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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. Phase Resolved Cyclotron Spectroscopy of Polars

    NASA Astrophysics Data System (ADS)

    Dealaman, Shannon J.

    2010-01-01

    This research was conducted through the REU program at Cerro Tololo Interamerican Observatory in La Serena, Chile. For this research we reduced and modeled phase-resolved cyclotron spectroscopy of four AM Her stars: MN Hya, HU Aqu, VV Pup, and QS Tel. Two of the four spectra show good cyclotron harmonics while the other two were taken during a high state with too much noise in the spectra. Using a Constant-Lambda code (Schwope et al., 1990) we modeled the two good spectra and further modeled the harmonic motion of HU Aqr. The models produced for MN Hya gave parameters with a magnetic field strength between 44 MG and 43.4 MG, a plasma temperature between 4.1 keV and 5.6 keV, a log Λ of 4.2 ± 0.3, and a viewing angle set between 83.0 degrees and 70.0 degrees and HU Aqr a magnetic field between 36.0 MG and 37.6 MG, a plasma temperature between 15.0 keV and 15.5 keV, a log Λ of 4.0 ± 0.3, and a viewing angle between 89.5 degrees and 70.5 degrees. This was the first attempt to model MN Hya with a constant lambda code and the first harmonic motion model of HU Aqr.

  3. Rotationally resolved electronic spectroscopy of 4-aminobenzonitrile

    NASA Astrophysics Data System (ADS)

    Berden, Giel; van Rooy, Jack; Meerts, W. Leo; Zachariasse, Klaas A.

    1997-10-01

    The rotationally resolved fluorescence excitation spectrum of the 0 00 band in the S 1 ← S 0 transition of 4-aminobenzonitrile (ABN) was recorded, at 299 nm, by using laser induced fluorescence in a molecular beam apparatus. This spectrum exhibits pure b-type character, which indicates that the electronic transition moment vector is oriented along the short molecular axis. The rotational constants of the S 0 and S 1 states were determined. In addition, the rotationally resolved fluorescence excitation spectra of two vibronic bands in the S 1 state, at 807 and 816 cm -1, were recorded. The molecular structure of the ABN molecule is discussed by comparing the rotational constants and the inertial defects.

  4. Research on time-resolved terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Deng, Yuqiang; Sun, Qing; Liu, Feng; Wang, Changlei; Xing, Qirong

    2010-10-01

    We have built a set of terahertz time-domain spectroscopy system using electro-optic crystals. Conventional terahertz time-domain spectroscopy based on Fourier-transform for spectra analysis, which mixes the frequency components of the entire temporal terahertz waveform in one frequency domain; therefore, it yields different terahertz spectra from a same terahertz pulse with different scanning lengths. We introduce a new technique for the joint time-frequency analysis of terahertz time-domain spectroscopy based on wavelet-transform technique. With this technique, the frequency components in different time locations are clearly exhibited on a two-dimensional plane; therefore, the noise in the pulse tail cannot affect the frequency in the main pulse. This technique clearly separates the frequency of terahertz from that of its echo in the time domain; therefore, the interference spectrum occur in Fourier-transform is naturally removed. By varying the shape of analysis wavelet, high time resolution and high frequency resolution are easily obtained. The absorption coefficients of envelope, plastic, foam and cotton have been measured with the wavelet technique.

  5. 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.

  6. 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.

  7. Time resolved spectroscopy using synchrotron infrared pulses

    SciTech Connect

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

    1997-09-01

    Electron synchrotron storage rings, such as the VUV ring at the National Synchrotron Light Source (NSLS), produce short pulses of infrared (IR) radiation suitable for investigating the time-dependent phenomena in a variety of interesting experimental systems. In contrast to other pulses sources of IR, the synchrotron produces a continuum spectral output over the entire IR (and beyond), though at power levels typically below those obtained from laser systems. The infrared synchrotron radiation (IRSR) source is therefore well-suited as a probe using standard FTIR spectroscopic techniques. Here the authors describe the pump-probe spectroscopy facility being established at the NSLS and demonstrate the technique by measuring the photocarrier decay in a semiconductor.

  8. 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.

  9. Ultrafast time resolved vibrational spectroscopy in liquid systems

    NASA Astrophysics Data System (ADS)

    Seifert, G.; Hofmann, M.; Weidlich, K.; Graener, H.

    1996-04-01

    The ultrafast dynamics of small molecules in the liquid phase can successfully be studied tracing the relaxation pathways of vibrational excess energy. Two complementing experimental techniques, picosecond IR double resonance spectroscopy and time resolved incoherent Anti-Stokes Raman spectroscopy, are very powerful tools for such studies. The capabilities of investigations combining these methods are discussed on the example of new experimental data on liquid dichloromethane (CH2Cl2).

  10. [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

  11. Time-resolved resonance Raman spectroscopy: exploring reactive intermediates.

    PubMed

    Sahoo, Sangram Keshari; Umapathy, Siva; Parker, Anthony W

    2011-10-01

    The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single "do-it-all" technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-μs) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy. PMID:21986070

  12. Spin-resolved electron spectroscopies of epitaxial magnetite (001) (abstract)

    NASA Astrophysics Data System (ADS)

    Shaw, Kimberly A.; Lochner, Eric; Lind, David M.; DiBari, Rebecca C.; Stoyanov, Plamen; Singer, Brian

    1996-04-01

    We will present the first spin-resolving electron spectroscopic studies of a magnetite (Fe3O4)(001) surface. Magnetite is a semimetal with a high density of states in the minority band, but a large band gap in the majority states at the Fermi energy. The polarization of the secondary emission cascade is measured using spin-resolved secondary electron emission spectroscopy (SRSEES), and reflects the semimetallic spin structure of Fe3O4. The polarization plateau of spin-resolved secondary emission (29.8%) matches the average 3D band polarization of stoichiometric Fe3O4 as determined from spin-resolved band structure calculations (34.2%). An enhancement of the polarization of the secondary electrons at lowest energies will also be discussed. Spin-resolved Auger emission spectroscopy (SRAES) of the Fe3O4 films have been measured and show correlation effects in the valence-valence Auger transitions. Suppressed intensity and polarization of M23M45M45 Auger emission relative to M1M45M45 Auger emission is observed, as well as strong resonant emission with shake-up. Conversely, no spin polarization is detected in the spin-resolved oxygen LMM Auger features, although oxygen Auger emission (in which we can distinguish between adsorbed and bonded oxygen) is used to verify surface cleanliness of the samples. The synthesis of Fe3O4 films grown on magnesium oxide (001) substrates using oxygen plasma-assisted molecular beam epitaxy will be discussed, as will thin-film characterization using SQUID magnetometry and x-ray and electron diffraction. A unique angle-, energy-, and spin-resolved electron spectrometer has been designed and built for the study of magnetic surfaces, and these studies represent its' first use. That spectrometer is based on a tandem configuration of an energy-dispersive energy analyzer and Mott spin polarimeter.

  13. Time-resolved photoelectron spectroscopy: from wavepackets to observables.

    PubMed

    Wu, Guorong; Hockett, Paul; Stolow, Albert

    2011-11-01

    Time-resolved photoelectron spectroscopy (TRPES) is a powerful tool for the study of intramolecular dynamics, particularly excited state non-adiabatic dynamics in polyatomic molecules. Depending on the problem at hand, different levels of TRPES measurements can be performed: time-resolved photoelectron yield; time- and energy-resolved photoelectron yield; time-, energy-, and angle-resolved photoelectron yield. In this pedagogical overview, a conceptual framework for time-resolved photoionization measurements is presented, together with discussion of relevant theory for the different aspects of TRPES. Simple models are used to illustrate the theory, and key concepts are further amplified by experimental examples. These examples are chosen to show the application of TRPES to the investigation of a range of problems in the excited state dynamics of molecules: from the simplest vibrational wavepacket on a single potential energy surface; to disentangling intrinsically coupled electronic and nuclear motions; to identifying the electronic character of the intermediate states involved in non-adiabatic dynamics by angle-resolved measurements in the molecular frame, the most complete measurement.

  14. 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

  15. Ultrafast angle-resolved photoemission spectroscopy of quantum materials

    NASA Astrophysics Data System (ADS)

    Smallwood, Christopher L.; Kaindl, Robert A.; Lanzara, Alessandra

    2016-07-01

    Techniques in time- and angle-resolved photoemission spectroscopy have facilitated a number of recent advances in the study of quantum materials. We review developments in this field related to the study of incoherent nonequilibrium electron dynamics, the analysis of interactions between electrons and collective excitations, the exploration of dressed-state physics, and the illumination of unoccupied band structure. Future prospects are also discussed.

  16. 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

  17. Spatially resolved solid-state MAS-NMR-spectroscopy.

    PubMed

    Scheler, U; Schauss, G; Blümich, B; Spiess, H W

    1996-07-01

    A comprehensive account of spatially resolved solid-state MAS NMR of 13C is given. A device generating field gradients rotating synchronously with the magic angle spinner is described. Spatial resolution and sensitivity are compared for phase and frequency encoding of spatial information. The suppression of spinning sidebands is demonstrated for both cases. Prior knowledge about the involved materials can be used for the reduction of data from spatially resolved spectra to map chemical structure. Indirect detection via 13C NMR gives access to the information about mobility from proton-wideline spectra. Two-dimensional solid-state spectroscopy with spatial resolution is demonstrated for a rotor synchronized MAS experiment which resolves molecular order as a function of space. By comparison of different experiments the factors affecting the spatial resolution are investigated.

  18. Time-resolved Raman spectroscopy for in situ planetary mineralogy.

    PubMed

    Blacksberg, Jordana; Rossman, George R; Gleckler, Anthony

    2010-09-10

    Planetary mineralogy can be revealed through a variety of remote sensing and in situ investigations that precede any plans for eventual sample return. We briefly review those techniques and focus on the capabilities for on-surface in situ examination of Mars, Venus, the Moon, asteroids, and other bodies. Over the past decade, Raman spectroscopy has continued to develop as a prime candidate for the next generation of in situ planetary instruments, as it provides definitive structural and compositional information of minerals in their natural geological context. Traditional continuous-wave Raman spectroscopy using a green laser suffers from fluorescence interference, which can be large (sometimes saturating the detector), particularly in altered minerals, which are of the greatest geophysical interest. Taking advantage of the fact that fluorescence occurs at a later time than the instantaneous Raman signal, we have developed a time-resolved Raman spectrometer that uses a streak camera and pulsed miniature microchip laser to provide picosecond time resolution. Our ability to observe the complete time evolution of Raman and fluorescence spectra in minerals makes this technique ideal for exploration of diverse planetary environments, some of which are expected to contain strong, if not overwhelming, fluorescence signatures. We discuss performance capability and present time-resolved pulsed Raman spectra collected from several highly fluorescent and Mars-relevant minerals. In particular, we have found that conventional Raman spectra from fine grained clays, sulfates, and phosphates exhibited large fluorescent signatures, but high quality spectra could be obtained using our time-resolved approach.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. Angle-resolved photoelectron spectroscopy of atomic oxygen

    NASA Astrophysics Data System (ADS)

    van der Meulen, P.; Krause, M. O.; de Lange, C. A.

    1991-06-01

    Using synchrotron-radiation-based, angle-resolved photoelectron spectroscopy, the relative partial photoionization cross sections for the production of the 4 S 0 and 2 D 0 ionic states in atomic oxygen, as well as the corresponding asymmetry parameters, are measured from threshold at 13.62 to about 30 eV. The cross sections are placed on an absolute scale using previous data obtained with an electron spectroscopy modulation method. Attention is focused on the numerous autoionization resonances below the 2p -12D0, 2p -12P0, and 2s -14Pe limits. The behavior of the asymmetry parameters across these resonances is observed for the first time. The 2s2p4(4Pe)3p(3S0,3P0,3D0) resonances are fitted by a Fano-type profile to obtain accurate values for the position, width, and q parameter.

  4. Multidimensional time-resolved spectroscopy of vibrational coherence in biopolyenes.

    PubMed

    Buckup, Tiago; Motzkus, Marcus

    2014-01-01

    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.

  5. 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.

  6. 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).

  7. 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.

  8. Time Resolved Single Wire Aluminum Optical Spectroscopy Experiments

    NASA Astrophysics Data System (ADS)

    Blesener, Kate; Pikuz, Sergey; Shelkovenko, Tatiana; Blesener, Isaac; Chalenski, David; Hammer, David; Maron, Yitzhak; Bernshtam, Vladimir

    2010-11-01

    We are exploring the conditions of plasmas generated by current-driven explosions of single fine aluminum wires, including temperatures, electron density, ionization state, and potentially magnetic field, using time-resolved emission spectroscopy at visible wavelengths. The experiments are being carried out with 15μm to 75μm Al wires driven by the 10kA, 500ns rise time LCP3 pulser. To determine the magnetic field, a new diagnostic method is being developed which makes use of Zeeman-effect-produced differences in the line shapes of two fine structure components of a multiplet that are equally broadened by Stark and Doppler effects. This method has been demonstrated at the Weizmann Institute of Science in laser-produced plasmas with lower energy densities [1]. [4pt] [1] E. Stambulchik, et al. Phys. Rev. Lett. 98, 225001 (2007).

  9. 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.

  10. 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

  11. 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

  12. 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

  13. 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.

  14. 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

  15. Orientation Characterisation of Aerospace Materials by Spatially Resolved Acoustic Spectroscopy

    NASA Astrophysics Data System (ADS)

    Li, Wenqi; Coulson, Jethro; Aveson, John W.; Smith, Richard J.; Clark, Matt; Somekh, Michael G.; Sharples, Steve D.

    2014-06-01

    Material characteristics in metals such as strength, stiffness and fracture resistance are strongly related to the underlying microstructure. The crystallographic structure and orientation are related to the ultrasonic properties through the stiffness matrix. In individual grains it is possible to analytically determine the ultrasonic velocity from the orientation and stiffness, or determine the stiffness from the known orientation and measured velocity. In this paper we present a technique for imaging the crystallographic orientation of grains in metals using spatially resolved acoustic spectroscopy (SRAS) and a novel inverse solver that can determine the crystallographic orientation from the known stiffness matrix for the material and the SRAS velocity measurement. Previously we have shown the ability of this technique to determine the orientation on single crystal nickel samples; we extended the technique to multigrain industrial metals, such as aluminium, nickel and Inconel. The comparison between SRAS and electron backscatter diffraction (EBSD) on the nickel sample is presented. SRAS is a fast, accurate, quantitative and robust technique for imaging material microstructure and orientation over a wide range of scales and industrial materials.

  16. Mass resolved resonance ionization spectroscopy of combustion radicals

    SciTech Connect

    Not Available

    1992-06-23

    This report discusses the following topics: REMPI spectroscopy of HCO and DCO; Rempi spectroscopy of the ethynyl radical; REMPI spectroscopy of new electronic states of C{sub 2}; and a flame sampling laser ionization mass spectrometer.

  17. 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.

  18. Surface Ice Spectroscopy of Pluto and Charon Resolved

    NASA Astrophysics Data System (ADS)

    Protopapa, Silvia; Boehnhardt, H.; Herbst, T.; Merlin, F.; Cruikshank, D. P.; Grundy, W. M.

