidative state of living cardiac cells identified by time-resolved fluorescence spectroscopy of mitochondrial NAD(P)H. Spectral unmixing is used to resolve individual NAD(P)H fluorescence components. Ouabain decreased the integral intensity of NAD(P)H fluorescence, leading to a reduced component amplitudes ratio corresponding to a change in metabolic state. We also noted that lactate/pyruvate, affecting the cytosolic NADH gradient, increased the effect of ouabain on the component amplitudes ratio. Cell oxidation levels, evaluated as the percentage of oxidized NAD(P)H, decreased exponentially with rising concentrations of the cardiac glycoside. Ouabain also stimulated the mitochondrial NADH production. Our study sheds a new light on the role that ouabain plays in the regulation of metabolic state, and presents perspective on a noninvasive, pharmaceutical approach for testing the effect of drugs on the mitochondrial metabolism by means of time-resolved fluorescence spectroscopy in living cells.

  13. Angle-resolved photoemission spectroscopy of strontium lanthanum copper oxide thin films grown by molecular-beam epitaxy

    NASA Astrophysics Data System (ADS)

    Harter, John Wallace

    Among the multitude of known cuprate material families and associated structures, the archetype is "infinite-layer" ACuO2, where perfectly square and flat CuO2 planes are separated by layers of alkaline earth atoms. The infinite-layer structure is free of magnetic rare earth ions, oxygen chains, orthorhombic distortions, incommensurate superstructures, ordered vacancies, and other complications that abound among the other material families. Furthermore, it is the only cuprate that can be made superconducting by both electron and hole doping, making it a potential platform for decoding the complex many-body interactions responsible for high-temperature superconductivity. Research on the infinite-layer compound has been severely hindered by the inability to synthesize bulk single crystals, but recent progress has led to high-quality superconducting thin film samples. Here we report in situ angle-resolved photoemission spectroscopy measurements of epitaxially-stabilized Sr1-chiLa chiCuO2 thin films grown by molecular-beam epitaxy. At low doping, the material exhibits a dispersive lower Hubbard band typical of other cuprate parent compounds. As carriers are added to the system, a continuous evolution from Mott insulator to superconducting metal is observed as a coherent low-energy band develops on top of a concomitant remnant lower Hubbard band, gradually filling in the Mott gap. For chi = 0.10, our results reveal a strong coupling between electrons and (pi,pi) anti-ferromagnetism, inducing a Fermi surface reconstruction that pushes the nodal states below the Fermi level and realizing nodeless superconductivity. Electron diffraction measurements indicate the presence of a surface reconstruction that is consistent with the polar nature of Sr1-chiLachiCuO2. Most knowledge about the electron-doped side of the cuprate phase diagram has been deduced by generalizing from a single material family, Re2-chi CechiCuO4, where robust antiferromagnetism has been observed past chi

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

    SciTech Connect

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

    2014-04-10

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

  15. Microsecond Time-Resolved Absorption Spectroscopy Used to Study CO Compounds of Cytochrome bd from Escherichia coli

    PubMed Central

    Siletsky, Sergey A.; Zaspa, Andrey A.; Poole, Robert K.; Borisov, Vitaliy B.

    2014-01-01

    Cytochrome bd is a tri-heme (b558, b595, d) respiratory oxygen reductase that is found in many bacteria including pathogenic species. It couples the electron transfer from quinol to O2 with generation of an electrochemical proton gradient. We examined photolysis and subsequent recombination of CO with isolated cytochrome bd from Escherichia coli in one-electron reduced (MV) and fully reduced (R) states by microsecond time-resolved absorption spectroscopy at 532-nm excitation. Both Soret and visible band regions were examined. CO photodissociation from MV enzyme possibly causes fast (τ<1.5 µs) electron transfer from heme d to heme b595 in a small fraction of the protein, not reported earlier. Then the electron migrates to heme b558 (τ∼16 µs). It returns from the b-hemes to heme d with τ∼180 µs. Unlike cytochrome bd in the R state, in MV enzyme the apparent contribution of absorbance changes associated with CO dissociation from heme d is small, if any. Photodissociation of CO from heme d in MV enzyme is suggested to be accompanied by the binding of an internal ligand (L) at the opposite side of the heme. CO recombines with heme d (τ∼16 µs) yielding a transient hexacoordinate state (CO-Fe2+-L). Then the ligand slowly (τ∼30 ms) dissociates from heme d. Recombination of CO with a reduced heme b in a fraction of the MV sample may also contribute to the 30-ms phase. In R enzyme, CO recombines to heme d (τ∼20 µs), some heme b558 (τ∼0.2–3 ms), and finally migrates from heme d to heme b595 (τ∼24 ms) in ∼5% of the enzyme population. Data are consistent with the recent nanosecond study of Rappaport et al. conducted on the membranes at 640-nm excitation but limited to the Soret band. The additional phases were revealed due to differences in excitation and other experimental conditions. PMID:24755641

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

    NASA Astrophysics Data System (ADS)

    Hebert, Philippe; Saint-Amans, Charles

    2013-06-01

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

  17. Rapid high-resolution spin- and angle-resolved photoemission spectroscopy with pulsed laser source and time-of-flight spectrometer

    SciTech Connect

    Gotlieb, K.; Hussain, Z.; Bostwick, A.; Jozwiak, C.; Lanzara, A.

    2013-09-15

    A high-efficiency spin- and angle-resolved photoemission spectroscopy (spin-ARPES) spectrometer is coupled with a laboratory-based laser for rapid high-resolution measurements. The spectrometer combines time-of-flight (TOF) energy measurements with low-energy exchange scattering spin polarimetry for high detection efficiencies. Samples are irradiated with fourth harmonic photons generated from a cavity-dumped Ti:sapphire laser that provides high photon flux in a narrow bandwidth, with a pulse timing structure ideally matched to the needs of the TOF spectrometer. The overall efficiency of the combined system results in near-E{sub F} spin-resolved ARPES measurements with an unprecedented combination of energy resolution and acquisition speed. This allows high-resolution spin measurements with a large number of data points spanning multiple dimensions of interest (energy, momentum, photon polarization, etc.) and thus enables experiments not otherwise possible. The system is demonstrated with spin-resolved energy and momentum mapping of the L-gap Au(111) surface states, a prototypical Rashba system. The successful integration of the spectrometer with the pulsed laser system demonstrates its potential for simultaneous spin- and time-resolved ARPES with pump-probe based measurements.

  18. Angle-resolved photoemission spectroscopy with 9-eV photon-energy pulses generated in a gas-filled hollow-core photonic crystal fiber

    SciTech Connect

    Bromberger, H. Liu, H.; Chávez-Cervantes, M.; Gierz, I.; Ermolov, A.; Belli, F.; Abdolvand, A.; Russell, P. St. J.; Travers, J. C.; Calegari, F.; Li, M. T.; Lin, C. T.; Cavalleri, A.

    2015-08-31

    A recently developed source of ultraviolet radiation, based on optical soliton propagation in a gas-filled hollow-core photonic crystal fiber, is applied here to angle-resolved photoemission spectroscopy (ARPES). Near-infrared femtosecond pulses of only few μJ energy generate vacuum ultraviolet radiation between 5.5 and 9 eV inside the gas-filled fiber. These pulses are used to measure the band structure of the topological insulator Bi{sub 2}Se{sub 3} with a signal to noise ratio comparable to that obtained with high order harmonics from a gas jet. The two-order-of-magnitude gain in efficiency promises time-resolved ARPES measurements at repetition rates of hundreds of kHz or even MHz, with photon energies that cover the first Brillouin zone of most materials.