    2007-10-01

    We present results of 1-5μm spectroscopy of the Pluto-Charon dwarf planet system. The observations were performed in August 2005 with the NACO instrument at the 8.2m-VLT telescope Yepun of the European Southern Observatory in Paranal/Chile. NACO's adaptive optics facility allowed to resolve easily this binary system, this way enabling spectroscopy of the two objects separately. These spectroscopic observations are complemented by a model interpretation of the surface ice composition of Pluto and Charon. For Pluto, it is the first time that the complete L band is measured without unresolved contamination by light from Charon, while its M band spectrum was never measured before. Using Hapke modeling of the spectrum, we find that a geographic mixture of pure methane ice, methane diluted in nitrogen and tholin fits Pluto's spectrum from 1 to 4μm, although not in all details. Our data suggest the presence of further so far unknown and thus unidentified absorption bands centered around 4.0μm and 4.6μm. The latter absorption could be related to the presence of nitriles, arising from C and N connected with a triple bond and possibly CO ice. The difficulty in the modeling is due to the fact that the nitrile band is highly variable in position as a result of variations in its chemical environment. Charon's spectrum is measured in the wavelength range (1-4)μm, for the first time simultaneously with, but isolated from that of Pluto. It was previously studied in some detail in the JHK wavelength region, but was never measured beyond 2.5μm. Since the JHK region of Charon's spectrum is dominated by water ice absorption, it came not unexpectedly that very deep and broad water ice signatures are found in the L band part of Charon's surface spectrum. We model Charon's spectrum with pure H2O ice darkened by a spectrally neutral continuum absorber.

  19. Time-resolved spectroscopy of the pulsating CV GW Lib

    NASA Astrophysics Data System (ADS)

    van Spaandonk, L.; Steeghs, D.; Marsh, T. R.; Torres, M. A. P.

    2010-01-01

    We present time-resolved optical spectroscopy of the dwarf nova GW Librae during its rare 2007 April superoutburst and compare these with quiescent epochs. The data provide the first opportunity to track the evolution of the principal spectral features. In the early stages of the outburst, the optically thick disc dominates the optical and the line components show clear orbital radial velocity excursions. In the course of several weeks, optically thin regions become more prominent as strong emission lines replace the broad disc absorption. Post-outburst spectroscopy covering the I band illustrates the advantages of CaII relative to the commonly used Balmer lines when attempting to constrain binary parameters. Due to the lower ionization energy combined with smaller thermal and shear broadening of these lines, a sharp emission component is seen to be moving in between the accretion disc peaks in the CaII line. No such component is visible in the Balmer lines. We interpret this as an emission component originating on the hitherto unseen mass donor star. This emission component has a mean velocity of ~ -15 +/- 5 kms-1 which is associated with the systemic velocity γ, and a velocity semi-amplitude of Kem = 82.2 +/- 4.9 kms-1. Doppler tomography reveals an asymmetric accretion disc, with the S-wave mapping to a sharp spot in the tomogram with a velocity consistent to what is obtained with line profile fitting. A centre of symmetry analysis of the disc component suggests a very small value for the WD orbital velocity K1 as is also inferred from double Gaussian fits to the spectral lines. While our conservative dynamical limits place a hard upper limit on the binary mass ratio of q < 0.23, we favour a significantly lower value near q ~ 0.06. Pulsation modelling suggests a white dwarf mass ~1Msolar. This, paired with a low-mass donor, near the empirical sequence of an evolved cataclysmic variable close to the period bounce, appears to be consistent with all the

  20. Time- and space-resolved spectroscopy of dynamic hohlraum interiors.

    SciTech Connect

    Maron, Yitzhak; Dunham, Gregory Sham; Lemke, Raymond William; Stambulchik, E.; Chandler, Gordon Andrew; MacFarlane, Joseph John; Schroen, Diana Grace; Lucas, J. M.; Moore, Tracy Croft; Youngblood, K.; Bailey, James E.; Lake, Patrick Wayne; Golovkin, I. E.; Mehlhorn, Thomas Alan; Slutz, Stephen A.

    2005-01-01

    A dynamic hohlraum is created when an annular z-pinch plasma implodes onto a cylindrical 0.014 g/cc 6-mm-diameter CH{sub 2} foam. The impact launches a radiating shock that propagates toward the axis at {approx}350 {micro}m/ns. The radiation trapped by the tungsten z-pinch plasma forms a {approx}200 eV hohlraum that provides X-rays for indirect drive inertial confinement fusion capsule implosion experiments. We are developing the ability to diagnose the hohlraum interior using emission and absorption spectroscopy of Si atoms added as a tracer to the central portion of the foam. Time- and space-resolved Si spectra are recorded with an elliptical crystal spectrometer viewing the cylindrical hohlraum end-on. A rectangular aperture at the end of the hohlraum restricts the field of view so that the 1D spectrometer resolution corresponds approximately to the hohlraum radial direction. This enables distinguishing between spectra from the unshocked radiation-heated foam and from the shocked foam. Typical spectral lines observed include the Si Ly{alpha} with its He-like satellites and the He-like resonance sequence including He{alpha}, He{beta}, and He{gamma}, along with some of their associated Li-like satellites. Work is in progress to infer the hohlraum conditions using collisional-radiative modeling that accounts for the radiation environment and includes both opacity effects and detailed Stark broadening calculations. These 6-mm-scale radiation-heated plasmas might eventually also prove suitable for testing Stark broadening line profile calculations or for opacity measurements.

  1. 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

  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. Time-resolved EPR spectroscopy in a Unix environment.

    PubMed

    Lacoff, N M; Franke, J E; Warden, J T

    1990-02-01

    A computer-aided time-resolved electron paramagnetic resonance (EPR) spectrometer implemented under version 2.9 BSD Unix was developed by interfacing a Varian E-9 EPR spectrometer and a Biomation 805 waveform recorder to a PDP-11/23A minicomputer having MINC A/D and D/A capabilities. Special problems with real-time data acquisition in a multiuser, multitasking Unix environment, addressing of computer main memory for the control of hardware devices, and limitation of computer main memory were resolved, and their solutions are presented. The time-resolved EPR system and the data acquisition and analysis programs, written entirely in C, are described. Furthermore, the benefits of utilizing the Unix operating system and the C language are discussed, and system performance is illustrated with time-resolved EPR spectra of the reaction center cation in photosystem 1 of green plant photosynthesis.

  4. Spatially Resolved Spectroscopy of the SNR IC443

    NASA Astrophysics Data System (ADS)

    Gorenstein, P.

    1998-07-01

    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.

  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. Time-resolved diffuse optical spectroscopy: a differential absorption approach

    NASA Astrophysics Data System (ADS)

    Taroni, Paola; Bassi, Andrea; Spinelli, Lorenzo; Cubeddu, Rinaldo; Pifferi, Antonio

    2009-07-01

    A method was developed to estimate spectral changes of the absorption properties of turbid media from time-resolved reflectance/transmittance measurements. It was derived directly from the microscopic Beer-Lambert law, and tested against simulations and phantom measurements.

  7. REsolved Spectroscopy Of a Local VolumE: The RESOLVE Survey in Stripe 82

    NASA Astrophysics Data System (ADS)

    Kannappan, Sheila; Eckert, Kathleen; Norman, Dara; Norris, Mark; Hoversten, Erik; Stark, David; Moffett, Amanda; Baker, Ashley D.; Berlind, Andreas A.; Crawford, Steve; Damjanov, Ivana; Dell'Antonio, Ian; Gonzalez, Roberto; Hall, Kirsten; Khochfar, Sadegh; Leroy, Adam; Lu, Yu; Maraston, Claudia; McGaugh, Stacy; Naluminsa, Liz; Salzer, John J.; Sellwood, Jerry A.; Vaisanen, Petri; Watson, Linda

    2013-08-01

    We request 14 nights of gray/dark time with the Goodman Spectrograph on SOAR and 88 hours of gray/dark time with the GMOS IFU on Gemini over two semesters to complete Phase 1 of the RESOLVE survey, providing a volume-limited gas, stellar, and dynamical mass census in the exceptionally complete Stripe 82 legacy equatorial strip. RESOLVE spans diverse large-scale cosmic structures and probes mass scales down to ~10^9 Msun in the gas-rich dwarf galaxy regime. With the proposed census, RESOLVE will (1) provide the first direct, complete, and environment-dependent measurement of the velocity function, potentially uncovering crucial clues to puzzling discrepancies in the dwarf galaxy inventory, and (2) put a unique constraint on the location of the ``missing baryons,'' via a comprehensive census of multiple mass components in relation to star formation and dynamical mass in a cosmological volume.

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

    SciTech Connect

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

    1999-07-19

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

  9. 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.

  10. Time-resolved fluorescence spectroscopy of spinach chloroplast.

    PubMed

    Yu, W; Pellegrino, F; Alfano, R R

    1977-04-11

    Picosecond fluorescent kinetics and time-resolved spectra of spinach chloroplast were measured at room temperature and low temperatures. The measurement is conducted with 530 nm excitation at an average intensity of 2-10(14) photons/cm2, pluse and at a pulse separation of 6 ns for the 100 pulses used. The 685 nm fluorescent kinetics was found to decay with two components, a fast component with a 56 ps lifetime, and a slow component with a 220 ps lifetime. The 730 nm fluorescent kinetics at room temperature is a single exponential decay with a 100 ps lifetime. The 730 nm fluorescence lifetime was found to increase by a factor of 6 when the temperature was lowered from room temperature to 90 K, while the 685 and 695 nm fluorescent kinetics were unchanged. The time-resolved spectra data obtained within 10 ps after excitation is consistent with the kinetic data reported here. A two-level fluorescence scheme is proposed to explain the kinetics. The effect of excitation with high light intensity and multiple pulses is discussed.

  11. Protein Dynamics from Time-Resolved UV Raman Spectroscopy

    PubMed Central

    Balakrishnan, Gurusamy; Weeks, Colin L.; Ibrahim, Mohammed; Soldatova, Alexandra V.; Spiro, Thomas G.

    2008-01-01

    Summary Raman spectroscopy can provide unique information on the evolution of structure in proteins over a wide range of time-scales; the picosecond to millisecond range can be accessed with pump-probe techniques. Specific parts of the molecule are interrogated by tuning the probe laser to a resonant electronic transition, including the UV transitions of aromatic residues and of the peptide bond. Advances in laser technology have enabled the characterization of transient species at an unprecedented level of structural detail. Applications to protein unfolding and allostery are reviewed. PMID:18606227

  12. Protein dynamics from time resolved UV Raman spectroscopy.

    PubMed

    Balakrishnan, Gurusamy; Weeks, Colin L; Ibrahim, Mohammed; Soldatova, Alexandra V; Spiro, Thomas G

    2008-10-01

    Raman spectroscopy can provide unique information on the evolution of structure in proteins over a wide range of time scales; the picosecond to millisecond range can be accessed with pump-probe techniques. Specific parts of the molecule are interrogated by tuning the probe laser to a resonant electronic transition, including the UV transitions of aromatic residues and of the peptide bond. Advances in laser technology have enabled the characterization of transient species at an unprecedented level of structural detail. Applications to protein unfolding and allostery are reviewed. PMID:18606227

  13. 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.

  14. 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

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

    PubMed

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

    2015-02-28

    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. PMID:25725724

  16. 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.

  17. 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.

  18. 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.

  19. Resonant and Time-Resolved Spin Noise Spectroscopy

    NASA Astrophysics Data System (ADS)

    Song, Xinlin; Pursley, Brennan; Sih, Vanessa

    Spin noise spectroscopy is a technique which can probe the system while it remains in equilibrium. It was first demonstrated in atomic gases and then in solid state systems. Most existing spin noise measurement setups digitize the spin fluctuation signal and then analyze the power spectrum. Recently, pulsed lasers have been used to expand the bandwidth of accessible dynamics and allow direct time-domain correlation measurements. Here we develop and test a model for ultrafast pulsed laser spin noise measurements as well as a scheme to measure spin lifetimes longer than the laser repetition period. For the resonant spin noise technique, analog electronics are used to capture correlations from the extended pulse train, and the signal at a fixed time delay is measured as a function of applied magnetic field.

  20. Time-resolved Spectroscopy of Active Binary Stars

    NASA Astrophysics Data System (ADS)

    Brown, Alexander

    EUVE has provided the first stellar coronal spectra showing individual emission lines, thereby allowing coronal modelling at a level of sophistication previously unattainable. Long EUVE observations have shown the prevalence of large-scale flaring in the coronae of active binary stars. We propose to obtain EUVE DSS spectra and photometry for 8 active binaries, four of which have never been observed by EUVE (EI Eri, AR Psc, V478 Lyr, BY Dra) and four EUV-bright systems that merit reobservation (Sigma CrB, Sigma Gem, Xi UMa, Lambda And). We shall use these observations to derive high quality quiescent coronal spectra for modelling, and to obtain new flare data. We shall try to coordinate these observations with ground-based radio observations and other spacecraft, if the scheduling allows. The proposed observations will significantly increase the available EUVE spectroscopy of active binaries.

  1. 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

  2. Phase-resolved reflectance spectroscopy on layered turbid media

    NASA Astrophysics Data System (ADS)

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

    1995-05-01

    In this study, we investigate the influence of layered tissue structures on the phase-resolved reflectance. As a particular example, we consider the affect of the skin, skull, and meninges on noninvasive blood oxygenation determination of the brain. In this case, it's important to know how accurate one can measure the absorption coefficient of the brain through the enclosing layers of different tissues. Experiments were performed on layered gelatin tissue phantoms and the results compared to diffusion theory. It is shown that when a high absorbing medium is placed on top of a low absorbing medium, the absorption coefficient of the lower layer is accessible. In the inverse case, where a low absorbing medium is placed on top of a high absorbing medium, the absorption coefficient of the underlying medium can only be determined if the differences in the absorption coefficient are small, or the top layer is very thin. Investigations on almost absorption and scattering free layers, like the cerebral fluid filled arachnoid, reveal that the determination of the absorption coefficient is barely affected by these kinds of structures.

  3. Picosecond time-resolved fluorescence spectroscopy of phytochrome and stentorin

    NASA Astrophysics Data System (ADS)

    Song, Pill-Soon

    1991-05-01

    Phytochrome is a tetrapyrrole chromoprotein. It serves as a sensitive photosensor for red lightmediated gene expression and other developmental/morphological responses in plants. In this paper photochemical dynamics of the phytochrome molecule have been described in terms of photoisomerization of the tetrapyrrole chromophore in its singlet excited state and subsequent thermal processes in the Pr Pfr phototransformation of phytochrome. Stentorin acts as the photosensor molecule in the ciliate Stentor coeruleus. This unicellular protozoan is most sensitive to red light (610-620 urn). Stentor also senses the direction of light propagation as evidenced by their light-avoiding and negative phototactic swimming behaviors. This aneural photosensory phenomenon is triggered by the photoreceptor stentorin. The possible involvement of a light-induced transient proton release from the photoreceptor as the primary mechanism of light-signal processing has been discussed on the basis of picosecond fluorescence decays and time-resolved fluorescence spectra of stentorin in solution. An initial sensory signal generated by the primary photoprocess of stentorin then triggers subsequent transduction steps that include calcium ion influx from the extracellular medium. Calcium ion influx from the extracellular medium to the cytosol causes the Stentor cell to reverse its ciliary beating and subsequently steer away from the light trap. II.

  4. Resolving Fast, Confined Diffusion in Bacteria with Image Correlation Spectroscopy.

    PubMed

    Rowland, David J; Tuson, Hannah H; Biteen, Julie S

    2016-05-24

    By following single fluorescent molecules in a microscope, single-particle tracking (SPT) can measure diffusion and binding on the nanometer and millisecond scales. Still, although SPT can at its limits characterize the fastest biomolecules as they interact with subcellular environments, this measurement may require advanced illumination techniques such as stroboscopic illumination. Here, we address the challenge of measuring fast subcellular motion by instead analyzing single-molecule data with spatiotemporal image correlation spectroscopy (STICS) with a focus on measurements of confined motion. Our SPT and STICS analysis of simulations of the fast diffusion of confined molecules shows that image blur affects both STICS and SPT, and we find biased diffusion rate measurements for STICS analysis in the limits of fast diffusion and tight confinement due to fitting STICS correlation functions to a Gaussian approximation. However, we determine that with STICS, it is possible to correctly interpret the motion that blurs single-molecule images without advanced illumination techniques or fast cameras. In particular, we present a method to overcome the bias due to image blur by properly estimating the width of the correlation function by directly calculating the correlation function variance instead of using the typical Gaussian fitting procedure. Our simulation results are validated by applying the STICS method to experimental measurements of fast, confined motion: we measure the diffusion of cytosolic mMaple3 in living Escherichia coli cells at 25 frames/s under continuous illumination to illustrate the utility of STICS in an experimental parameter regime for which in-frame motion prevents SPT and tight confinement of fast diffusion precludes stroboscopic illumination. Overall, our application of STICS to freely diffusing cytosolic protein in small cells extends the utility of single-molecule experiments to the regime of fast confined diffusion without requiring advanced

  5. Spatially resolved sulfur K-edge XANES spectroscopy of wheat leaves infected by Puccinia triticina

    NASA Astrophysics Data System (ADS)

    Lichtenberg, H.; Prange, A.; Steiner, U.; Oerke, E.-C.; Hormes, J.

    2009-11-01

    In this study, wheat leaves infected with brown rust, a plant disease of serious economic concern caused by the fungus Puccinia triticina, were investigated using spatially resolved XANES (X-ray Absorption Near Edge Structure) spectroscopy at the sulfur K-absorption edge.

  6. Studies of multifrequency phase-resolved fluorescence spectroscopy for spectral fingerprinting

    SciTech Connect

    McGown, L.B.

    1990-01-01

    During the past two project periods (7/1/88--12/31/90), we have made significant advances towards our goal of characterizing samples in terms of their dynamic spectral characteristics through the use of phase-resolved fluorescence spectroscopy. Specific achievements are discussed, each of which describes a particular area of focus in our studies.

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

    NASA Astrophysics Data System (ADS)

    Hedqvist, Anders; Rachlew-Källne, Elisabeth

    1998-09-01

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

  8. Vibrational spectroscopy of a transient species through time-resolved Fourier transform infrared emission spectroscopy: The vinyl radical

    SciTech Connect

    Letendre, Laura; Liu, Dean-Kuo; Pibel, Charles D.; Halpern, Joshua B.; Dai, Hai-Lung

    2000-06-01

    An approach for detecting the vibrational spectrum of transient species is demonstrated on the vinyl radical. Photodissociation of carefully chosen precursors at selected photolysis wavelengths produce highly vibrationally excited radicals. Infrared (IR) emission from these radicals is then measured by time-resolved Fourier transform spectroscopy with nanosecond time resolution. All nine vibrational bands of the vinyl radical, generated from four different precursors, are obtained and reported here for the first time. (c) 2000 American Institute of Physics.

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

    NASA Astrophysics Data System (ADS)

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

    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.

  10. Excitation emission and time-resolved fluorescence spectroscopy of selected varnishes used in historical musical instruments.

    PubMed

    Nevin, Austin; Echard, Jean-Philippe; Thoury, Mathieu; Comelli, Daniela; Valentini, Gianluca; Cubeddu, Rinaldo

    2009-11-15

    The analysis of various varnishes from different origins, which are commonly found on historical musical instruments was carried out for the first time with both fluorescence excitation emission spectroscopy and laser-induced time-resolved fluorescence spectroscopy. Samples studied include varnishes prepared using shellac, and selected diterpenoid and triterpenoid resins from plants, and mixtures of these materials. Fluorescence excitation emission spectra have been collected from films of naturally aged varnishes. In parallel, time-resolved fluorescence spectroscopy of varnishes provides means for discriminating between short- (less than 2.0 ns) and long-lived (greater than 7.5 ns) fluorescence emissions in each of these complex materials. Results suggest that complementary use of the two non destructive techniques allows a better understanding of the main fluorophores responsible for the emission in shellac, and further provides means for distinguishing the main classes of other varnishes based on differences in fluorescence lifetime behaviour. Spectrofluorimetric data and time resolved spectra presented here may form the basis for the interpretation of results from future in situ fluorescence examination and time resolved fluorescence imaging of varnished musical instruments.

  11. Classification of aortic atherosclerotic lesions with time-resolved fluorescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Maarek, Jean-Michel I.; Marcu, Laura; Grundfest, Warren S.; Fishbein, Michael C.

    1999-07-01

    In this study, we examine the possibility of differentiating between classes of atherosclerotic lesions based on time- resolved fluorescence spectroscopy and we compare the performance of classification schemes that use either the time-resolved spectra or only the intensity spectra. Transient fluorescence emissions induced by pulsed nitrogen laser excitation was measured on 87 excised samples of human aorta. The samples were classified histologically using the AHA classification Predictor variables derived from the time-resolved spectra included the spectral intensities at 360-510 nm and parameters of a biexponential fit of the fluorescence impulse response function. Stepwise discriminant analysis using these predict variables showed that a few predictor variables sufficed to correctly classify 89 percent of the samples. Excluding the time- dependent decay and using only the spectral intensities, the percentage of correctly classified cases was significantly lower: 51 percent. These results establish that time- resolved fluorescence spectroscopy markedly improved on the performance of steady-state fluorescence spectroscopy for fine classification of atherosclerotic lesions.

  12. 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

  13. 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.

  14. [A method for time-resolved laser-induced breakdown spectroscopy measurement].

    PubMed

    Pan, Cong-Yuan; Han, Zhen-Yu; Li, Chao-Yang; Yu, Yun-Si; Wang, Sheng-Bo; Wang, Qiu-Ping

    2014-04-01

    Laser-Induced Breakdown Spectroscopy (LIBS) is strongly time related. Time-resolved LIBS measurement is an important technique for the research on laser induced plasma evolution and self-absorption of the emission lines. Concerning the temporal characteristics of LIBS spectrum, a method is proposed in the present paper which can achieve micros-scale time-resolved LIBS measurement by using general ms-scale detector. By setting different integration delay time of the ms-scale spectrum detector, a series of spectrum are recorded. And the integration delay time interval should be longer than the worst temporal precision. After baseline correction and spectrum fitting, the intensity of the character line was obtained. Calculating this intensity with differential method at a certain time interval and then the difference value is the time-resolved line intensity. Setting the plasma duration time as X-axis and the time-resolved line intensity as Y-axis, the evolution curve of the character line intensity can be plotted. Character line with overlap-free and smooth background should be a priority to be chosen for analysis. Using spectrometer with ms-scale integration time and a control system with temporal accuracy is 0.021 micros, experiments carried out. The results validate that this method can be used to characterize the evolution of LIBS characteristic lines and can reduce the cost of the time-resolved LIBS measurement system. This method makes high time-resolved LIBS spectrum measurement possible with cheaper system.

  15. 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

  16. The Chandra Survey of Outflows in AGN with Resolved Spectroscopy (SOARS)

    NASA Astrophysics Data System (ADS)

    Marshall, Herman; Evans, Daniel

    2012-07-01

    We present results from the Chandra SOARS (Survey Outflows in AGN with Resolved Spectroscopy) program, using spatially resolved Chandra High Energy Transmission Grating spectroscopy of the kpc-scale narrow line regions around some of our nearest AGN, including the Circinus Galaxy, NGC 1068, Mrk 3, and NGC 3393. We use the neutral and photoexcited lines measurable using the HETG Spectrometer to (1) measure the mass and energy imparted by the AGN outflow into its kpc-scale environment; and (2) create a full kinematic map of the galaxy, thereby directly constraining the extent of the outflow. Our results have key implications for the role of galactic-scale outflows in AGN as moderators of galaxy evolution

  17. 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.

  18. 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.

  19. Properties of Liquid Silicon Observed by Time-Resolved X-Ray Absorption Spectroscopy

    NASA Astrophysics Data System (ADS)

    Johnson, S. L.; Heimann, P. A.; Lindenberg, A. M.; Jeschke, H. O.; Garcia, M. E.; Chang, Z.; Lee, R. W.; Rehr, J. J.; Falcone, R. W.

    2003-10-01

    Time-resolved x-ray spectroscopy at the Si L edges is used to probe the electronic structure of an amorphous Si foil as it melts following absorption of an ultrafast laser pulse. Picosecond temporal resolution allows observation of the transient liquid phase before vaporization and before the liquid breaks up into droplets. The melting causes changes in the spectrum that match predictions of molecular dynamics and ab initio x-ray absorption codes.

  20. 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

  1. Time- and Angle-Resolved Photoemission Spectroscopy of Hydrated Electrons Near a Liquid Water Surface

    NASA Astrophysics Data System (ADS)

    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.

  2. 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).

  3. Microscopic particle discrimination using spatially-resolved Fourier-holographic light scattering angular spectroscopy

    NASA Astrophysics Data System (ADS)

    Hillman, Timothy R.; Alexandrov, Sergey A.; Gutzler, Thomas; Sampson, David D.

    2006-11-01

    We utilize Fourier-holographic light scattering angular spectroscopy to record the spatially resolved complex angular scattering spectra of samples over wide fields of view in a single or few image captures. Without resolving individual scatterers, we are able to generate spatially-resolved particle size maps for samples composed of spherical scatterers, by comparing generated spectra with Mie-theory predictions. We present a theoretical discussion of the fundamental principles of our technique and, in addition to the sphere samples, apply it experimentally to a biological sample which comprises red blood cells. Our method could possibly represent an efficient alternative to the time-consuming and laborious conventional procedure in light microscopy of image tiling and inspection, for the characterization of microscopic morphology over wide fields of view.

  4. Imaging electron dynamics with time- and angle-resolved photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Popova-Gorelova, Daria; Küpper, Jochen; Santra, Robin

    2016-07-01

    We theoretically study how time- and angle-resolved photoemission spectroscopy can be applied for imaging coherent electron dynamics in molecules. We consider a process in which a pump pulse triggers coherent electronic dynamics in a molecule by creating a valence electron hole. An ultrashort extreme ultraviolet probe pulse creates a second electron hole in the molecule. Information about the electron dynamics is accessed by analyzing angular distributions of photoemission probabilities at a fixed photoelectron energy. We demonstrate that a rigorous theoretical analysis, which takes into account the indistinguishability of transitions induced by the ultrashort, broadband probe pulse and electron hole correlation effects, is necessary for the interpretation of time- and angle-resolved photoelectron spectra. We show how a Fourier analysis of time- and angle-resolved photoelectron spectra from a molecule can be applied to follow its electron dynamics by considering photoelectron distributions from an indole molecular cation with coherent electron dynamics.

  5. 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.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-09-01

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

  8. 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.

  9. Kerr-gated time-resolved Raman spectroscopy of equine cortical bone tissue.

    PubMed

    Morris, Michael D; Matousek, Pavel; Towrie, Michael; Parker, Anthony W; Goodship, Allen E; Draper, Edward R C

    2005-01-01

    Picosecond time-resolved Raman spectroscopy in equine cortical bone tissue is demonstrated. Using 400-nm pulsed laser excitation (1 ps at 1 kHz) it is shown that Kerr cell gating with a 4-ps window provides simultaneously time-resolved rejection of fluorescence and time-resolved Raman scatter enabling depth profiling through tissue. The Raman shifts are the same as those observed by conventional cw Raman spectroscopy using deep-red or near-infrared lasers. The time decay of Raman photons is shown to fit an inverse square root of time function, suggesting propagation by a diffusive mechanism. Using polystyrene behind a bone specimen, it is shown that the 400-nm laser light penetrates at least 0.31 mm below the surface of a fully mineralized bone tissue specimen and generates observable bone Raman scatter (approximately 415 to 430 nm) through most of this depth. These novel results demonstrate great promise for in vivo applications for studying diseased bone tissue, and ways to optimize the setup are discussed.

  10. Validation of a time-resolved fluorescence spectroscopy apparatus in a rabbit atherosclerosis model

    NASA Astrophysics Data System (ADS)

    Fang, Qiyin; Jo, Javier A.; Papaioannou, Thanassis; Dorafshar, Amir; Reil, Todd; Qiao, Jian-Hua; Fishbein, Michael C.; Freischlag, Julie A.; Marcu, Laura

    2004-07-01

    Time-resolved laser-induced fluorescence spectroscopy (tr-LIFS) has been studied as a potential tool for in vivo diagnosis of atherosclerotic lesions. This study is to evaluate the potential of a compact fiber-optics based tr-LIFS instrument developed in our laboratory for in vivo analysis of atherosclerotic plaque composition. Time-resolved fluorescence spectroscopy studies were performed in vivo on fifteen New Zealand White rabbits (atherosclerotic: N=8, control: N=7). Time-resolved fluorescence spectra were acquired (range: 360-600 nm, increment: 5 nm, total acquisition time: 65 s) from normal aorta wall and lesions in the abdominal aorta. Data were analyzed in terms of fluorescence emission spectra and wavelength specific lifetimes. Following trichrome staining, tissue specimens were analyzed histopathologically in terms of intima/media thickness and biochemical composition (collagen, elastin, foam cells, and etc). Based on intimal thickness, the lesions were divided into thin and thick lesions. Each group was further separated into two categories: collagen rich lesions and foam cell rich lesions based on their biochemical composition. The obtained spectral and time domain fluorescence signatures were subsequently correlated to the histopathological findings. The results have shown that time-domain fluorescence spectral features can be used in vivo to separate atherosclerotic lesions from normal aorta wall as well discrimination within certain types of lesions.

  11. Implementation and evaluation of data analysis strategies for time-resolved optical spectroscopy.

    PubMed

    Slavov, Chavdar; Hartmann, Helvi; Wachtveitl, Josef

    2015-02-17

    Time-resolved optical spectroscopy plays a key role in illuminating the mechanisms of many fundamental processes in physics, chemistry, and biology. However, to extract the essential information from the highly complex time-resolved data, advanced data analysis techniques are required. Here we present the implementation strategies and the evaluation of the familiar global lifetime and target analysis as well as the not so widely adopted lifetime distribution analysis (LDA). Furthermore, we demonstrate the implementation of analysis strategies dealing with a number of artifacts inherently present in data from ultrafast optical experiments. The focus of the work is placed on LDA as it allows invaluable exploration depth of the kinetic information contained in the experimental data. We establish a clear regularization procedure for the use of LDA in ultrafast optical spectroscopy and evaluate the performance of a number of factors that play a role in the reliable reconstruction of lifetime distributions. Our results show that the optimal regularization factor can be determined well with the L-curve and the generalized cross-validation techniques. Moreover, the performance evaluations indicate that the most efficient regularization norm is the identity matrix. The analytical procedures described in this work can be readily implemented and used for the analysis of any time-resolved data.