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

    DOE PAGESBeta

    Nilson, P. M.; Solodov, A. A.; Davies, J. R.; Theobald, W.; Mileham, C.; Stoeckl, C.; Begishev, I. A.; Zuegel, J. D.; Froula, D. H.; Betti, R.; et al

    2015-09-25

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

  20. Employing time-resolved terahertz spectroscopy to analyze carrier dynamics in thin-film Cu{sub 2}ZnSn(S,Se){sub 4} absorber layers

    SciTech Connect

    Guglietta, Glenn W.; Baxter, Jason B.; Choudhury, Kaushik Roy; Caspar, Jonathan V.

    2014-06-23

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

  1. Space-resolved keV spectroscopy study of neonlike x-ray laser plasmas created with low-level prepulse irradiation

    NASA Astrophysics Data System (ADS)

    Nantel, Marc; Klisnick, Annie; Jamelot, Gerard; Holden, P. B.; Jaegle, Pierre; Zeitoun, Philippe; Tallents, Gregory J.; MacPhee, Andrew G.; Lewis, Ciaran L. S.

    1995-09-01

    Through the use of time-integrated space-resolved keV spectroscopy, we investigate line plasmas showing gain for irradiation using the prepulse technique. The experiments were conducted with the LULI laser of the Ecole Polytechnique, Palaiseau, France), at 1.06 micrometer with prepulse-to-main pulse intensity ratio ranging from 10-6 to 10-2. The particular x-ray lasers which were studied were the collisionally excited Ne-like zinc, copper and nickel systems. The effect of the prepulses on plasma conditions are inferred through spectroscopic line ratio diagnostics. It is observed that the value of the electron temperature for each system does not vary significantly with prepulse levels, nor does their spatially resolved profile along the line. The lateral width and density of the Ne-like regions in the plasmas of all three x-ray lasers are seen to increase with the prepulse level.

  2. Time-resolved Kα spectroscopy measurements of hot-electron equilibration dynamics in thin-foil solid targets: Collisional and collective effects

    SciTech Connect

    Nilson, P. M.; Solodov, A. A.; Davies, J. R.; Theobald, W.; Mileham, C.; Stoeckl, C.; Begishev, I. A.; Zuegel, J. D.; Froula, D. H.; Betti, R.; Meyerhofer, D. D.

    2015-09-25

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

  3. Electronic Structure of the Topological Insulator Bi2Se3 Using Angle-Resolved Photoemission Spectroscopy: Evidence for a Nearly Full Surface Spin Polarization

    SciTech Connect

    Z Pan; E Vescovo; A Fedorov; D Gardner; Y Lee; S Chu; G Gu; T Valla

    2011-12-31

    We performed high-resolution spin- and angle-resolved photoemission spectroscopy studies of the electronic structure and the spin texture on the surface of Bi{sub 2}Se{sub 3}, a model TI. By tuning the photon energy, we found that the topological surface state is well separated from the bulk states in the vicinity of k{sub z} = Z plane of the bulk Brillouin zone. The spin-resolved measurements in that region indicate a very high degree of spin polarization of the surface state, {approx}0.75, much higher than previously reported. Our results demonstrate that the topological surface state on Bi{sub 2}Se{sub 3} is highly spin polarized and that the dominant factors limiting the polarization are mainly extrinsic.

  4. Electronic Structure of the Topological Insulator Bi2Se3 Using Angle-Resolved Photoemission Spectroscopy: Evidence for a Nearly Full Surface Spin Polarization

    SciTech Connect

    Pan, Z.H.; Vescovo, E.; Fedorov, A.V.; Gardner, D.; Lee, Y.S.; Chu, S.; Gu, G.D.; Valla, T.

    2011-06-22

    We performed high-resolution spin- and angle-resolved photoemission spectroscopy studies of the electronic structure and the spin texture on the surface of Bi{sub 2}Se{sub 3}, a model TI. By tuning the photon energy, we found that the topological surface state is well separated from the bulk states in the vicinity of k{sub z} = Z plane of the bulk Brillouin zone. The spin-resolved measurements in that region indicate a very high degree of spin polarization of the surface state, {approx}0.75, much higher than previously reported. Our results demonstrate that the topological surface state on Bi{sub 2}Se{sub 3} is highly spin polarized and that the dominant factors limiting the polarization are mainly extrinsic.

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

    NASA Astrophysics Data System (ADS)

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

    2015-06-01

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

  6. Angle-resolved photoemission spectroscopy with 9-eV photon-energy pulses generated in a gas-filled hollow-core photonic crystal fiber

    NASA Astrophysics Data System (ADS)

    Bromberger, H.; Ermolov, A.; Belli, F.; Liu, H.; Calegari, F.; Chávez-Cervantes, M.; Li, M. T.; Lin, C. T.; Abdolvand, A.; Russell, P. St. J.; Cavalleri, A.; Travers, J. C.; Gierz, I.

    2015-08-01

    A recently developed source of ultraviolet radiation, based on optical soliton propagation in a gas-filled hollow-core photonic crystal fiber, is applied here to angle-resolved photoemission spectroscopy (ARPES). Near-infrared femtosecond pulses of only few μJ energy generate vacuum ultraviolet radiation between 5.5 and 9 eV inside the gas-filled fiber. These pulses are used to measure the band structure of the topological insulator Bi2Se3 with a signal to noise ratio comparable to that obtained with high order harmonics from a gas jet. The two-order-of-magnitude gain in efficiency promises time-resolved ARPES measurements at repetition rates of hundreds of kHz or even MHz, with photon energies that cover the first Brillouin zone of most materials.

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

    PubMed

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

    2004-03-30

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

  8. Compact all-fiber quartz-enhanced photoacoustic spectroscopy sensor with a 30.72 kHz quartz tuning fork and spatially resolved trace gas detection

    NASA Astrophysics Data System (ADS)

    Ma, Yufei; He, Ying; Yu, Xin; Zhang, Jingbo; Sun, Rui; Tittel, Frank K.

    2016-02-01

    An ultra compact all-fiber quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor using quartz tuning fork (QTF) with a low resonance frequency of 30.72 kHz was demonstrated. Such a sensor architecture has the advantages of easier optical alignment, lower insertion loss, lower cost, and more compact compared with a conventional QEPAS sensor using discrete optical components for laser delivery and coupling to the QTF. A fiber beam splitter and three QTFs were employed to perform multi-point detection and demonstrated the potential of spatially resolved measurements.

  9. Electronic band structure and momentum dependence of the superconducting gap in Ca1-xNaxFe2As2 from angle-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Evtushinsky, D. V.; Zabolotnyy, V. B.; Harnagea, L.; Yaresko, A. N.; Thirupathaiah, S.; Kordyuk, A. A.; Maletz, J.; Aswartham, S.; Wurmehl, S.; Rienks, E.; Follath, R.; Büchner, B.; Borisenko, S. V.

    2013-03-01

    Electronic structure of newly synthesized single crystals of calcium iron arsenide doped with sodium with Tc ranging from 33 to 14 K has been determined by angle-resolved photoemission spectroscopy (ARPES). The measured band dispersion is in general agreement with theoretical calculations, nonetheless implies absence of Fermi-surface nesting at an antiferromagnetic vector. A clearly developing below Tc strongly band-dependant superconducting gap has been revealed for samples with various doping levels. The BCS ratio for optimal doping, 2Δ/kBTc=5.5, is substantially smaller than the numbers observed for related compounds.