  12. Time-resolved spatially offset Raman spectroscopy for depth analysis of diffusely scattering layers.

    PubMed

    Iping Petterson, Ingeborg E; Dvořák, Patrick; Buijs, Joost B; Gooijer, Cees; Ariese, Freek

    2010-12-01

    The objective of this study is to use time-resolved (TR) Raman spectroscopy, spatially offset Raman spectroscopy (SORS), and a combination of these approaches to obtain high quality Raman spectra from materials hidden underneath an opaque layer. Both TR Raman and SORS are advanced techniques that allow for an increased relative selectivity of photons from deeper layers within a sample. Time-resolved detection reduces fluorescence background, and the selectivity for the second layer is improved. By combining this with spatially offset excitation we additionally increased selectivity for deeper layers. Test samples were opaque white polymer blocks of several mm thicknesses. Excitation was carried out with a frequency-doubled Ti:sapphire laser at 460 nm, 3 ps pulse width and 76 MHz repetition rate. Detection was either with a continuous-wave CCD camera or in time-resolved mode using an intensified CCD camera with a 250 ps gate width. The Raman photons were collected in backscatter mode, with or without lateral offset. By measuring the delay of the Raman signal from the second layer (polyethylene terephthalate/PET/Arnite), the net photon migration speeds through Teflon, polythene, Delrin and Nylon were determined. Raman spectra could be obtained from a second layer of PET through Teflon layers up to 7 mm of thickness. The ability to obtain chemical information through layers of diffusely scattering materials has powerful potential for biomedical applications.

  13. 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

  14. Ultrafast Time-Resolved Hard X-Ray Emission Spectroscopy on a Tabletop

    NASA Astrophysics Data System (ADS)

    Miaja-Avila, Luis; O'Neil, Galen C.; Joe, Young I.; Alpert, Bradley K.; Damrauer, Niels H.; Doriese, William B.; Fatur, Steven M.; Fowler, Joseph W.; Hilton, Gene C.; Jimenez, Ralph; Reintsema, Carl D.; Schmidt, Daniel R.; Silverman, Kevin L.; Swetz, Daniel S.; Tatsuno, Hideyuki; Ullom, Joel N.

    2016-07-01

    Experimental tools capable of monitoring both atomic and electronic structure on ultrafast (femtosecond to picosecond) time scales are needed for investigating photophysical processes fundamental to light harvesting, photocatalysis, energy and data storage, and optical display technologies. Time-resolved hard x-ray (>3 keV ) spectroscopies have proven valuable for these measurements due to their elemental specificity and sensitivity to geometric and electronic structures. Here, we present the first tabletop apparatus capable of performing time-resolved x-ray emission spectroscopy. The time resolution of the apparatus is better than 6 ps. By combining a compact laser-driven plasma source with a highly efficient array of microcalorimeter x-ray detectors, we are able to observe photoinduced spin changes in an archetypal polypyridyl iron complex [Fe (2 ,2'-bipyridine)3]2 + and accurately measure the lifetime of the quintet spin state. Our results demonstrate that ultrafast hard x-ray emission spectroscopy is no longer confined to large facilities and now can be performed in conventional laboratories with 10 times better time resolution than at synchrotrons. Our results are enabled, in part, by a 100- to 1000-fold increase in x-ray collection efficiency compared to current techniques.

  15. 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.

  16. A method for resolving overlapped peaks in laser-induced breakdown spectroscopy (LIBS).

    PubMed

    Zhang, Bo; Yu, Haibin; Sun, Lanxiang; Xin, Yong; Cong, Zhibo

    2013-09-01

    Spectral peak overlapping is a basic problem in analytical data processing of laser-induced breakdown spectroscopy (LIBS). Curve fitting is the typical method of resolving overlapped peaks. For preventing ambiguous fitting, appropriate initial values must be known. The aim of this work was to present a method that could be used to determine appropriate initial values of the curve-fitting method by using fractional differential theory. According to the variation of characteristic points of Lorentzian peaks at different fractional differential orders, parameter estimators were obtained that were used to calculate the initial values of the curve-fitting method. As it is a widely used optimization method, the Levenberg-Marquardt method was used in curve fitting. Simulation and LIBS experimental results proved that the proposed method of the initial value estimation can effectively resolve the overlapped peaks in LIBS data processing.

  17. 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.

  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. Spatially resolved acoustic spectroscopy for rapid imaging of material microstructure and grain orientation

    NASA Astrophysics Data System (ADS)

    Smith, Richard J.; Li, Wenqi; Coulson, Jethro; Clark, Matt; Somekh, Michael G.; Sharples, Steve D.

    2014-05-01

    Measuring the grain structure of aerospace materials is very important to understand their mechanical properties and in-service performance. Spatially resolved acoustic spectroscopy is an acoustic technique utilizing surface acoustic waves to map the grain structure of a material. When combined with measurements in multiple acoustic propagation directions, the grain orientation can be obtained by fitting the velocity surface to a model. The new instrument presented here can take thousands of acoustic velocity measurements per second. The spatial and velocity resolution can be adjusted by simple modification to the system; this is discussed in detail by comparison of theoretical expectations with experimental data.

  20. Use of angle-resolved photoelectron spectroscopy in the study of autoionization in molecules

    SciTech Connect

    Carlson, T.A.

    1985-01-01

    A discussion is made of the types of information available from angle-resolved photoelectron spectroscopy coupled to synchrotron radiation that can be used to study the dynamics of autoionization in molecules. In particular, the importance is brought out of studying the changes in the angular distribution parameter, ..beta.., as one goes over an autoionization resonance. To illustrate this discussion, recent unpublished data are presented on N/sub 2/O, N/sub 2/, and HI, which have employed the CIS (constant ionic state) method to yield simultaneous cross sections and ..beta.. values over various regions of autoionization. 10 refs., 5 figs.

  1. Application of time-resolved luminescence spectroscopy to a remote uranyl sensor

    NASA Astrophysics Data System (ADS)

    Varineau, Pierre T.; Duesing, Richard W., Jr.; Wangen, Larry E.

    1992-03-01

    Time-resolved luminescence spectroscopy is an effective method for the determination of a wide range of uranyl concentrations in aqueous samples. We have applied this technique to the development of a remote-sensing device using fiber optic cables coupled with a microflow cell to probe for uranyl in aqueous samples. This sensor incorporates a Nafion membrane through which UO22+ can diffuse into a reaction/analysis chamber containing phosphoric acid, a reagent that enhances the uranyl luminescence intensity and lifetime. With this device, anionic and fluorescing organic interferences could be eliminated, allowing for the determination of uranyl over a concentration range of 10-4 to 10-9 M.

  2. 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.

  3. 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.

  4. Time-Resolved Mid-Infrared Frequency Comb Spectroscopy of Transient Radical Species

    NASA Astrophysics Data System (ADS)

    Bui, Thinh; Fleisher, Adam; Bjork, Bryce; Cossel, Kevin; Ye, Jun; Okumura, Michio; JILA Collaboration; California Institute Of Technology Collaboration

    2014-05-01

    Understanding chemical reactions require unambiguous determinations of reactant, intermediate, and product concentrations on time scales faster than the reaction rate. For high detection sensitivities, direct absorption spectroscopy in the mid-infrared can often be desirable due to strongly absorbing fundamental molecular vibrations. Here, we demonstrate time-resolved frequency comb spectroscopy (TRFCS), a mid-infrared broadband technique for the study of chemical reactions on the μs timescale, to measure an important transient free radicals species, hydroxyformyl radical trans-DOCO. Directly after photolysis of the chemical precursor acrylic acid-d1, we measure absolute trans-DOCO product concentrations as well as its subsequent loss with a time resolution of 25 μs. In addition to trans-DOCO product formation, we observed unexpected C-H bond fission channels in photoexcited acrylic acid.

  5. Time-resolved EUV photoelectron spectroscopy of dissociating I2 by laser harmonics at 80 nm.

    PubMed

    Fushitani, Mizuho; Matsuda, Akitaka; Hishikawa, Akiyoshi

    2011-05-01

    Generation of single-order laser harmonics in extreme ultraviolet (EUV) and the application to the time-resolved photoelectron spectroscopy of I(2) are demonstrated. The EUV pulses at 80 nm were generated from Kr as the 5th order harmonics of intense 400 nm laser pulses and then separated from other harmonic orders by a thin indium foil. The pump-probe photoelectron spectroscopy of I(2) in the B (3)Π(0(u)(+)) and B" (1)Π(1(u)) states excited by visible laser pulses at 490 nm showed a rapid increase in the yield of atomic iodine (~400 fs), reflecting the dissociation dynamics evolving simultaneously in the two excited states.

  6. 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.

  7. 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.

  8. 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.

  9. The analysis of time-resolved optical waveguide absorption spectroscopy based on positive matrix factorization.

    PubMed

    Liu, Ping; Li, Zhu; Li, Bo; Shi, Guolong; Li, Minqiang; Yu, Daoyang; Liu, Jinhuai

    2013-08-01

    Time-resolved optical waveguide absorption spectroscopy (OWAS) makes use of an evanescent field to detect the polarized absorption spectra of sub-monomolecular adlayers. This technique is suitable for the investigation of kinetics at the solid/liquid interface of dyes, pigments, fluorescent molecules, quantum dots, metallic nanoparticles, and proteins with chromophores. In this work, we demonstrate the application of positive matrix factorization (PMF) to analyze time-resolved OWAS for the first time. Meanwhile, PCA is researched to compare with PMF. The absorption/desorption kinetics of Rhodamine 6G (R6G) onto a hydrophilic glass surface and the dynamic process of Meisenheimer complex between Cysteine and TNT are selected as samples to verify experimental system and analytical methods. The results are shown that time-resolved OWAS can well record the absorption/desorption of R6G onto a hydrophilic glass surface and the dynamic formation process of Meisenheimer complexes. The feature of OWAS extracted by PMF is dynamic and consistent with the results analyzed by the traditional function of time/wavelength-absorbance. Moreover, PMF prevents the negative factors from occurring, avoids contradicting physical reality, and makes factors more easily interpretable. Therefore, we believe that PMF will provide a valuable analysis route to allow processing of increasingly large and complex data sets.

  10. 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

  11. 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.

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

    PubMed

    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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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

  18. 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).

  19. 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

  20. 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.

  1. 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.

  2. Imaging buried organic islands by spatially resolved ballistic electron emission spectroscopy.

    PubMed

    Goh, Kuan Eng J; Bannani, A; Troadec, C

    2008-11-01

    The well-known Au/n-Si(111) Schottky interface is modified by a discontinuous pentacene film (∼1.5 nm thick) and studied using spatially resolved ballistic electron emission spectroscopy (BEES). The pentacene film introduced subtle changes to the interface which cannot be definitively detected by current-voltage measurements or a standard BEES analysis of the barrier height. In contrast, analyzing the BEES results in a dual-parameter (transmission attenuation and barrier height) space allows the effect of the pentacene film on the Au/n-Si(111) interface to be clearly demonstrated. We found that the pentacene film behaves like a tunneling barrier and increases the distribution of local barrier heights with a tendency toward lower values. Our results highlight the potential of the dual-parameter BEES analysis for understanding local interface modification by molecules.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Electronic structure of MgB2 from angle-resolved photoemission spectroscopy.

    PubMed

    Uchiyama, H; Shen, K M; Lee, S; Damascelli, A; Lu, D H; Feng, D L; Shen, Z-X; Tajima, S

    2002-04-15

    The first angle-resolved photoemission spectroscopy results from MgB2 single crystals are reported. Along the GammaK and GammaM directions, we observed three distinct dispersive features approaching the Fermi energy. These can be assigned to the theoretically predicted sigma (B 2p(x,y)) and pi (B 2p(z)) bands. In addition, a small parabolic-like band is detected around the Gamma point, which can be attributed to a surface-derived state. The overall agreement between our results and the band calculations suggests that the electronic structure of MgB2 is of a conventional nature, thus implying that electron correlations are weak and may be of little importance to superconductivity in this system.

  8. 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.

  9. 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.

  10. 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.

  11. Time-resolved laser fluorescence spectroscopy of UO2(CO3)3(4-).

    PubMed

    Jung, E C; Cho, H-R; Baik, M H; Kim, H; Cha, W

    2015-11-21

    The objective of the present study is to examine the luminescence characteristics of UO2(CO3)3(4-) in detail using time-resolved laser fluorescence spectroscopy. The peak wavelengths and lifetime of UO2(CO3)3(4-) were determined at room temperature using the two excitation laser wavelengths of 266 and 448 nm. The peak wavelengths in the luminescence spectrum exhibited hypsochromic shifts compared with those of UO2(2+). The lifetime determined from several samples containing various uranium concentrations was 8.9 ± 0.8 ns. Explanations for the hindrance to the observation of the luminescence spectrum of UO2(CO3)3(4-) in previous investigations are discussed. The representative experimental parameters, which might interrupt the measurement of weak luminescence, are the insertion delay time of the detection device, the overlapped luminescence of the background materials and the primary inner filter effect in the sample solution.

  12. Study of nanosecond laser-produced plasmas in atmosphere by spatially resolved optical emission spectroscopy

    SciTech Connect

    Wei, Wenfu; Wu, Jian; Li, Xingwen; Jia, Shenli; Qiu, Aici

    2013-09-21

    We investigate the evolution of the species from both the target and the air, and the plasma parameter distribution of the nanosecond laser-produced plasmas in atmospheric air. The technique used is spatially resolved optical emission spectroscopy. It is argued that the N II from the air, which is distributed over a wider region than the target species in the early stages of the discharge, is primarily formed by the shock wave. The ionized species have a larger expansion velocity than the excited atoms in the first ∼100 ns, providing direct evidence for space-charge effects. The electron density decreases with the distance from the target surface in the early stages of the discharge, and both the electron density and the excited temperature variation in the axial direction are found to become insignificant at later stages.

  13. 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.

  14. Angle resolved photo-emission spectroscopy signature of the resonant excitonic state

    NASA Astrophysics Data System (ADS)

    Montiel, X.; Kloss, T.; Pépin, C.

    2016-09-01

    We calculate the angle resolved photo-emission spectroscopy (ARPES) signature of the resonant excitonic state (RES) that was proposed as the pseudo-gap state of cuprate superconductors (Kloss T. et al., arXiv:1510.03038 (2015)). This new state can be described as a set of excitonic (particle-hole) patches with an internal checkerboard modulation. Here, we modelize the RES as a charge order with 2\\textbf{p}F wave vectors, where 2\\textbf{p}F is the ordering vector connecting two opposite sides of the Fermi surface. We calculate the spectral weight and the density of states in the RES and we find that our model correctly reproduces the opening of the PG in Bi-2201.

  15. 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

  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. Time-resolved laser fluorescence spectroscopy of UO2(CO3)3(4-).

    PubMed

    Jung, E C; Cho, H-R; Baik, M H; Kim, H; Cha, W

    2015-11-21

    The objective of the present study is to examine the luminescence characteristics of UO2(CO3)3(4-) in detail using time-resolved laser fluorescence spectroscopy. The peak wavelengths and lifetime of UO2(CO3)3(4-) were determined at room temperature using the two excitation laser wavelengths of 266 and 448 nm. The peak wavelengths in the luminescence spectrum exhibited hypsochromic shifts compared with those of UO2(2+). The lifetime determined from several samples containing various uranium concentrations was 8.9 ± 0.8 ns. Explanations for the hindrance to the observation of the luminescence spectrum of UO2(CO3)3(4-) in previous investigations are discussed. The representative experimental parameters, which might interrupt the measurement of weak luminescence, are the insertion delay time of the detection device, the overlapped luminescence of the background materials and the primary inner filter effect in the sample solution. PMID:26460936

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

    PubMed Central

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

    2014-01-01

    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

  19. 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

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

    PubMed

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

    2014-03-01

    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 lifetime

  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

    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

  3. 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

  4. 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.

  5. 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

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

    NASA Astrophysics Data System (ADS)

    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.

  7. Spatially resolved electron energy loss spectroscopy of crescent-shaped plasmonic antennas.

    PubMed

    Křápek, V; Koh, A L; Břínek, L; Hrtoň, M; Tomanec, O; Kalousek, R; Maier, S A; Šikola, T

    2015-05-01

    We present a study of the optical properties of gold crescent-shaped antennas by means of electron energy loss spectroscopy. These structures exhibit particularly large field enhancement near their sharp features, support two non-degenerate dipolar (i.e., optically active) localised surface plasmon resonances, and are widely tunable by a choice of their shape and dimensions. Depending on the volume and shape, we resolved up to four plasmon resonances in metallic structures under study in the energy range of 0.8 - 2.4 eV: two dipolar and quadrupolar mode and a multimodal assembly. The boundary-element-method calculations reproduced the observed spectra and helped to identify the character of the resonances. The two lowest modes are of particular importance owing to their dipolar nature. Remarkably, they are both concentrated near the tips of the crescent, spectrally well resolved and their energies can be tuned between 0.8 - 1.5 eV and 1.2 - 2.0 eV, respectively. As the lower spectral range covers the telecommunication wavelengths 1.30 and 1.55 μm, we envisage the possible use of such nanostructures in infrared communication technology.

  8. Optimizing the sensitivity of photoluminescent probes using time-resolved spectroscopy: a molecular beacon case study.

    PubMed

    Huang, Kewei; Martí, Angel A

    2012-09-18

    Improving probes so that they can perform more sensitive and accurate detections is at the heart of much fundamental and applied research. Within the past few years a considerable amount of effort has been devoted to the study of photoluminescent probes in combination with time-resolved photoluminescence spectroscopy (TRPS). Although TRPS is a powerful and important technique for improving the sensitivity of long-lived probes, there is a lack of a general methodology that would allow one to unambiguously optimize the parameter affecting this technique. In this manuscript it will be shown how parameters that are probe- and technique-specific can affect the effectiveness of TRPS in improving sensitivity. Furthermore, it will be demonstrated that, when TRPS is used, the sensitivity of the probe is strongly dependent on the time window used to generate the time-resolved emission spectra (TRES). A method will be described that will allow one to remove the uncertainty in the selection of the time window that would yield the optimum improvement in probe performance, as well as the experimental parameters that need to be considered. Molecular beacon probes (MBs) were used to demonstrate these points. These probes show signal-to-background ratios (S/B) of less than 9 when SSPS is used, which can be easily enhanced to 17 using TRPS. The detection limits were also improved when TRPS is used allowing detecting target DNA with concentrations as low as 13.6 nM.

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

    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.

  11. 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.

  12. Spectrally resolved measurement of small optical losses by cavity enhanced spectroscopy techniques

    NASA Astrophysics Data System (ADS)

    Zeuner, T.; Paa, W.; Schmidl, G.; Mühlig, Ch.

    2011-05-01

    In general losses of optical of less than 1 % cannot be measured precisely with the best-established techniques (e.q. two-beam spectroscopy). However, it is possible to measure losses in the 0.0001 - 0.5 % range with high accuracy using cavity enhanced spectroscopy (CES) methods. Such low losses can be measured with CES, due to an increased interaction path way with the object. The Cavity Ring-Down (CRD) technique takes advantage of the CES method and transforms the optical loss information into the time domain. Two types of CRD setups for spectrally resolved loss measurement of laser mirrors will be presented. The first setup uses a tunable laser system for serial detection of the reflectivity spectra. The second method determines the spectral losses using a super continuum source. Here, simultaneous excitation and a spectrometer based camera system for separate detection of several wavelengths is used. Results will be shown and compared with direct absorption measurements of the same sample.

  13. 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.

  14. 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.

  15. SPATIALLY RESOLVED SPECTROSCOPY OF THE GLOBULAR CLUSTER RZ 2109 AND THE NATURE OF ITS BLACK HOLE

    SciTech Connect

    Peacock, Mark B.; Zepf, Stephen E.; Kundu, Arunav; Maccarone, Thomas J.; Rhode, Katherine L.; Salzer, John J.; Waters, Christopher Z.; Ciardullo, Robin; Gronwall, Caryl; Stern, Daniel

    2012-11-10

    We present optical Hubble Space Telescope/Space Telescope Imaging Spectrograph (HST/STIS) spectroscopy of RZ 2109, a globular cluster (GC) in the elliptical galaxy NGC 4472. This GC is notable for hosting an ultraluminous X-ray source as well as associated strong and broad [O III] {lambda}{lambda}4959, 5007 emission. We show that the HST/STIS spectroscopy spatially resolves the [O III] emission in RZ 2109. While we are unable to make a precise determination of the morphology of the emission-line nebula, the best-fitting models all require that the [O III] {lambda}5007 emission has a half-light radius in the range 3-7 pc. The extended nature of the [O III] {lambda}5007 emission is inconsistent with published models that invoke an intermediate-mass black hole origin. It is also inconsistent with the ionization of ejecta from a nova in the cluster. The spatial scale of the nebula could be produced via the photoionization of a strong wind driven from a stellar mass black hole accreting at roughly its Eddington rate.

  16. 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

  17. Time resolved metal line profile by near-ultraviolet tunable diode laser absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Vitelaru, C.; de Poucques, L.; Minea, T. M.; Popa, G.

    2011-03-01

    Pulsed systems are extensively used to produce active species such as atoms, radicals, excited states, etc. The tunable diode laser absorption spectroscopy (TD-LAS) is successfully used to quantify the density of absorbing species, but especially for stationary or slow changing systems. The time resolved-direct absorption profile (TR-DAP) measurement method by TD-LAS, with time resolution of μs is proposed here as an extension of the regular use of diode laser absorption spectroscopy. The spectral narrowness of laser diodes, especially in the blue range (˜0.01 pm), combined with the nanosecond fast trigger of the magnetron pulsed plasma and long trace recording on the oscilloscope (period of second scale) permit the detection of the sputtered titanium metal evolution in the afterglow (˜ms). TR-DAP method can follow the time-dependence of the temperature (Doppler profile) and the density (deduced from the absorbance) of any medium and heavy species in a pulsed system.

  18. 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

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. High-Resolution Two-Dimensional J-Resolved NMR Spectroscopy for Biological Systems

    PubMed Central

    Huang, Yuqing; Cai, Shuhui; Zhang, Zhiyong; Chen, Zhong

    2014-01-01

    NMR spectroscopy is a principal tool in metabolomic studies and can, in theory, yield atom-level information critical for understanding biological systems. Nevertheless, NMR investigations on biological tissues generally have to contend with field inhomogeneities originating from variations in macroscopic magnetic susceptibility; these field inhomogeneities broaden spectral lines and thereby obscure metabolite signals. The congestion in one-dimensional NMR spectra of biological tissues often leads to ambiguities in metabolite identification and quantification. We propose an NMR approach based on intermolecular double-quantum coherences to recover high-resolution two-dimensional (2D) J-resolved spectra from inhomogeneous magnetic fields, such as those created by susceptibility variations in intact biological tissues. The proposed method makes it possible to acquire high-resolution 2D J-resolved spectra on intact biological samples without recourse to time-consuming shimming procedures or the use of specialized hardware, such as magic-angle-spinning probes. Separation of chemical shifts and J couplings along two distinct dimensions is achieved, which reduces spectral crowding and increases metabolite specificity. Moreover, the apparent J coupling constants observed are magnified by a factor of 3, facilitating the accurate measurement of small J couplings, which is useful in metabolic analyses. Dramatically improved spectral resolution is demonstrated in our applications of the technique on pig brain tissues. The resulting spectra contain a wealth of chemical shift and J-coupling information that is invaluable for metabolite analyses. A spatially localized experiment applied on an intact fish (Crossocheilus siamensis) reveals the promise of the proposed method in in vivo metabolite studies. Moreover, the proposed method makes few demands on spectrometer hardware and therefore constitutes a convenient and effective manner for metabonomics study of biological systems

  5. 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

  6. 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

  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.

  8. 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.

  9. 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

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

    NASA Astrophysics Data System (ADS)

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

    2000-06-01

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

  11. 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

  12. Two-dimensional proton J-resolved NMR spectroscopy of neomycin B

    SciTech Connect

    Botto, R.E.; Coxon, B.

    1984-01-01

    The /sup 1/H NMR spectrum of a solution of neomycin B free base (Structure 1) in D/sub 2/O has been assigned completely by two-dimensional, homonuclear J-resolved NMR spectroscopy and spin decoupling at 400 MHz. Proton chemical shifts and proton-proton couplings are reported for all glycoside residues in neomycin B along with their computer simulated spectra. The /sup 4/C/sub 1/ chair conformation has been assigned to the 2,6-diamino-2,6-dideoxy-..beta..-L-idopyranosyl (ring D) portion of the antibiotic (1b) by analysis of the proton coupling constants and chemical shifts. The ..beta..-furanose form of the ribosyl portion (ring C) has been assigned. Vicinal proton couplings for the 2-deoxystreptaminyl group (ring B) are consistent with a chair conformation in which all ring substituents are equatorial, and proton chemical shift assignments are based on protonation studies. A computer simulated composite of the individual calculated spectra is presented for comparison with the experimental spectrum of neomycin B. 30 references, 5 figures, 3 tables.

  13. 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.

  14. Velocity distribution function of sputtered Cu atoms obtained by time resolved optical absorption spectroscopy

    SciTech Connect

    Kang, Namjun; Gaboriau, Freddy; Ricard, Andre; Oh, Soo-ghee

    2010-01-15

    A new method based on time resolved optical absorption spectroscopy is proposed to determine the velocity distribution function of sputtered Cu atoms in a magnetron plasma discharge. The method consists of applying a short pulse of 1.5 {mu}s and of recording time variations in copper atom density in off pulse at different positions (1, 2, and 3 cm) from target surface under 3-30 mTorr. The time evolution of the density is then converted into velocity distribution. We estimate that only sputtered atoms with radial velocity component lower than 0.5 km/s are detected. The average velocity of Cu atoms is evaluated as the first order moment of the velocity distribution functions. The velocity distribution functions become the more dispersive the farther from target surface. The average velocities vary in the range of 2.5-3 km/s at the vicinity of target surface whereas at 3 cm a decrease from 2.5 to 1.2 km/s is observed at 30 mTorr.

  15. 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.

  16. 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

  17. 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

  18. [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.

  19. Conductivity of ZnO nanowires, nanoparticles, and thin films using time-resolved terahertz spectroscopy.

    PubMed

    Baxter, Jason B; Schmuttenmaer, Charles A

    2006-12-21

    The terahertz absorption coefficient, index of refraction, and conductivity of nanostructured ZnO have been determined using time-resolved terahertz spectroscopy, a noncontact optical probe. ZnO properties were measured directly for thin films and were extracted from measurements of nanowire arrays and mesoporous nanoparticle films by applying Bruggeman effective medium theory to the composite samples. Annealing significantly reduces the intrinsic carrier concentration in the ZnO films and nanowires, which were grown by chemical bath deposition. The complex-valued, frequency-dependent photoconductivities for all morphologies were found to be similar at short pump-probe delay times. Fits using the Drude-Smith model show that films have the highest mobility, followed by nanowires and then nanoparticles, and that annealing the ZnO increases its mobility. Time constants for decay of photoinjected electron density in films are twice as long as those in nanowires and more than 5 times those for nanoparticles due to increased electron interaction with interfaces and grain boundaries in the smaller-grained materials. Implications for electron transport in dye-sensitized solar cells are discussed.

  20. 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

  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. 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.

  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.

  4. Applications of time-resolved laser fluorescence spectroscopy to the environmental biogeochemistry of actinides.

    PubMed

    Collins, Richard N; Saito, Takumi; Aoyagi, Noboru; Payne, Timothy E; Kimura, Takaumi; Waite, T David

    2011-01-01

    Time-resolved laser fluorescence spectroscopy (TRLFS) is a useful means of identifying certain actinide species resulting from various biogeochemical processes. In general, TRLFS differentiates chemical species of a fluorescent metal ion through analysis of different excitation and emission spectra and decay lifetimes. Although this spectroscopic technique has largely been applied to the analysis of actinide and lanthanide ions having fluorescence decay lifetimes on the order of microseconds, such as UO , Cm, and Eu, continuing development of ultra-fast and cryogenic TRLFS systems offers the possibility to obtain speciation information on metal ions having room-temperature fluorescence decay lifetimes on the order of nanoseconds to picoseconds. The main advantage of TRLFS over other advanced spectroscopic techniques is the ability to determine in situ metal speciation at environmentally relevant micromolar to picomolar concentrations. In the context of environmental biogeochemistry, TRLFS has principally been applied to studies of (i) metal speciation in aqueous and solid phases and (ii) the coordination environment of metal ions sorbed to mineral and bacterial surfaces. In this review, the principles of TRLFS are described, and the literature reporting the application of this methodology to the speciation of actinides in systems of biogeochemical interest is assessed. Significant developments in TRLFS methodology and advanced data analysis are highlighted, and we outline how these developments have the potential to further our mechanistic understanding of actinide biogeochemistry.

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

    PubMed

    Adámek, P; Olejníček, J; Čada, M; Kment, Š; Hubička, Z

    2013-07-15

    A method for time-resolved tunable diode laser absorption spectroscopy (LAS) has been developed. In this Letter, we describe in detail a developed electronic module that controls the time resolution of the LAS system. The transistor-transistor logic signal triggering the plasma pulse is used for generation of two signals: the first one triggers fine tuning of the laser wavelength and the second one controls time-defined signal sampling from the absorption detector. The described method and electronic system enable investigation of the temporal evolution of the density and temperature of selected particles in technological plasma systems. The high-power impulse magnetron sputtering system with a period of 10 ms and a duty cycle of 1% has been used to verify this method. The temporal evolution of argon metastable density was measured in the active part of the pulse and in the afterglow. The resulting density of Ar* displays a double-peak structure with a first peak in the plasma "ON" phase and a second peak in the afterglow approximately 1 ms after the end of the pulse.