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

    NASA Technical Reports Server (NTRS)

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

    1995-01-01

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

  11. Analysis of electronic structure of amorphous InGaZnO/SiO{sub 2} interface by angle-resolved X-ray photoelectron spectroscopy

    SciTech Connect

    Ueoka, Y.; Ishikawa, Y.; Maejima, N.; Matsui, F.; Matsui, H.; Yamazaki, H.; Urakawa, S.; Horita, M.; Daimon, H.; Uraoka, Y.

    2013-10-28

    The electronic structures of amorphous indium gallium zinc oxide (a-IGZO) on a SiO{sub 2} layers before and after annealing were observed by constant final state X-ray photoelectron spectroscopy (CFS-XPS) and X-ray adsorption near-edge structure spectroscopy (XANES). From the results of angle-resolved CFS-XPS, the change in the electronic state was clearly observed in the a-IGZO bulk rather than in the a-IGZO/SiO{sub 2} interface. This suggests that the electronic structures of the a-IGZO bulk strongly affected the thin-film transistor characteristics. The results of XANES indicated an increase in the number of tail states upon atmospheric annealing (AT). We consider that the increase in the number of tail states decreased the channel mobility of AT samples.

  12. Fluorescence polarization spectroscopy and time-resolved fluorescence kinetics of native cancerous and normal rat kidney tissues.

    PubMed Central

    Tata, D B; Foresti, M; Cordero, J; Tomashefsky, P; Alfano, M A; Alfano, R R

    1986-01-01

    Steady state fluorescence polarization spectra and time-resolved emission decay kinetics have been measured in vitro from malignant and normal rat kidney tissue. The degrees of polarization and emission lifetimes from the cancerous and normal systems are different. The spectroscopic differences are attributed to environmental transformations local to the native flavin and porphyrin fluorophors' binding sites. PMID:3489490

  13. Wavelength-resolved optical extinction measurements of aerosols using broad-band cavity-enhanced absorption spectroscopy over the spectral range of 445-480 nm.

    PubMed

    Zhao, Weixiong; Dong, Meili; Chen, Weidong; Gu, Xuejun; Hu, Changjin; Gao, Xiaoming; Huang, Wei; Zhang, Weijun

    2013-02-19

    Despite the significant progress in the measurements of aerosol extinction and absorption using spectroscopy approaches such as cavity ring-down spectroscopy (CRDS) and photoacoustic spectroscopy (PAS), the widely used single-wavelength instruments may suffer from the interferences of gases absorption present in the real environment. A second instrument for simultaneous measurement of absorbing gases is required to characterize the effect of light extinction resulted from gases absorption. We present in this paper the development of a blue light-emitting diode (LED)-based incoherent broad-band cavity-enhanced spectroscopy (IBBCEAS) approach for broad-band measurements of wavelength-resolved aerosol extinction over the spectral range of 445-480 nm. This method also allows for simultaneous measurement of trace gases absorption present in the air sample using the same instrument. On the basis of the measured wavelength-dependent aerosol extinction cross section, the real part of the refractive index (RI) can be directly retrieved in a case where the RI does not vary strongly with the wavelength over the relevant spectral region. Laboratory-generated monodispersed aerosols, polystyrene latex spheres (PSL) and ammonium sulfate (AS), were employed for validation of the RI determination by IBBCEAS measurements. On the basis of a Mie scattering model, the real parts of the aerosol RI were retrieved from the measured wavelength-resolved extinction cross sections for both aerosol samples, which are in good agreement with the reported values. The developed IBBCEAS instrument was deployed for simultaneous measurements of aerosol extinction coefficient and NO(2) concentration in ambient air in a suburban site during two representative days. PMID:23320530

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

    SciTech Connect

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

    2015-12-15

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

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

    PubMed

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

    2016-01-01

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

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

    PubMed

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

    2015-12-01

    Superfluorescence appears as an intense background in femtosecond time-resolved fluorescence noncollinear optical parametric amplification spectroscopy, which severely interferes the reliable acquisition of the time-resolved fluorescence spectra especially for an optically dilute sample. Superfluorescence originates from the optical amplification of the vacuum quantum noise, which would be inevitably concomitant with the amplified fluorescence photons during the optical parametric amplification process. Here, we report the development of a femtosecond time-resolved fluorescence non-collinear optical parametric amplification spectrometer assisted with a 32-channel lock-in amplifier for efficient rejection of the superfluorescence background. With this spectrometer, the superfluorescence background signal can be significantly reduced to 1/300-1/100 when the seeding fluorescence is modulated. An integrated 32-bundle optical fiber is used as a linear array light receiver connected to 32 photodiodes in one-to-one mode, and the photodiodes are further coupled to a home-built 32-channel synchronous digital lock-in amplifier. As an implementation, time-resolved fluorescence spectra for rhodamine 6G dye in ethanol solution at an optically dilute concentration of 10(-5)M excited at 510 nm with an excitation intensity of 70 nJ/pulse have been successfully recorded, and the detection limit at a pump intensity of 60 μJ/pulse was determined as about 13 photons/pulse. Concentration dependent redshift starting at 30 ps after the excitation in time-resolved fluorescence spectra of this dye has also been observed, which can be attributed to the formation of the excimer at a higher concentration, while the blueshift in the earlier time within 10 ps is attributed to the solvation process. PMID:26724012

  18. Resolving the build-up of femtosecond mode-locking with single-shot spectroscopy at 90 MHz frame rate

    NASA Astrophysics Data System (ADS)

    Herink, G.; Jalali, B.; Ropers, C.; Solli, D. R.

    2016-05-01

    Mode-locked lasers have enabled some of the most precise measurements ever performed, from attosecond time-domain spectroscopy to metrology with frequency combs. However, such extreme precision belies the complexity of the underlying mode-locking dynamics. This complexity is particularly evident in the emergence of the mode-locked state, an intrinsically singular, non-repetitive transition. Many details of mode-locking are well understood, yet conventional spectroscopy cannot resolve the nascent dynamics in passive mode-locking on their natural nanosecond timescale, the single pulse period. Here, we capture the pulse-resolved spectral evolution of a femtosecond pulse train from the initial fluctuations, recording ∼900,000 consecutive periods. We directly observe critical phenomena on timescales from tens to thousands of roundtrips, including the birth of the broadband spectrum, accompanying wavelength shifts and transient interference dynamics described as auxiliary-pulse mode-locking. Enabled by the time-stretch transform, the results may impact laser design, ultrafast diagnostics and nonlinear optics.

  19. Depth profiling for the identification of unknown substances and concealed content at remote distances using time-resolved stand-off Raman spectroscopy.

    PubMed

    Zachhuber, Bernhard; Gasser, Christoph; Ramer, Georg; Chrysostom, Engelene t H; Lendl, Bernhard

    2012-08-01

    Time-resolved stand-off Raman spectroscopy was used to determine both the position and identity of substances relative to each other at remote distances (up to tens of meters). Spectral information of three xylene isomers, toluene, and sodium chlorate was obtained at a distance of 12 m from the setup. Pairs and triplets of these samples were placed at varying distances (10-60 cm) relative to each other. Via the photon time of flight the distance between the individual samples was determined to an accuracy of 7% (corresponding to a few cm) of the physically measured distance. Furthermore, at a distance of 40 m, time-resolved Raman depth profiling was used to detect sodium chlorate in a white plastic container that was non-transparent to the human eye. The combination of the ranging capabilities of Raman LIDAR (sample location usually determined using prior knowledge of the analyte of interest) with stand-off Raman spectroscopy (analyte detection at remote distances) provides the capability for depth profile identification of unknown substances and analysis of concealed content in distant objects. To achieve these results, a 532 nm laser with a pulse length of 4.4 ns was synchronized to an intensified charge-coupled device camera with a minimum gate width of 500 ps. For automated data analysis a multivariate curve resolution algorithm was employed. PMID:22800681

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

    SciTech Connect

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

    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.

  1. Development of a rapid Buffer-exchange system for time-resolved ATR-FTIR spectroscopy with the step-scan mode

    PubMed Central

    Furutani, Yuji; Kimura, Tetsunari; Okamoto, Kido

    2013-01-01

    Attenuated total reflectance (ATR)-FTIR spectroscopy has been widely used to probe protein structural changes under various stimuli, such as light absorption, voltage change, and ligand binding, in aqueous conditions. Time-resolved measurements require a trigger, which can be controlled electronically; therefore, light and voltage changes are suitable. Here we developed a novel, rapid buffer-exchange system for time-resolved ATR-FTIR spectroscopy to monitor the ligand- or ion-binding re-action of a protein. By using the step-scan mode (time resolution; 2.5 ms), we confirmed the completion of the buffer-exchange reaction within ∼25 ms; the process was monitored by the infrared absorption change of a nitrate band at 1,350 cm−1. We also demonstrated the anion-binding reaction of a membrane protein, Natronomonas pharaonis halorhodopsin (pHR), which binds a chloride ion in the initial anion-binding site near the retinal chromophore. The formation of chloride- or nitrate-bound pHR was confirmed by an increase of the retinal absorption band at 1,528 cm−1. It also should be noted that low sample consumption (∼1 µg of protein) makes this new method a powerful technique to understand ligand–protein and ion–protein interactions, particularly for membrane proteins. PMID:27493550

  2. Time-resolved x-ray photoelectron spectroscopy techniques for real-time studies of interfacial charge transfer dynamics

    SciTech Connect

    Shavorskiy, Andrey; Hertlein, Marcus; Guo Jinghua; Tyliszczak, Tolek; Cordones, Amy; Vura-Weis, Josh; Siefermann, Katrin; Slaughter, Daniel; Sturm, Felix; Weise, Fabian; Khurmi, Champak; Belkacem, Ali; Weber, Thorsten; Gessner, Oliver; Bluhm, Hendrik; Strader, Matthew; Cho, Hana; Coslovich, Giacomo; Kaindl, Robert A.; Lin, Ming-Fu; and others

    2013-04-19

    X-ray based spectroscopy techniques are particularly well suited to gain access to local oxidation states and electronic dynamics in complex systems with atomic pinpoint accuracy. Traditionally, these techniques are applied in a quasi-static fashion that usually highlights the steady-state properties of a system rather than the fast dynamics that often define the system function on a molecular level. Novel x-ray spectroscopy techniques enabled by free electron lasers (FELs) and synchrotron based pump-probe schemes provide the opportunity to monitor intramolecular and interfacial charge transfer processes in real-time and with element and chemical specificity. Two complementary time-domain xray photoelectron spectroscopy techniques are presented that are applied at the Linac Coherent Light Source (LCLS) and the Advanced Light Source (ALS) to study charge transfer processes in N3 dye-sensitized ZnO semiconductor nanocrystals, which are at the heart of emerging light-harvesting technologies.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    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.

  4. Intrinsic spin polarized electronic structure of CrO{sub 2} epitaxial film revealed by bulk-sensitive spin-resolved photoemission spectroscopy

    SciTech Connect

    Fujiwara, Hirokazu; Sunagawa, Masanori; Kittaka, Tomoko; Terashima, Kensei; Wakita, Takanori; Muraoka, Yuji; Yokoya, Takayoshi

    2015-05-18

    We have performed bulk-sensitive spin-resolved photoemission spectroscopy in order to clarify the intrinsic spin-resolved electronic states of half-metallic ferromagnet CrO{sub 2}. We used CrO{sub 2} epitaxial films on TiO{sub 2}(100), which shows a peak at 1 eV with a clear Fermi edge, consistent with the bulk-sensitive PES spectrum for CrO{sub 2}. In spin-resolved spectra at 40 K, while the Fermi edge was observed in the spin up (majority spin) state, no states at the Fermi level (E{sub F}) with an energy gap of 0.5 eV below E{sub F} were observed in the spin down (minority spin) state. At 300 K, the gap in the spin down state closes. These results are consistent with resistivity measurements and magnetic hysteresis curves of the fabricated CrO{sub 2} film, constituting spectroscopic evidence for the half-metallicity of CrO{sub 2} at low temperature and reducing the spin polarization at room temperature. We also discuss the electron correlation effects of Cr 3d.

  5. Superatom State-Resolved Dynamics of the Au25(SC8H9)18(-) Cluster from Two-Dimensional Electronic Spectroscopy.

    PubMed

    Stoll, Tatjana; Sgrò, Enrico; Jarrett, Jeremy W; Réhault, Julien; Oriana, Aurelio; Sala, Luca; Branchi, Federico; Cerullo, Giulio; Knappenberger, Kenneth L

    2016-02-17

    Superatom state-resolved dynamics of the Au25(SC8H9)18(-) monolayer-protected cluster (MPC) were examined using femtosecond two-dimensional electronic spectroscopy (2DES). The electronic ground state of the Au25(SC8H9)18(-) MPC is described by an eight-electron P-like superatom orbital. Hot electron relaxation (200 ± 15 fs) within the superatom D manifold of lowest-unoccupied molecular orbitals was resolved from hot hole relaxation (290 ± 20 fs) in the superatom P states by using 2DES in a partially collinear pump-probe geometry. Electronic relaxation dynamics mediated by specific superatom states were distinguished by examining the time-dependent cross-peak amplitudes for specific excitation and detection photon energy combinations. Quantification of the time-dependent amplitudes and energy positions of cross peaks in the 2.21/1.85 eV (excitation/detection) region confirmed that an apparent energetic blue shift observed for transient bleach signals results from rapid hot electron relaxation in the superatom D states. The combination of structurally precise MPCs and state-resolved 2DES can be used to examine directly the influence of nanoscale structural modifications on electronic carrier dynamics, which are critical for developing nanocluster-based photonic devices. PMID:26814560

  6. Intrinsic spin polarized electronic structure of CrO2 epitaxial film revealed by bulk-sensitive spin-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Fujiwara, Hirokazu; Sunagawa, Masanori; Terashima, Kensei; Kittaka, Tomoko; Wakita, Takanori; Muraoka, Yuji; Yokoya, Takayoshi

    2015-05-01

    We have performed bulk-sensitive spin-resolved photoemission spectroscopy in order to clarify the intrinsic spin-resolved electronic states of half-metallic ferromagnet CrO2. We used CrO2 epitaxial films on TiO2(100), which shows a peak at 1 eV with a clear Fermi edge, consistent with the bulk-sensitive PES spectrum for CrO2. In spin-resolved spectra at 40 K, while the Fermi edge was observed in the spin up (majority spin) state, no states at the Fermi level (EF) with an energy gap of 0.5 eV below EF were observed in the spin down (minority spin) state. At 300 K, the gap in the spin down state closes. These results are consistent with resistivity measurements and magnetic hysteresis curves of the fabricated CrO2 film, constituting spectroscopic evidence for the half-metallicity of CrO2 at low temperature and reducing the spin polarization at room temperature. We also discuss the electron correlation effects of Cr 3d.