  6. Characterization of powellite-based solid solutions by site-selective time resolved laser fluorescence spectroscopy.

    PubMed

    Schmidt, Moritz; Heck, Stephanie; Bosbach, Dirk; Ganschow, Steffen; Walther, Clemens; Stumpf, Thorsten

    2013-06-21

    We present a comprehensive study of the solid solution system Ca2(MoO4)2-NaGd(MoO4)2 on the molecular scale, by means of site-selective time resolved laser fluorescence spectroscopy (TRLFS). Eu(3+) is used as a trace fluorescent probe, homogeneously substituting for Gd(3+) in the solid solution crystal structure. Site-selective TRLFS of a series of polycrystalline samples covering the whole composition range of the solid solution series from 10% substitution of Ca(2+) to the NaGd end-member reveals it to be homogeneous throughout the whole range. The trivalent ions are incorporated into the powellite structure in only one coordination environment, which exhibits a very strong ligand-metal interaction. Polarization-dependent measurements of a single crystal of NaGd(Eu)(MoO4)2 identify the coordination geometry to be of C2v point symmetry. The S4 symmetry of the Ca site within the powellite lattice can be transformed into C2v assuming minor motion in the first coordination sphere.

  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. 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).

  9. 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.

  10. 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

  11. 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.

  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. Monitoring brain temperature by time-resolved near-infrared spectroscopy: pilot study

    NASA Astrophysics Data System (ADS)

    Bakhsheshi, Mohammad Fazel; Diop, Mamadou; St. Lawrence, Keith; Lee, Ting-Yim

    2014-05-01

    Mild hypothermia (HT) is an effective neuroprotective strategy for a variety of acute brain injuries. However, the wide clinical adaptation of HT has been hampered by the lack of a reliable noninvasive method for measuring brain temperature, since core measurements have been shown to not always reflect brain temperature. The goal of this work was to develop a noninvasive optical technique for measuring brain temperature that exploits both the temperature dependency of water absorption and the high concentration of water in brain (80%-90%). Specifically, we demonstrate the potential of time-resolved near-infrared spectroscopy (TR-NIRS) to measure temperature in tissue-mimicking phantoms (in vitro) and deep brain tissue (in vivo) during heating and cooling, respectively. For deep brain tissue temperature monitoring, experiments were conducted on newborn piglets wherein hypothermia was induced by gradual whole body cooling. Brain temperature was concomitantly measured by TR-NIRS and a thermocouple probe implanted in the brain. Our proposed TR-NIRS method was able to measure the temperature of tissue-mimicking phantoms and brain tissues with a correlation of 0.82 and 0.66 to temperature measured with a thermometer, respectively. The mean difference between the TR-NIRS and thermometer measurements was 0.15°C±1.1°C for the in vitro experiments and 0.5°C±1.6°C for the in vivo measurements.

  14. 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.

  15. Multiple regimes of carrier cooling in photoexcited graphene probed by time-resolved terahertz spectroscopy

    NASA Astrophysics Data System (ADS)

    Frenzel, A. J.; Gabor, N. M.; Herring, P. K.; Fang, W.; Kong, J.; Jarillo-Herrero, P.; Gedik, N.

    2013-03-01

    Energy relaxation and cooling of photoexcited charge carriers in graphene has recently attracted significant attention due to possible hot carrier effects, large quantum efficiencies, and photovoltaic applications. However, the details of these processes remain poorly understood, with many conflicting interpretations reported. Here we use time-resolved terahertz spectroscopy to explore multiple relaxation and cooling regimes in graphene in order to elucidate the fundamental physical processes which occur upon photoexcitation of charge carriers. We observe a novel negative terahertz photoconductivity that results from the unique linear dispersion and allows us to measure the electron temperature with ultrafast time resolution. Additionally, we present measurements of the relaxation dynamics over a wide range of excitation fluence. By varying the pump photon energy, we demonstrate that cooling dynamics of photoexcited carriers depend on the amount of energy deposited in the graphene system by the pump pulse, not the number of absorbed photons. The data suggest that fundamentally different regimes are encountered for different excitation fluences. These results may provide a unifying framework for reconciling various measurements of energy relaxation and cooling in graphene.

  16. 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

  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. Measurement of the optical properties of rat brain tissue using contact spatially resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Gysbrechts, Barbara; Nguyen Do Trong, Nghia; Wang, Ling; Cabral, Henrique; Navratilova, Zaneta; Battaglia, Francesco P.; Saeys, Wouter; Bartic, Carmen

    2014-05-01

    Nowadays, biophotonics is widely used in neuroscience. The effectiveness of biophotonic techniques, such as fluorescence imaging and optogenetics, is affected by the optical properties of the examined tissue. Therefore, knowledge of these properties is essential to carefully plan experiments. Mice and rats are widely used in neuroscience studies. However, reports about optical properties of their brains are very rare. We measured optical absorption μa and reduced scattering μ's coefficients of native rat brain in the visible and near-infrared wavelength region, using contact spatially resolved spectroscopy (SRS). In this study, we estimate μa and μ's for the rat cortex and discuss their stability in time. Additionally, variations in optical properties within and between samples were characterized. The results extend the range of known optical properties for the rat cortex, especially in the visible range, relevant to optogenetics. μa and μ's are stable within a time span of four hours, and show low variation in and between brain samples. This indicates that a suitable protocol was used to estimate optical properties of rodent brain tissue. Since contact SRS is a non-destructive method, this technique could be used also to measure μa and μ's in living animals. Moreover, the probe has small dimensions, allowing the characterization of optical properties in different structures of the brain.

  19. 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.

  20. 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

  1. Spatially resolved scanning tunneling spectroscopy of single-layer steps on Si(100) surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Xiqiao; Namboodiri, Pradeep; Li, Kai; Deng, Xiao; Silver, Richard

    2016-09-01

    Single-layer steps at Si(100) surfaces/interfaces present significant challenges to the quantitative characterization of buried dopant devices as well as the accurate imaging and relocation of fabricated quantum structures. We demonstrate the detailed spatially resolved scanning tunneling spectroscopy study across monolayer step edges on Si(100) surfaces and quantitative determination of the local density of state distributions and behavior of the band gap at step edges. The influence on the local electrostatic environment due to step edge states has been quantified while accounting for the effects of scanning tunneling measurement conditions. The dangling bond states on Si(100) surfaces are utilized as a fingerprint to quantify the local band bending landscape and to make corrections to the experimentally observed surface state energy levels and band gap values at the step edge regions. We observe a significant band gap narrowing behavior along a rebonded single-layer type B step edge on a degenerately boron-doped p -type Si substrate.

  2. 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.

  3. 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

  4. 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

  5. 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

  6. Direct angle resolved photoemission spectroscopy and superconductivity of strained high-Tc films

    NASA Astrophysics Data System (ADS)

    Pavuna, Davor; Ariosa, Daniel; Cloetta, Dominique; Cancellieri, Claudia; Abrecht, Mike

    2008-02-01

    Since 1997 we systematically perform direct angle resolved photoemission spectroscopy (ARPES) on in-situ grown thin (<30 nm) cuprate films. Specifically, we probe low-energy electronic structure and properties of high-T_{c} superconductors (HTSC) under different degrees of epitaxial ({compressive vs. tensile}) strain. In overdoped and underdoped in-plane compressed (the strain is induced by the choice of substrate) ≈15 nm thin La_{2-x}Sr_{x}CuO_{4} (LSCO) films we almost double T_{c} to 40 K, from 20 K and 24 K, respectively. Yet the Fermi surface (FS) remains essentially two-dimensional. In contrast, ARPES data under {tensile} strain exhibit the dispersion that is three-dimensional, yet T_{c} drastically decreases. It seems that the in-plane compressive strain tends to push the apical oxygen far away from the CuO_{2} plane, enhances the two-dimensional character of the dispersion and increases T_{c}, while the tensile strain acts in the opposite direction and the resulting dispersion is three-dimensional. We have established the shape of the FS for both cases, and all our data are consistent with other ongoing studies, like EXAFS. As the actual lattice of cuprates is like a `Napoleon-cake', i.e. rigid CuO_{2 } planes alternating with softer `reservoir', that distort differently under strain, our data rule out all oversimplified two-dimensional (rigid lattice) mean field models. The work is still in progress on optimized La-doped Bi-2201 films with enhanced T_{c}.

  7. Time-resolved stand-off UV-Raman spectroscopy for planetary exploration

    NASA Astrophysics Data System (ADS)

    Skulinova, M.; Lefebvre, C.; Sobron, P.; Eshelman, E.; Daly, M.; Gravel, J.-F.; Cormier, J.-F.; Châteauneuf, F.; Slater, G.; Zheng, W.; Koujelev, A.; Léveillé, R.

    2014-03-01

    The exploration of Mars, Europa and Enceladus has provided evidence that support the existence of present or past potentially habitable environments, which may shelter signatures of extinct or extant life. A search for further evidence for habitability or for life requires the development of sophisticated instruments and techniques that enable detailed investigations of locations, which are of great interest to planetary scientists and astrobiologists. Raman spectroscopy is a powerful and versatile technique; a rover based Raman Laser Spectrometer (RLS) operating at 532 nm excitation wavelength has been selected for the 2018 ExoMars mission. In this study, we demonstrate the feasibility of the utilisation of a time-resolved stand-off UV-Raman prototype for the detection and identification of pure organics, organics mixed in a quartz matrix and minerals that have been selected based on their potential relevance to astrobiology and planetary exploration. The samples of organics (β-carotene, L-ascorbic acid, thiamine hydrochloride, L-alanine, L-serine, thymine), carbonates (calcite, dolomite), sulfates (gypsum), silicates (quartz), and natural rock (an altered meta-volcanic rock featuring quartz inclusions) were analyzed at a distance of 6 m using a 355 nm excitation source and a gated intensified charged-coupled device (ICCD) as the detector. We were able to obtain spectra with clear Raman signals enabling unequivocal identification of all selected samples. We assert for the first time, that such an instrument can effectively identify minerals and a wide range of organics that may serve as geo- and biomarkers thus showing great potential for the exploration of planets and astrobiology.

  8. 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.

  9. Molecular orbital imaging of the acetone S2 excited state using time-resolved (e, 2e) electron momentum spectroscopy.

    PubMed

    Yamazaki, Masakazu; Oishi, Keiya; Nakazawa, Hiroyuki; Zhu, Chaoyuan; Takahashi, Masahiko

    2015-03-13

    We report a time-resolved (e, 2e) experiment on the deuterated acetone molecule in the S2 Rydberg state with a lifetime of 13.5 ps. The acetone S2 state was prepared by a 195 nm pump laser and probed with electron momentum spectroscopy using a 1.2 keV incident electron beam of 1 ps temporal width. In spite of the low data statistics as well as of the limited time resolution (±35  ps) due to velocity mismatch, the experimental results clearly demonstrate that electron momentum spectroscopy measurements of short-lived transient species are feasible, opening the door to time-resolved orbital imaging in momentum space.

  10. Early Results from the VENGA Integral Field Spectroscopy Survey: Current and Past Spatially-Resolved Star Formation in NGC2903

    NASA Astrophysics Data System (ADS)

    Song, Mimi; Gebhardt, K.; Jogee, S.; VENGA

    2012-01-01

    We present spatially-resolved integral field spectroscopy of the nearby isolated spiral galaxy NGC 2903 from the VIRUS-P Exploration of Nearby Spiral Galaxies (VENGA) survey. Among science goals that the survey aims at, here we focus on its star formation activity, stellar population modeling and constraining its star formation history. We acknowledge support from the Norman Hackerman Advanced Research Program (NHARP) ARP-03658-0234-2009.

  11. 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.

  12. Synchrotron-based rotationally resolved high-resolution FTIR spectroscopy of azulene and the unidentified infrared bands of astronomy.

    PubMed

    Albert, Sieghard; Lerch, Philippe; Quack, Martin

    2013-10-01

    Chasing the unidentified IR bands: The first rotationally resolved high-resolution infrared spectrum of azulene is reported using synchrotron Fourier transform infrared spectroscopy including a rovibrational analysis of the out-of-plane fundamental ν44. Comparison of azulene, naphthalene, indole, and biphenyl infrared bands leads to coincidences with UIR bands at 12.8 μm with naphthalene and at 13.55 and 14.6 μm with biphenyl bands, but excluding azulene as a strong absorber.

  13. High-pressure-low-temperature cryostat designed for use with fourier transform infrared spectrometers and time-resolved infrared spectroscopy.

    PubMed

    Calladine, James A; Love, Ashley; Fields, Peter A; Wilson, Richard G M; George, Michael W

    2014-01-01

    The design for a new high-pressure-low-temperature infrared (IR) cell for performing experiments using conventional Fourier transform infrared or fast laser-based time-resolved infrared spectroscopy, in a range of solvents, is described. The design builds upon a commercially available compressor and cold end (Polycold PCC(®) and CryoTiger(®)), which enables almost vibration-free operation, ideal for use with sensitive instrumentation. The design of our cell and cryostat allows for the study of systems at temperatures from 77 to 310 K and at pressures up to 250 bar. The CaF2 windows pass light from the mid-IR to the ultraviolet (UV), enabling a number of experiments to be performed, such as Raman, UV-visible absorption spectroscopy, and time-resolved techniques where sample excitation/probing using continuous wave or pulsed lasers is required. We demonstrate the capabilities of this cell by detailing two different applications: (i) the reactivity of a range of Group V-VII organometallic alkane complexes using time-resolved spectroscopy on the millisecond timescale and (ii) the gas-to-liquid phase transition of CO2 at low temperature, which is applicable to measurements associated with transportation issues related to carbon capture and storage.

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

    PubMed

    Fujimori, Shin-ichi

    2016-04-20

    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 eV) or high-energy synchrotron radiations (hν >/~ 400 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 CeMIn5(M = Rh, Ir, and Co) and YbRh2Si2 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 U5f compounds such as UFeGa5, their electronic structures can be well-described by the band-structure calculation assuming that all U5f electrons are itinerant. In contrast, the band structures of localized U5f compounds such as UPd3 and UO2 are essentially explained by the localized model that treats U5f electrons as localized core states. In regards to heavy fermion U-based compounds such as the hidden-order compound URu2Si2, their electronic structures exhibit complex behaviors. Their overall band structures are generally well-explained by the band-structure calculation, whereas the states in the vicinity of EF show some deviations due to electron correlation effects. Furthermore, the electronic structures of URu2Si2 in the paramagnetic and hidden-order phases are

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

    PubMed

    Fujimori, Shin-ichi

    2016-04-20

    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 eV) or high-energy synchrotron radiations (hν >/~ 400 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 CeMIn5(M = Rh, Ir, and Co) and YbRh2Si2 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 U5f compounds such as UFeGa5, their electronic structures can be well-described by the band-structure calculation assuming that all U5f electrons are itinerant. In contrast, the band structures of localized U5f compounds such as UPd3 and UO2 are essentially explained by the localized model that treats U5f electrons as localized core states. In regards to heavy fermion U-based compounds such as the hidden-order compound URu2Si2, their electronic structures exhibit complex behaviors. Their overall band structures are generally well-explained by the band-structure calculation, whereas the states in the vicinity of EF show some deviations due to electron correlation effects. Furthermore, the electronic structures of URu2Si2 in the paramagnetic and hidden-order phases are

  16. Phase-Resolved Infrared H- and K-Band Spectroscopy of EF Eridani

    NASA Astrophysics Data System (ADS)

    Harrison, Thomas E.; Howell, Steve B.; Szkody, Paula; Homeier, Derek; Johnson, Joni J.; Osborne, Heather L.