  7. Spin-resolved photoelectron spectroscopy using femtosecond extreme ultraviolet light pulses from high-order harmonic generation.

    PubMed

    Plötzing, M; Adam, R; Weier, C; Plucinski, L; Eich, S; Emmerich, S; Rollinger, M; Aeschlimann, M; Mathias, S; Schneider, C M

    2016-04-01

    The fundamental mechanism responsible for optically induced magnetization dynamics in ferromagnetic thin films has been under intense debate since almost two decades. Currently, numerous competing theoretical models are in strong need for a decisive experimental confirmation such as monitoring the triggered changes in the spin-dependent band structure on ultrashort time scales. Our approach explores the possibility of observing femtosecond band structure dynamics by giving access to extended parts of the Brillouin zone in a simultaneously time-, energy- and spin-resolved photoemission experiment. For this purpose, our setup uses a state-of-the-art, highly efficient spin detector and ultrashort, extreme ultraviolet light pulses created by laser-based high-order harmonic generation. In this paper, we present the setup and first spin-resolved spectra obtained with our experiment within an acquisition time short enough to allow pump-probe studies. Further, we characterize the influence of the excitation with femtosecond extreme ultraviolet pulses by comparing the results with data acquired using a continuous wave light source with similar photon energy. In addition, changes in the spectra induced by vacuum space-charge effects due to both the extreme ultraviolet probe- and near-infrared pump-pulses are studied by analyzing the resulting spectral distortions. The combination of energy resolution and electron count rate achieved in our setup confirms its suitability for spin-resolved studies of the band structure on ultrashort time scales. PMID:27131684

  8. Spin-resolved photoelectron spectroscopy using femtosecond extreme ultraviolet light pulses from high-order harmonic generation

    NASA Astrophysics Data System (ADS)

    Plötzing, M.; Adam, R.; Weier, C.; Plucinski, L.; Eich, S.; Emmerich, S.; Rollinger, M.; Aeschlimann, M.; Mathias, S.; Schneider, C. M.

    2016-04-01

    The fundamental mechanism responsible for optically induced magnetization dynamics in ferromagnetic thin films has been under intense debate since almost two decades. Currently, numerous competing theoretical models are in strong need for a decisive experimental confirmation such as monitoring the triggered changes in the spin-dependent band structure on ultrashort time scales. Our approach explores the possibility of observing femtosecond band structure dynamics by giving access to extended parts of the Brillouin zone in a simultaneously time-, energy- and spin-resolved photoemission experiment. For this purpose, our setup uses a state-of-the-art, highly efficient spin detector and ultrashort, extreme ultraviolet light pulses created by laser-based high-order harmonic generation. In this paper, we present the setup and first spin-resolved spectra obtained with our experiment within an acquisition time short enough to allow pump-probe studies. Further, we characterize the influence of the excitation with femtosecond extreme ultraviolet pulses by comparing the results with data acquired using a continuous wave light source with similar photon energy. In addition, changes in the spectra induced by vacuum space-charge effects due to both the extreme ultraviolet probe- and near-infrared pump-pulses are studied by analyzing the resulting spectral distortions. The combination of energy resolution and electron count rate achieved in our setup confirms its suitability for spin-resolved studies of the band structure on ultrashort time scales.

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

    NASA Astrophysics Data System (ADS)

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

    2004-03-01

    A compact and fast multi-channel time-resolved near-infrared spectroscopy system for tissue oximetry was developed. It employs semiconductor laser and fibre optics for delivery of optical signals. Photons are collected by eight 1 mm fibres and detected by a multianode photomultiplier. A time-correlated single photon counting board is used for the parallel acquisition of time-resolved reflectance curves. Estimate of the reduced scattering coefficient is achieved by fitting with a standard model of diffusion theory, while the modified Lambert-Beer law is used to assess the absorption coefficient. In vivo measurements were performed on five healthy volunteers to monitor spatial changes in calf muscle (medial and lateral gastrocnemius; MG, LG) oxygen saturation (SmO2) and total haemoglobin concentration (tHb) during dynamic plantar flexion exercise performed at 50% of the maximal voluntary contraction. At rest SmO2 was 73.0 ± 0.9 and 70.5 ± 1.7% in MG and LG, respectively (P = 0.045). At the end of the exercise, SmO2 decreased (69.1 ± 1.8 and 63.8 ± 2.1% in MG and LG, respectively; P < 0.01). The LG desaturation was greater than the MG desaturation (P < 0.02). These results strengthen the role of time-resolved near-infrared spectroscopy as a powerful tool for investigating the spatial and temporal features of muscle SmO2 and tHb.

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

    PubMed

    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. PMID:25840439

  11. Homogeneous and inhomogeneous broadenings and the Voigt line shapes in the phase-resolved and intensity sum-frequency generation vibrational spectroscopy.

    PubMed

    Chen, Shun-Li; Fu, Li; Gan, Wei; Wang, Hong-Fei

    2016-01-21

    In this report, we show that the ability to measure the sub-1 cm(-1) resolution phase-resolved and intensity high-resolution broadband sum frequency generation vibrational spectra of the -CN stretch vibration of the Langmuir-Blodgett (LB) monolayer of the 4-n-octyl-4'-cyanobiphenyl (8CB) on the z-cut α-quartz surface allows the direct comparison and understanding of the homogeneous and inhomogeneous broadenings in the imaginary and intensity SFG vibrational spectral line shapes in detail. The difference of the full width at half maximum (FWHM) of the imaginary and intensity sum-frequency generation vibrational spectroscopy spectra of the same vibrational mode is the signature of the Voigt line shape and it measures the relative contribution to the overall line shape from the homogeneous and inhomogeneous broadenings in SFG vibrational spectra. From the phase-resolved and intensity spectra, we found that the FWHM of the 2238.00 ± 0.02 cm(-1) peak in the phase-resolved imaginary and intensity spectra is 19.2 ± 0.2 cm(-1) and 21.6 ± 0.4 cm(-1), respectively, for the -CN group of the 8CB LB monolayer on the z-cut α-quartz crystal surface. The FWHM width difference of 2.4 cm(-1) agrees quantitatively with a Voigt line shape with a homogeneous broadening half width of Γ = 5.29 ± 0.08 cm(-1) and an inhomogeneous standard derivation width Δω = 5.42 ± 0.07 cm(-1). These results shed new lights on the understanding and interpretation of the line shapes of both the phase-resolved and the intensity SFG vibrational spectra, as well as other incoherent and coherent spectroscopic techniques in general. PMID:26801040

  12. Homogeneous and inhomogeneous broadenings and the Voigt line shapes in the phase-resolved and intensity sum-frequency generation vibrational spectroscopy

    NASA Astrophysics Data System (ADS)

    Chen, Shun-Li; Fu, Li; Gan, Wei; Wang, Hong-Fei

    2016-01-01

    In this report, we show that the ability to measure the sub-1 cm-1 resolution phase-resolved and intensity high-resolution broadband sum frequency generation vibrational spectra of the -CN stretch vibration of the Langmuir-Blodgett (LB) monolayer of the 4-n-octyl-4'-cyanobiphenyl (8CB) on the z-cut α-quartz surface allows the direct comparison and understanding of the homogeneous and inhomogeneous broadenings in the imaginary and intensity SFG vibrational spectral line shapes in detail. The difference of the full width at half maximum (FWHM) of the imaginary and intensity sum-frequency generation vibrational spectroscopy spectra of the same vibrational mode is the signature of the Voigt line shape and it measures the relative contribution to the overall line shape from the homogeneous and inhomogeneous broadenings in SFG vibrational spectra. From the phase-resolved and intensity spectra, we found that the FWHM of the 2238.00 ± 0.02 cm-1 peak in the phase-resolved imaginary and intensity spectra is 19.2 ± 0.2 cm-1 and 21.6 ± 0.4 cm-1, respectively, for the -CN group of the 8CB LB monolayer on the z-cut α-quartz crystal surface. The FWHM width difference of 2.4 cm-1 agrees quantitatively with a Voigt line shape with a homogeneous broadening half width of Γ = 5.29 ± 0.08 cm-1 and an inhomogeneous standard derivation width Δω = 5.42 ± 0.07 cm-1. These results shed new lights on the understanding and interpretation of the line shapes of both the phase-resolved and the intensity SFG vibrational spectra, as well as other incoherent and coherent spectroscopic techniques in general.

  13. Role of polyplex intermediate species on gene transfer efficiency: polyethylenimine-DNA complexes and time-resolved fluorescence spectroscopy.

    PubMed

    Ketola, Tiia-Maaria; Hanzlíková, Martina; Urtti, Arto; Lemmetyinen, Helge; Yliperttula, Marjo; Vuorimaa, Elina

    2011-03-01

    Polyethylenimine (PEI) is a cationic DNA condensing polymer that facilitates gene transfer into the mammalian cells. The highest gene transfer with branched PEI is obtained at high nitrogen/phosphate (N/P) ratios with free PEI present. The small molecular weight PEI alone is not able to mediate DNA transfection. Here, we used recently developed time-resolved fluorescence spectroscopic method to study the mechanism of PEI-DNA complex formation and to investigate how free PEI, mean molecular weight, and branching of PEI affect the complexes. Analysis of fluorescence lifetimes and time-resolved spectra revealed that for both linear and branched high-molecular-weight PEI the complexation takes place in two steps, but the small-molecular-weight branched PEI complexed DNA at a single step. According to the binding constants obtained from time-resolved spectroscopic measurements, the affinity of N/P complexation per nitrogen atom is highest for LPEI and weakest for BPEI, whereas SPEI-DNA complexation showed intermediate values. Thus, the binding constant alone does not give adequate measure for transfection efficiency. On the other hand, the presence of intermediate states during the polyplex formation seems to be favorable for the gene transfection. Free PEI had no impact on the physical state of PEI-DNA complexes, even though it was essential for gene transfection in the cell culture. In conclusion, the molecular size and topology of PEI have direct influence on the DNA complexation but the free PEI does not. Free PEI must facilitate transfection at the cellular level and not via indirect effects on the PEI-DNA complexes. PMID:21291220

  14. Spatially resolved diffuse reflectance spectroscopy of two-layer turbid media by densely packed multi-pixel photodiode reflectance probe

    NASA Astrophysics Data System (ADS)

    Senlik, Ozlem; Greening, Gage; Muldoon, Timothy J.; Jokerst, Nan M.

    2016-03-01

    Spatially-resolved diffuse reflectance (SRDR) measurements provide photon path information, and enable layered tissue analysis. This paper presents experimental SRDR measurements on two-layer PDMS skin tissue-mimicking phantoms of varying top layer thicknesses, and bulk phantoms of varying optical properties using concentric multi-pixel photodiode array (CMPA) probes, and corresponding forward Monte Carlo simulations. The CMPA is the most densely packed semiconductor SRDR probe reported to date. Signal contrasts between the single layer phantom and bi-layer phantoms with varying top layer thicknesses are as high as 80%. The mean error between the Monte Carlo simulations and the experiment is less than 6.2 %.

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

    SciTech Connect

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

    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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-05-01

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

  17. Transmission electron microscopy and time resolved optical spectroscopy study of the electronic and structural interactions of ZnO nanorods with bovine serum albumin.

    PubMed

    Klaumünzer, M; Weichsel, U; Mačković, M; Spiecker, E; Peukert, W; Kryschi, C

    2013-08-22

    The adsorption behavior and electronic interactions of bovine serum albumin (BSA) with ZnO nanorod surfaces were investigated using high-resolution transmission electron microscopy as well as stationary and time-resolved optical spectroscopy techniques. Transmission electron microscopy shows that ZnO nanorod surfaces are surrounded by a homogeneous amorphous BSA film with thicknesses between ~2.5 and 5.0 nm. The electronic structure and adsorption geometry of BSA were examined using high-angle annular dark field scanning transmission electron microscopy combined with electron energy loss spectroscopy. The adsorption process was observed to result into an unfolded conformation of BSA becoming predominantly bound in the side-on orientation at the ZnO surface. This adsorption mode of the BSA molecules allows for a strong interaction with surface states of the ZnO nanorods. This is obvious from its efficient quenching of the defect-center photoluminescence of ZnO. Complementary information of electronic interactions across the ZnO nanorod interface was obtained from femtosecond transient absorption spectroscopy experiments. The rise dynamics of the measured transients revealed altered hole trapping dynamics and, thus, indicated to heterogeneous charge transfer as emerging from adsorbed BSA molecules to defect centers of the ZnO interface. PMID:23889004

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

    SciTech Connect

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

    2007-02-02

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  1. Fast spatially resolved exhaust gas recirculation (EGR) distribution measurements in an internal combustion engine using absorption spectroscopy.

    PubMed

    Yoo, Jihyung; Prikhodko, Vitaly; Parks, James E; Perfetto, Anthony; Geckler, Sam; Partridge, William P

    2015-09-01

    Exhaust gas recirculation (EGR) in internal combustion engines is an effective method of reducing NOx emissions while improving efficiency. However, insufficient mixing between fresh air and exhaust gas can lead to cycle-to-cycle and cylinder-to-cylinder non-uniform charge gas mixtures of a multi-cylinder engine, which can in turn reduce engine performance and efficiency. A sensor packaged into a compact probe was designed, built and applied to measure spatiotemporal EGR distributions in the intake manifold of an operating engine. The probe promotes the development of more efficient and higher-performance engines by resolving high-speed in situ CO2 concentration at various locations in the intake manifold. The study employed mid-infrared light sources tuned to an absorption band of CO2 near 4.3 μm, an industry standard species for determining EGR fraction. The calibrated probe was used to map spatial EGR distributions in an intake manifold with high accuracy and monitor cycle-resolved cylinder-specific EGR fluctuations at a rate of up to 1 kHz. PMID:26253286

  2. Tracking the photodissociation dynamics of liquid nitromethane at 266 nm by femtosecond time-resolved broadband transient grating spectroscopy

    NASA Astrophysics Data System (ADS)

    Wu, Honglin; Song, Yunfei; Yu, Guoyang; Wang, Yang; Wang, Chang; Yang, Yanqiang

    2016-05-01

    Femtosecond time-resolved transient grating (TG) technique was employed to get insight into the photodissociation mechanism of liquid nitromethane (NM). Broadband white-light continuum was introduced as the probe to observe the evolution of electronic excited states of NM molecules and the formation of photodissociation products simultaneously. The reaction channel of liquid NM under 266 nm excitation was obtained that NM molecules in excited state S2 relax through two channels: about 73% relax to low lying S1 state through S2/S1 internal conversion with a time constant of 0.24 ps and then go back to the ground state through S1/S0 internal conversion; the other 27% will dissociate with a time constant of 2.56 ps. NO2 was found to be one of the products from the experimental TG spectra, which confirmed that C-N bond rupture was the primary dissociation channel of liquid NM.