    2004-10-01

    We present new phase-resolved H- and K-band spectroscopy of the ultrashort-period magnetic cataclysmic variable EF Eri in its current prolonged ``low'' state obtained using NIRI on Gemini North and NIRSPEC on Keck II. These new data show that the H-band spectrum of EF Eri appears to be dominated by cyclotron emission during the entire orbital cycle. The K-band spectrum of EF Eri is likewise dominated by cyclotron emission during most of an orbital period, but near binary phase 0.0 the secondary star spectrum may be visible. The lack of strong CO or CH4 absorption features and the weakness of the water vapor features in this spectrum, however, suggests the possibility of peculiar abundances for carbon and/or oxygen. We have used the PHOENIX stellar atmosphere code to produce model brown dwarf spectra with nonsolar abundances of carbon, nitrogen, and oxygen, and achieved limited success in fitting the observed spectra. We conclude that strong, highly variable cyclotron emission is responsible for the photometric variation previously reported for EF Eri. The nature of this cyclotron emission is complex: the H-band spectra show that the dominant cyclotron harmonic at phase 0.5 peaks at 1.65 μm, but at phase 0.0 the harmonic peaks near 1.72 μm. At phase 0.5, there is another cyclotron feature present that peaks in between the H and K bands (near 1.93 μm), but at phase 0.0 no such feature is present. These data suggest that cyclotron emission from both poles is occurring. In the high state, the cyclotron emission has been modeled as coming from the pole that is oriented toward the secondary star. One interpretation for the phase 0.5 cyclotron emission is that it originates from the opposite pole. In its current ultralow state, EF Eri reveals no outward signs of accretion (such as H I emission) but continues to have a few, strong cyclotron features. Thus, EF Eri joins the small group of magnetic cataclysmic variables whose accretion rate is so low that they are in the

  17. 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

  18. 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

  19. 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

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

    PubMed

    Smith, Adam W

    2015-01-01

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

  1. 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

  2. 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.

  3. 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.

  4. In vivo optical characterization of human tissues from 610 to 1010 nm by time-resolved reflectance spectroscopy.

    PubMed

    Torricelli, A; Pifferi, A; Taroni, P; Giambattistelli, E; Cubeddu, R

    2001-08-01

    A fully automated system for time-resolved reflectance spectroscopy based on tunable mode-locked laser sources and on time-correlated single-photon counting for the detection of time-resolved reflectance data was applied to the evaluation of the optical properties of biological tissues (arm, abdomen and forehead) in vivo from 610 to 1010 nm. The scattering decreases progressively with increasing wavelength, while the absorption line shapes show the typical spectral features of the principal tissue components (haemoglobin, water and lipid), with different weights depending on the tissue type. The best fit of the absorption spectra measured in vivo with the spectra of the pure constituents yielded information on the percentage composition of the different tissues. The interpretation of transport scattering spectra with Mie theory provided information on tissue structure.

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

    PubMed

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

    2016-09-16

    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.

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

    PubMed

    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.

  7. 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.

  8. 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.

  9. Calculating singlet excited states: Comparison with fast time-resolved infrared spectroscopy of coumarins

    NASA Astrophysics Data System (ADS)

    Hanson-Heine, Magnus W. D.; Wriglesworth, Alisdair; Uroos, Maliha; Calladine, James A.; Murphy, Thomas S.; Hamilton, Michelle; Clark, Ian P.; Towrie, Michael; Dowden, James; Besley, Nicholas A.; George, Michael W.

    2015-04-01

    In contrast to the ground state, the calculation of the infrared (IR) spectroscopy of molecular singlet excited states represents a substantial challenge. Here, we use the structural IR fingerprint of the singlet excited states of a range of coumarin dyes to assess the accuracy of density functional theory based methods for the calculation of excited state IR spectroscopy. It is shown that excited state Kohn-Sham density functional theory provides a high level of accuracy and represents an alternative approach to time-dependent density functional theory for simulating the IR spectroscopy of singlet excited states.

  10. Calculating singlet excited states: Comparison with fast time-resolved infrared spectroscopy of coumarins.

    PubMed

    Hanson-Heine, Magnus W D; Wriglesworth, Alisdair; Uroos, Maliha; Calladine, James A; Murphy, Thomas S; Hamilton, Michelle; Clark, Ian P; Towrie, Michael; Dowden, James; Besley, Nicholas A; George, Michael W

    2015-04-21

    In contrast to the ground state, the calculation of the infrared (IR) spectroscopy of molecular singlet excited states represents a substantial challenge. Here, we use the structural IR fingerprint of the singlet excited states of a range of coumarin dyes to assess the accuracy of density functional theory based methods for the calculation of excited state IR spectroscopy. It is shown that excited state Kohn-Sham density functional theory provides a high level of accuracy and represents an alternative approach to time-dependent density functional theory for simulating the IR spectroscopy of singlet excited states.

  11. 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.

  12. Native point defect formation in flash sintered ZnO studied by depth-resolved cathodoluminescence spectroscopy

    NASA Astrophysics Data System (ADS)

    Gao, Hantian; Asel, Thaddeus J.; Cox, Jon W.; Zhang, Yuanyao; Luo, Jian; Brillson, L. J.

    2016-09-01

    Depth-resolved cathodoluminescence spectroscopy studies of flash sintered ZnO reveal that thermal runaway induces the formation of native point defects inside individual grains. Defects associated with oxygen vacancies (VO) form preferentially, contributing additional donors that increase conductivity within the grains of the polycrystalline material. Hyperspectral imaging of the granular cross sections shows filaments of increased VO following thermal runaway between the capacitor anode and cathode, supporting a heating mechanism localized on a granular scale. Within the grains, these defects form preferentially inside rather than at their boundaries, further localizing the dominant heating mechanism.

  13. 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.

  14. Growth and spin-resolved photoemission spectroscopy of the epitaxial α-Al2O3/Fe(110) system

    NASA Astrophysics Data System (ADS)

    Dedkov, Yu. S.; Fonin, M.; Rüdiger, U.; Güntherodt, G.

    2002-09-01

    Electronic and structural properties of epitaxial ultrathin aluminum oxide layers grown on epitaxial Fe(110) films were investigated at room temperature by means of spin-, angle- and energy-resolved photoemission spectroscopy. A spin polarization of -(15±5)% near the Fermi energy EF is found for 1 (ML) of α-Al2O3 on epitaxial Fe(110). This value results from the attenuation of -80% of Fe(110) by the oxide layer thickness and the spin-independent part of the scattering cross section.

  15. Excited-state dynamics of guanosine in aqueous solution revealed by time-resolved photoelectron spectroscopy: experiment and theory.

    PubMed

    Buchner, Franziska; Heggen, Berit; Ritze, Hans-Hermann; Thiel, Walter; Lübcke, Andrea

    2015-12-21

    Time-resolved photoelectron spectroscopy is performed on aqueous guanosine solution to study its excited-state relaxation dynamics. Experimental results are complemented by surface hopping dynamic simulations and evaluation of the excited-state ionization energy by Koopmans' theorem. Two alternative models for the relaxation dynamics are discussed. The experimentally observed excited-state lifetime is about 2.5 ps if the molecule is excited at 266 nm and about 1.1 ps if the molecule is excited at 238 nm. The experimental probe photon energy dependence of the photoelectron kinetic energy distribution suggests that the probe step is not vertical and involves a doubly-excited autoionizing state.

  16. Resolving a Long-Standing Ambiguity: the Non-Planarity of gauche-1,3-BUTADIENE Revealed by Microwave Spectroscopy

    NASA Astrophysics Data System (ADS)

    Martin-Drumel, Marie-Aline; McCarthy, Michael C.; Patterson, David; Eibenberger, Sandra; Buckingham, Grant; Baraban, Joshua H.; Ellison, Barney; Stanton, John F.

    2016-06-01

    The preferred conformation of cis-1,3-butadiene (CH_2=CH-CH=CH_2) has been of long-standing importance in organic chemistry because of its role in Diels-Alder transition states. The molecule could adopt a planar s-cis conformation, in favor of conjugations in the carbon chain, or a non-planar gauche conformation, as a result of steric interactions between the terminal H atoms. To resolve this ambiguity, we have now measured the pure rotational spectrum of this isomer in the microwave region, unambiguously establishing a significant inertial defect, and therefore a gauche conformation. Experimental measurements of gauche-1,3-butadiene and several of its isotopologues using cavity Fourier-transform microwave (FTMW) spectroscopy in a supersonic expansion and chirped-pulse FTMW spectroscopy in a 4 K buffer gas cell will be summarized, as will new quantum chemical calculations.

  17. Dynamic structural science: recent developments in time-resolved spectroscopy and X-ray crystallography.

    PubMed

    Trincao, Jose; Hamilton, Michelle L; Christensen, Jeppe; Pearson, Arwen R

    2013-10-01

    To understand the mechanism of biological processes, time-resolved methodologies are required to investigate how functionality is linked to changes in molecular structure. A number of spectroscopic techniques are available that probe local structural rearrangements with high temporal resolution. However, for macromolecules, these techniques do not yield an overall high-resolution description of the structure. Time-resolved X-ray crystallographic methods exist, but, due to both instrument availability and stringent sample requirements, they have not been widely applied to macromolecular systems, especially for time resolutions below 1 s. Recently, there has been a resurgent interest in time-resolved structural science, fuelled by the recognition that both chemical and life scientists face many of the same challenges. In the present article, we review the current state-of-the-art in dynamic structural science, highlighting applications to enzymes. We also look to the future and discuss current method developments with the potential to widen access to time-resolved studies across discipline boundaries.

  18. 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

  19. 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.

  20. 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.

  1. Time-resolved spectroscopy in ZnWO4 and ZnWO4 : Fe

    NASA Astrophysics Data System (ADS)

    Grigorjeva, L.; Pankratov, V.; Millers, D.; Chernov, S.; Nagirnyi, V.; Kotlov, A.; Watterich, A.

    2003-01-01

    Time-resolved luminescence and absorption of ZnWO4 and ZnWO4:Fe have been studied. The fast decaying luminescence at similar to 1.7 eV is attributed to either Fe2+ or a Fe3+ related center. The two observed stages in luminescence decay kinetics under ionising radiation are suggested to be due to two types of self-trapped excitons.

  2. 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.

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

    PubMed

    Jozwiak, C; Graf, J; Lebedev, G; Andresen, N; Schmid, A K; Fedorov, A V; El Gabaly, F; Wan, W; Lanzara, A; Hussain, Z

    2010-05-01

    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. PMID:20515152

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

    NASA Astrophysics Data System (ADS)

    Jozwiak, C.; Graf, J.; Lebedev, G.; Andresen, N.; Schmid, A. K.; Fedorov, A. V.; El Gabaly, F.; Wan, W.; Lanzara, A.; Hussain, Z.

    2010-05-01

    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° 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Ferryl intermediates of catalase captured by time-resolved Weissenberg crystallography and UV-VIS spectroscopy.

    PubMed

    Gouet, P; Jouve, H M; Williams, P A; Andersson, I; Andreoletti, P; Nussaume, L; Hajdu, J

    1996-11-01

    Various enzymes use semi-stable ferryl intermediates and free radicals during their catalytic cycle, amongst them haem catalases. Structures for two transient intermediates (compounds I and II) of the NADPH-dependent catalase from Proteus mirabilis (PMC) have been determined by time-resolved X-ray crystallography and single crystal microspectrophotometry. The results show the formation and transformation of the ferryl group in the haem, and the unexpected binding of an anion during this reaction at a site distant from the haem.

  12. Laser-based spin- and angle-resolved photoemission spectroscopy for rapid, high-resolution measurements

    NASA Astrophysics Data System (ADS)

    Gotlieb, Kenneth; Bostwick, Aaron; Hussain, Zahid; Lanzara, Alessandra; Jozwiak, Christopher

    2014-03-01

    A unique spin-and angle-resolved photoemission spectrometer (spin-ARPES) is coupled with a 6 eV laser to achieve unprecedented measurements of near-EF physics in topological insulators and Rashba systems. The pairing of the spin-ARPES system with the laser allows for energy and angular resolutions never before seen in a spin-ARPES experiment. Most importantly, the high efficiency of the system and high photon flux of the laser make measurements very rapid, permitting exploration of a large experimental phase space.

  13. Discrimination of molecular thin films by surface-sensitive time-resolved optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Peli, Simone; Nembrini, Nicola; Damin, Francesco; Chiari, Marcella; Giannetti, Claudio; Banfi, Francesco; Ferrini, Gabriele

    2015-10-01

    An optical discrimination technique, tailored to nanometric-sized, low optical absorbance molecular complexes adhering to thin metal films, is proposed and demonstrated. It is based on a time-resolved evanescent-wave detection scheme in conjunction with hierarchical cluster analysis and principal value decomposition. The present approach aims to differentiate among molecular films based on statistical methods, without using previous detailed knowledge of the physical mechanisms responsible for the detected signal. The technique is open to integration in lab-on-a-chip architectures and nanoscopy platforms for applications ranging from medical screening to material diagnostics.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

    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 a TOF Electron Energy Analyzer for photoemission spectroscopy. The electron optical scheme of the analyzer includes an electrostatic objective lens, three columns of transport lenses and a 90 degree energy band pass filter (BPF). High efficiency exchange scattering based spin polarimeter [1] is used for electron spin detection. The analyzer support two modes of operation: Spectrometer Mode allowing the entire spectrum to be measured, and Monochromator Mode in which the BPF passes a specified energy window inside the scope of the electron energy spectrum. [1] J. Graf, C. Jozwiak, A. K. Schmid, Z. Hussain, and A. Lanzara, Physical. Rev. B 71, 144429 (2005)

  16. 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.

  17. 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.

  18. [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.

  19. Time resolved diffuse optical spectroscopy with geometrically accurate models for bulk parameter recovery

    PubMed Central

    Guggenheim, James A.; Bargigia, Ilaria; Farina, Andrea; Pifferi, Antonio; Dehghani, Hamid

    2016-01-01

    A novel straightforward, accessible and efficient approach is presented for performing hyperspectral time-domain diffuse optical spectroscopy to determine the optical properties of samples accurately using geometry specific models. To allow bulk parameter recovery from measured spectra, a set of libraries based on a numerical model of the domain being investigated is developed as opposed to the conventional approach of using an analytical semi-infinite slab approximation, which is known and shown to introduce boundary effects. Results demonstrate that the method improves the accuracy of derived spectrally varying optical properties over the use of the semi-infinite approximation. PMID:27699137

  20. 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.