  3. Observations of a mode transition in a hydrogen hollow cathode discharge using phase resolved optical emission spectroscopy

    SciTech Connect

    Dixon, Sam Charles, Christine; Dedrick, James; Boswell, Rod; Gans, Timo; O'Connell, Deborah

    2014-07-07

    Two distinct operational modes are observed in a radio frequency (rf) low pressure hydrogen hollow cathode discharge. The mode transition is characterised by a change in total light emission and differing expansion structures. An intensified CCD camera is used to make phase resolved images of Balmer α emission from the discharge. The low emission mode is consistent with a typical γ discharge, and appears to be driven by secondary electrons ejected from the cathode surface. The bright mode displays characteristics common to an inductive discharge, including increased optical emission, power factor, and temperature of the H{sub 2} gas. The bright mode precipitates the formation of a stationary shock in the expansion, observed as a dark region adjacent to the source-chamber interface.

  4. Optical emission spectroscopy of metal-halide lamps: Radially resolved atomic state distribution functions of Dy and Hg

    SciTech Connect

    Nimalasuriya, T.; Flikweert, A.J.; Stoffels, W.W.; Haverlag, M.; Mullen, J.J.A.M. van der; Pupat, N.B.M.

    2006-03-01

    Absolute line intensity measurements are performed on a metal-halide lamp. Several transitions of atomic and ionic Dy and atomic Hg are measured at different radial positions from which we obtain absolute atomic and ionic Dy intensity profiles. From these profiles we construct the radially resolved atomic state distribution function (ASDF) of the atomic and ionic Dy and the atomic Hg. From these ASDFs several quantities are determined as functions of radial position, such as the (excitation) temperature, the ion ratio Hg{sup +}/Dy{sup +}, the electron density, the ground state, and the total density of Dy atoms and ions. Moreover, these ASDFs give us insight about the departure from equilibrium. The measurements show a hollow density profile for the atoms and the ionization of atoms in the center. In the outer parts of the lamp molecules dominate.

  5. Optical emission spectroscopy of metal-halide lamps: Radially resolved atomic state distribution functions of Dy and Hg

    NASA Astrophysics Data System (ADS)

    Nimalasuriya, T.; Flikweert, A. J.; Stoffels, W. W.; Haverlag, M.; van der Mullen, J. J. A. M.; Pupat, N. B. M.

    2006-03-01

    Absolute line intensity measurements are performed on a metal-halide lamp. Several transitions of atomic and ionic Dy and atomic Hg are measured at different radial positions from which we obtain absolute atomic and ionic Dy intensity profiles. From these profiles we construct the radially resolved atomic state distribution function (ASDF) of the atomic and ionic Dy and the atomic Hg. From these ASDFs several quantities are determined as functions of radial position, such as the (excitation) temperature, the ion ratio Hg+/Dy+, the electron density, the ground state, and the total density of Dy atoms and ions. Moreover, these ASDFs give us insight about the departure from equilibrium. The measurements show a hollow density profile for the atoms and the ionization of atoms in the center. In the outer parts of the lamp molecules dominate.

  6. Femtosecond time-resolved ionization spectroscopy of Na 3(B) and the question of the geometric phase

    NASA Astrophysics Data System (ADS)

    Schön, J.; Köppel, H.

    1994-12-01

    The femtosecond time-resolved ionization spectrum of the B-state of Na 3 has been studied theoretically, taking two nuclear degrees of freedom into account (bending mode and pseudorotation). Special emphasis is put on a comparison between different approaches to the pseudorotational dynamics of Na 3(B) proposed earlier in the literature: a Jahn-Teller treatment invoked in the original work versus a pseudo-Jahn-Teller treatment advanced in later studies. The time-dependent wave-packet dynamics is found to differ drastically in the two cases although it proceeds on (virtually) the same potential energy surface. This is interpreted as a consequence of the geometric phase which is nontrivial only in the Jahn-Teller case. A low-energy peak in the Fourier transform of the pump-probe spectrum of Baumert et al. (Chem. Phys. Letters 209 (1993) 29) is tentatively interpreted as evidence in favour of the pseudo-Jahn-Teller mechanism.

  7. Rotationally resolved photoelectron spectroscopy of a triatomic molecule: Photoionization of the C (0.0.0) state of water

    SciTech Connect

    Glab, W.L.; Glynn, P.T.; Dehmer, P.M.; Dehmer, J.L.

    1996-05-01

    The authors have used a magnetic bottle photoelectron spectrometer to study the distribution of ion rotational states following photoionization of selected rotational states of the {tilde C}(0,0,0) state of water by 355 nm light. The spectrometer`s kinetic energy resolution of about 4 meV was sufficient to yield rotationally resolved time-of-flight photoelectron spectra. Comparison of the measured and calculated photoelectron spectra is encouraging and reveals unusual photoionization dynamics due to very nonatomic-like behavior in the photoionization continuum and to the presence of Cooper minima. This is the first time that such a test of photoionization theory for a polyatomic molecule at finite kinetic energy has been possible.

  8. Spatially resolved high-resolution x-ray spectroscopy of high-current plasma-focus discharges

    SciTech Connect

    ZajaPc, S.; Rzadkiewicz, J.; Scholz, M.; Paduch, M.; Zielinska, E.; Rosmej, O.; Yongtao, Zhao; Gojska, A.

    2010-10-15

    Soft x-ray emission from a Mather-type plasma-focus device (PF-1000) operated at {approx}400 kJ was measured. The high density and temperature plasma were generated by the discharge in the deuterium-argon gas mixture in the modified (high-current) plasma-focus configuration. A spherically bent mica crystal spectrograph viewing the axial output of the pinch region was used to measure the x-ray spectra. Spatially resolved spectra including the characteristic x-ray lines of highly ionized Ar and continua were recorded by means of an x-ray film. The x-ray emission of PF-1000 device was studied at different areas of the pinch.

  9. Picosecond-resolved X-ray absorption spectroscopy at low signal contrast using a hard X-ray streak camera

    SciTech Connect

    Adams, Bernhard W.; Rose-Petruck, Christoph; Jiao, Yishuo

    2015-06-24

    A picosecond-resolving hard-X-ray streak camera has been in operation for several years at Sector 7 of the Advanced Photon Source (APS). Several upgrades have been implemented over the past few years to optimize integration into the beamline, reduce the timing jitter, and improve the signal-to-noise ratio. These include the development of X-ray optics for focusing the X-rays into the sample and the entrance slit of the streak camera, and measures to minimize the amount of laser light needed to generate the deflection-voltage ramp. For the latter, the photoconductive switch generating the deflection ramp was replaced with microwave power electronics. With these, the streak camera operates routinely at 88 MHz repetition rate, thus making it compatible with all of the APS fill patterns including use of all the X-rays in the 324-bunch mode. Sample data are shown to demonstrate the performance.

  10. Time- and spatial-resolved XAFS spectroscopy in a single shot: new analytical possibilities for in situ material characterization.

    PubMed

    Buzanich, Ana Guilherme; Radtke, Martin; Reinholz, Uwe; Riesemeier, Heinrich; Emmerling, Franziska

    2016-05-01

    A new concept that comprises both time- and lateral-resolved X-ray absorption fine-structure information simultaneously in a single shot is presented. This uncomplicated set-up was tested at the BAMline at BESSY-II (Berlin, Germany). The primary broadband beam was generated by a double multilayer monochromator. The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by either an energy-sensitive area detector, the so-called color X-ray camera, or by an area-sensitive detector based on a CCD camera, in θ-2θ geometry. The first tests were performed with thin metal foils and some iron oxide mixtures. A time resolution of lower than 1 s together with a spatial resolution in one dimension of at least 50 µm is achieved. PMID:27140157

  11. Photocycles of bacteriorhodopsin in light- and dark-adapted purple membrane studied by time-resolved absorption spectroscopy.

    PubMed Central

    Hofrichter, J; Henry, E R; Lozier, R H

    1989-01-01

    Nanosecond time-resolved absorption spectra have been measured throughout the photocycle of bacteriorhodopsin in both light-adapted and dark-adapted purple membrane (PM). The data from dark-adapted samples are interpretable as the superposition of two photocycles arising independently from the all-trans and 13-cis retinal isomers that coexist in the dark-adapted state. The presence of a photocycle in dark-adapted PM which is indistinguishable from that observed for light-adapted PM under the same experimental conditions is demonstrated by the observation of the same five relaxation rates associated with essentially identical changes in the photoproduct spectra. This cycle is attributed to the all-trans component. The cycle of the 13-cis component is revealed by scaling the data measured for the light-adapted sample and subtracting it from the data on the dark-adapted mixture. At times less than 1 ms, the resulting difference spectra are nearly time-independent. The peak of the difference spectrum is near 600 nm, although there appears to be a slight (approximately 2 nm) blue-shift in the first few microseconds. Subsequently the amplitude of this spectrum decays and the peak of the difference spectrum shifts in two relaxations. Most of the amplitude of the photoproduct difference spectrum (approximately 80%) decays in a single relaxation having a time constant of approximately 35 ms. The difference spectrum remaining after this relaxation peaks at approximately 590 nm and is indistinguishable from the classical light-dark difference spectrum, which we find, in experiments performed on a much longer time scale, to peak at 588 nm. The decay of this remaining photo-product is not resolvable in the nanosecond kinetic experiments, but dark adaptation of a completely light-adapted sample is found to occur exponentially with a relaxation time of approximately 2,000 s under the conditions of our experiments. PMID:2819234

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

    NASA Astrophysics Data System (ADS)

    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.

  13. Photosystem II Does Not Possess a Simple Excitation Energy Funnel: Time-Resolved Fluorescence Spectroscopy Meets Theory

    PubMed Central

    2013-01-01

    The experimentally obtained time-resolved fluorescence spectra of photosystem II (PS II) core complexes, purified from a thermophilic cyanobacterium Thermosynechococcus vulcanus, at 5–180 K are compared with simulations. Dynamic localization effects of excitons are treated implicitly by introducing exciton domains of strongly coupled pigments. Exciton relaxations within a domain and exciton transfers between domains are treated on the basis of Redfield theory and generalized Förster theory, respectively. The excitonic couplings between the pigments are calculated by a quantum chemical/electrostatic method (Poisson-TrEsp). Starting with previously published values, a refined set of site energies of the pigments is obtained through optimization cycles of the fits of stationary optical spectra of PS II. Satisfactorily agreement between the experimental and simulated spectra is obtained for the absorption spectrum including its temperature dependence and the linear dichroism spectrum of PS II core complexes (PS II-CC). Furthermore, the refined site energies well reproduce the temperature dependence of the time-resolved fluorescence spectrum of PS II-CC, which is characterized by the emergence of a 695 nm fluorescence peak upon cooling down to 77 K and the decrease of its relative intensity upon further cooling below 77 K. The blue shift of the fluorescence band upon cooling below 77 K is explained by the existence of two red-shifted chlorophyll pools emitting at around 685 and 695 nm. The former pool is assigned to Chl45 or Chl43 in CP43 (Chl numbering according to the nomenclature of Loll et al. Nature2005, 438, 1040) while the latter is assigned to Chl29 in CP47. The 695 nm emitting chlorophyll is suggested to attract excitations from the peripheral light-harvesting complexes and might also be involved in photoprotection. PMID:23537277

  14. Layer-Resolved Evolution of Organic Thin Films Monitored by Photoelectron Emission Microscopy and Optical Reflectance Spectroscopy

    PubMed Central

    2015-01-01

    Photoelectron emission microscopy (PEEM) and differential (optical) reflectance spectroscopy (DRS) have proven independently to be versatile analytical tools for monitoring the evolution of organic thin films during growth. In this paper, we present the first experiment in which both techniques have been applied simultaneously and synchronously. We illustrate how the combined PEEM and DRS results can be correlated to obtain an extended perspective on the electronic and optical properties of a molecular film dependent on the film thickness and morphology. As an example, we studied the deposition of the organic molecule α-sexithiophene on Ag(111) in the thickness range from submonolayers up to several monolayers. PMID:26523159

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

    SciTech Connect

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

    2005-11-11

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

  16. Atomic Resolution Mapping of the Excited-State Electronic Structure of Cu2O with Time-Resolved X-Ray Absorption Spectroscopy

    SciTech Connect

    Hillyard, Patrick B.; Kuchibhatla, Satyanarayana V N T; Glover, T. E.; Hertlein, M. P.; Huse, N.; Nachimuthu, Ponnusamy; Saraf, Laxmikant V.; Thevuthasan, Suntharampillai; Gaffney, Kelly J.

    2009-09-29

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

  17. Numerical and Experimental Aspects of Data Acquisition and Processing in Application to Temperature Resolved 3-D Sub-Millimeter Spectroscopy for Astrophysics and Spectral Assignment.

    NASA Astrophysics Data System (ADS)

    Medvedev, Ivan R.; Fortman, Sarah M.; Neese, Christopher F.; De Lucia, Frank C.

    2009-06-01

    Experimental determination of the lower state energy for every transition in molecular spectra, made possible by temperature resolved 3-D spectroscopy, opens new frontiers in our ability to predict molecular spectra over a wide range of temperatures and to assign rotational spectra in many vibrational states. Our improved collisional cooling cell design extends temperature coverage of this technique to 77 K. This enhances our ability to simulate molecular spectra at temperatures of astronomical relevance. We are reporting on experimental and numerical aspects of dealing with exceptionally high information content of these spectra. New data reduction algorithms allow us to process this data in timely fashion in an attempt to make them available to astronomical community.

  18. A shock pressure induced phase transition from liquid to solid of cyclohexane using time-resolved coherent anti-Stokes Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Oguchi, Shiro; Sato, Akira; Kondo, Ken-Ichi; Nakamura, Kazutaka

    2007-06-01

    The liquid-solid phase transition of cyclohexane has been studied under laser shock compression up to 3.8 GPa by using nanosecond time-resolved Coherent Anti-stokes Raman Spectroscopy (CARS) and laser shock compression. The shock wave is generated by irradiation of 10 ns pulsed laser beam on the plasma confinement target and its pressure is estimated from a particle velocity, which is measured by optically recording velocity interferometer system (ORVIS). Higher frequency shift of the Raman peaks (ring-breathing, C-C stretching, and CH2 twist modes) was observed at high pressure. At 3.8 GPa, splitting of the peak (CH2 twist mode) due to change in symmetry of surrounding molecules, which corresponds to phase transition to solid IV, was observed at delay time of 20 ns. Rapid liquid-solid phase transition has been directly observed to occur within 20 ns.

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

    PubMed

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

    2011-03-01

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

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

    NASA Astrophysics Data System (ADS)

    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 <0.13 and >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.