  1. Time resolved diffuse optical spectroscopy with geometrically accurate models for bulk parameter recovery

    PubMed Central

    Guggenheim, James A.; Bargigia, Ilaria; Farina, Andrea; Pifferi, Antonio; Dehghani, Hamid

    2016-01-01

    A novel straightforward, accessible and efficient approach is presented for performing hyperspectral time-domain diffuse optical spectroscopy to determine the optical properties of samples accurately using geometry specific models. To allow bulk parameter recovery from measured spectra, a set of libraries based on a numerical model of the domain being investigated is developed as opposed to the conventional approach of using an analytical semi-infinite slab approximation, which is known and shown to introduce boundary effects. Results demonstrate that the method improves the accuracy of derived spectrally varying optical properties over the use of the semi-infinite approximation.

  2. Monochromatic imaging camera for spectrally and spatially resolved optical emission spectroscopy

    SciTech Connect

    Hareland, W.A.

    1994-12-31

    Spectrally and spatially resolved emissions have been measured from argon plasmas in an experimental radio-frequency plasma reactor. The monochromatic imaging camera records 2-dimensional images at a single wavelength of light, and the 2-dimensional images are treated by Abel inversion to produce 3-dimensional maps of single excited species in radio-frequency plasmas. Monochromatic images of argon were measured at a spectral bandwidth of 2.4 nm over the wavelength range from 394 to 912 nm. The spatial distribution of excited argon varies with excitation state. Lower-energy argon (< 13 eV) is found throughout the plasma, whereas, higher-energy argon is observed in and directly above the sheath in capacitively coupled discharges. Monochromatic imaging provides new optical diagnostics for measuring and monitoring plasmas.

  3. Spatially resolved modal spectroscopy of Er:Yb doped multifilament-core fiber amplifier.

    PubMed

    Le Gouët, Julien; Delaporte, Julien; Lombard, Laurent; Canat, Guillaume

    2012-02-27

    The spatially resolved spectral (S2) imaging method is applied on an active microstructured fiber, with a multi-filament core (MFC). This type of fiber has been designed to be the last amplifying stage of a source for a long range coherent lidar. Studying the influence of the bending radius on the modal content with or without gain, we demonstrate that an upper-bound of the high-order modes content can be found by performing the S2 imaging on the bleached fiber. S2 imaging is then used to verify that the output beam of the MFC fiber can be made effectively single-mode. We also show that it can be simply adapted for measuring the fiber birefringence. Finally, a comparison of the MFC fiber mode area with that of a standard large mode area Erbium doped step index fiber illustrates the interest of the MFC structure for high power amplifiers.

  4. 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.

  5. 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.

  6. 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.

  7. 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-.

  8. 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.

  9. 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.

  10. Spatially resolved modal spectroscopy of Er:Yb doped multifilament-core fiber amplifier.

    PubMed

    Le Gouët, Julien; Delaporte, Julien; Lombard, Laurent; Canat, Guillaume

    2012-02-27

    The spatially resolved spectral (S2) imaging method is applied on an active microstructured fiber, with a multi-filament core (MFC). This type of fiber has been designed to be the last amplifying stage of a source for a long range coherent lidar. Studying the influence of the bending radius on the modal content with or without gain, we demonstrate that an upper-bound of the high-order modes content can be found by performing the S2 imaging on the bleached fiber. S2 imaging is then used to verify that the output beam of the MFC fiber can be made effectively single-mode. We also show that it can be simply adapted for measuring the fiber birefringence. Finally, a comparison of the MFC fiber mode area with that of a standard large mode area Erbium doped step index fiber illustrates the interest of the MFC structure for high power amplifiers. PMID:22418363

  11. 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.

  12. 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

  13. 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.

  14. 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.

  15. 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.

  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. 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.

  18. 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.

  19. Angle-resolved photoemission spectroscopy study of adsorption process and electronic structure of silver on ZnO(1010).

    PubMed

    Ozawa, K; Sato, T; Kato, M; Edamoto, K; Aiura, Y

    2005-08-01

    The adsorption process and valence band structure of Ag on ZnO(1010) have been investigated by angle-resolved photoelectron spectroscopy utilizing synchrotron radiation. The coverage-dependent measurements of the Ag 4d band structure reveal that the Ag bands with a dispersing feature are formed even at low coverages and that the basic structure of the bands is essentially the same throughout the submonolayer region. These results indicate that the Ag atoms aggregate to form islands with an atomically ordered structure from the low coverages. Upon annealing the Ag-covered surface at 900 K, the Ag 4d band undergoes only a minor change, suggesting that the ordered structure within the Ag islands is persistent against mild annealing. From the dispersive feature of the Ag 4d states, we propose that the atomic structure has locally rectangular symmetry with a good lattice matching with the ZnO(1010) surface.

  20. 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

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

    PubMed

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

    2015-06-22

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

  2. Angle-resolved photoelectron spectroscopy of HCl from a photon energy of 16 to 80 eV

    SciTech Connect

    Carlson, T.A.; Krause, M.O.; Fahlman, A.; Keller, P.R.; Taylor, J.W.; Whitley, T.; Grimm, F.A.

    1983-09-01

    Angle-resolved photoelectron spectroscopy was performed on HCl using synchrotron radiation over a photon energy from 16 to 80 eV. The partial cross sections and angular distribution parameters ..beta.. were obtained for photoionization of both the 2..pi.. and 5sigma orbitals. Multiple scattering X..cap alpha.. calculations were also carried out for the cross sections and ..beta.. values. The calculations, together with previously published results on the cross section using a Hartree--Fock model, were compared with experiment and gave reasonable qualitative agreement. Both experimental and theoretical results were examined with particular regard to the nature of the Cooper minimum, and the differences between the behavior of the minima for the two orbitals are discussed in detail.

  3. Light-induced switching of HAMP domain conformation and dynamics revealed by time-resolved EPR spectroscopy.

    PubMed

    Klose, Daniel; Voskoboynikova, Natalia; Orban-Glass, Ioan; Rickert, Christian; Engelhard, Martin; Klare, Johann P; Steinhoff, Heinz-Jürgen

    2014-11-01

    HAMP domains are widely abundant signaling modules. The putative mechanism of their function comprises switching between two distinct states. To unravel these conformational transitions, we apply site-directed spin labeling and time-resolved EPR spectroscopy to the phototactic receptor/transducer complex NpSRII/NpHtrII. We characterize the kinetic coupling of NpHtrII to NpSRII along with the activation period of the transducer and follow the transient conformational signal. The observed transient shift towards a more compact state of the HAMP domain upon light-activation agrees with structure-based calculations. It thereby validates the two modeled signaling states and integrates the domain's dynamics into the current model.

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

    NASA Astrophysics Data System (ADS)

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

    2015-02-01

    The electric discharge spark dissociation of gas CH3I is found to be similar to its femtosecond laser photodissociation. The almost identical spectra of the two processes show that their initial ionization conditions are very similar. The initial ionization followed by molecular fragmentation is proposed as the dissociation mechanism, in which the characteristic emissions of I+, CH3, CH2, CH, H, and I2 are identified as the dissociation products. The emission band of 505 nm I2 is clearly observed in the time-resolved laser induced breakdown spectroscopy (LIBS). The dynamic curve indicates that I2∗ molecules are formed after the delay time of ∼4.7 ns. The formation of I2∗ molecule results from the bimolecular collision of the highly excited iodine atom I∗(4P) and CH3I molecule. This dynamical information can help understand the process of electric discharge spark dissociation of CH3I.

  5. 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.

  6. Hemodynamic Measurements of the Human Adult Head in Transmittance Mode by Near-Infrared Time-Resolved Spectroscopy.

    PubMed

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

    2016-01-01

    Using a near-infrared time-resolved spectroscopy (TRS) system, we measured the human head in transmittance mode to obtain the optical properties and the hemodynamic changes of deep brain tissues in seven healthy adult volunteers during hyperventilation. For six out of seven volunteers, we obtained the optical signals with sufficient intensity within 10 sec. of sampling. We confirmed that it is possible to non-invasively measure the hemodynamic changes of the human head during hyperventilation, even in the transmittance measurements by the developed TRS system. These results showed that the level of deoxygenated hemoglobin was significantly increased, and the level of oxygenated and total hemoglobin and tissue oxygen saturation were also significantly decreased during hyperventilation. We expect that this TRS technique will be applied to clinical applications for measuring deep brain tissues and deep biological organs. PMID:26782238

  7. Time-resolved photoluminescence spectroscopy and imaging: new approaches to the analysis of cultural heritage and its degradation.

    PubMed

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

    2014-04-02

    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.

  8. 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

  9. Time-resolved evanescent wave absorption spectroscopy for real-time monitoring of heme protein adsorption to glass.

    PubMed

    Qi, Zhi-Mei; Xia, Shanhong; Matsuda, Naoki

    2008-03-01

    Evanescent wave has been recognized as a highly sensitive optical probe for surface monitoring. By use of slab optical waveguides, time-resolved evanescent wave absorption spectroscopy was developed for the investigation of the interfacial behavior of biomolecules with a chromophore. In this study, 30-microm thick glass sheets served as freestanding multimode waveguides that were combined with a simple fiber-coupling method to lead to a broadband evanescent wave absorption spectrometer. With such a homemade instrument, adsorption of heme proteins onto glass slides from static aqueous solution was monitored in situ. The experimental results reveal that the interfacial behavior of myoglobin (Mb) is different from that of hemoglobin (Hb) and cytochrome c (Cc). Formation of dynamic equilibrium for Mb adsorption at both hydrophilic and hydrophobic surfaces always is behind the occurrence of the maximum coverage. However, simultaneous formation of the dynamic equilibrium and the maximum coverage was observed for Hb and Cc adsorptions.

  10. 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.

  11. Structural changes in bacteriorhodopsin during the photocycle measured by time-resolved polarized Fourier transform infrared spectroscopy.

    PubMed

    Kelemen, L; Ormos, P

    2001-12-01

    The structural changes in bacteriorhodopsin during the photocycle are investigated. Time resolved polarized infrared spectroscopy in combination with photoselection is used to determine the orientation and motion of certain structural units of the molecule: Asp-85, Asp-96, Asp-115, the Schiff base, and several amide I vibrations. The results are compared with recently published x-ray diffraction data with atomic resolution about conformational motions during the photocycle. The orientation of the measured vibrations are also calculated from the structure data, and based on the comparison of the values from the two techniques new information is obtained: several amide I bands in the infrared spectrum are assigned, and we can also identify the position of the proton in the protonated Asp residues.

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

    PubMed

    Ponseca, C S; Sundström, V

    2016-03-28

    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.

  13. 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}.

  14. 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

  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. 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.

  17. 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).

  18. Orbital-dependent electron correlation in LiFeAs revealed by angle-resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Hajiri, T.; Ito, T.; Matsunami, M.; Min, B. H.; Kwon, Y. S.; Kuroki, K.; Kimura, S.

    2016-01-01

    We report on the electronic structure of the 111-type iron pnictide superconductor LiFeAs as a function of temperature using angle-resolved photoemission spectroscopy. Below approximately 50 K, both the dy z hole band at the Z point and the dx z /y z electron band at the A point shift to a higher binding energy side. However, at the high-symmetry points Z ,A ,Γ , and M , the remaining bands are almost independent of temperature. One of the possible scenarios for these observations is that a strong, three-dimensional orbital-dependent correlation exists in the normal state of LiFeAs in relation to short-range spin fluctuations.

  19. Cage-Like Nanoclusters of ZnO Probed by Time-Resolved Photoelectron Spectroscopy and Theory.

    PubMed

    Heinzelmann, Julian; Koop, Alexander; Proch, Sebastian; Ganteför, Gerd F; Łazarski, Roman; Sierka, Marek

    2014-08-01

    Zinc oxide nanoclusters have been predicted as promising building blocks for cluster-assembled materials with unprecedented properties. Here, for the first time these clusters are probed by time-resolved photoelectron spectroscopy and characterized in detail by density functional theory. Their validity as building blocks for cluster-assembled materials is confirmed via rigid cage-like structures facilitating three-dimensional aggregation in combination with large band gaps that are nevertheless significantly lower than any known ZnO polymorph. In addition, electron-hole pair localization in the excited state of the cluster anions combined with their structural rigidity leads to extraordinary long-lived states above the band gap virtually independent of the cluster size, defying the rule "every atom counts". PMID:26277957

  20. 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.

  1. 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.

  2. Long-Lived Excited-State Dynamics of i-Motif Structures Probed by Time-Resolved Infrared Spectroscopy.

    PubMed

    Keane, Páraic M; Baptista, Frederico R; Gurung, Sarah P; Devereux, Stephen J; Sazanovich, Igor V; Towrie, Michael; Brazier, John A; Cardin, Christine J; Kelly, John M; Quinn, Susan J

    2016-05-01

    UV-generated excited states of cytosine (C) nucleobases are precursors to mutagenic photoproduct formation. The i-motif formed from C-rich sequences is known to exhibit high yields of long-lived excited states following UV absorption. Here the excited states of several i-motif structures have been characterized following 267 nm laser excitation using time-resolved infrared spectroscopy (TRIR). All structures possess a long-lived excited state of ∼300 ps and notably in some cases decays greater than 1 ns are observed. These unusually long-lived lifetimes are attributed to the interdigitated DNA structure which prevents direct base stacking overlap.

  3. Rotationally-Resolved Infrared Spectroscopy of the νb{16} Band of 1,3,5-TRIOXANE

    NASA Astrophysics Data System (ADS)

    Gibson, Bradley M.; Koeppen, Nicole; McCall, Benjamin J.

    2015-06-01

    1,3,5-trioxane is the simplest cyclic form of polyoxymethylene (POM), a class of formaldehyde polymers that has been proposed as the origin of distributed formaldehyde formation in comet comae and a potential source of formaldehyde in prebiotic chemistry. Although claimed POM detections have since been proven to be inconclusive, laboratory simulations of cometary conditions have yielded trioxane and other POMs While the microwave spectrum of 1,3,5-trioxane has been studied extensively, 4-7.}, to date only one rotationally-resolved ro-vibrational spectrum has been published. Here, we present our studies of the νb{16} band of gas-phase trioxane centered at 1177 wn. Trioxane was entrained in a supersonic expansion of argon and characterized by continuous-wave cavity ringdown spectroscopy using an etalon-stabilized external-cavity quantum cascade laser. Rotationally resolved spectra were obtained with less than 15 MHz resolution. Cottin, H., Bénilan, Y., Gazeau, M-C., and Raulin, F. Origin of Cometary Extended Sources from Degradation of Refractory Organics on Grains: Polyoxymethylene as Formaldehyde Parent Molecule. Icarus 167 (2004), 397-416. Oka, T., Tsuchiya, K., Iwata, S., and Morino, Y. Microwave Spectrum of s-Trioxane. Bull. Chem. Soc. Jpn. 37 (1964), 4-7. Henninot, J-F., Bolvin, H., Demaison, J., and Lemoine, B. The Infrared Spectrum of Trioxane in a Supersonic Slit Jet. J. Mol. Spect. 152 (1992), 62-68. Gibson, B.M. and McCall, B.J., contribution TJ08, presented at the 69th International Symposium on Molecular Spectroscopy, Urbana, IL, USA, 2014.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. Depth-resolved confocal micro-Raman spectroscopy for characterizing GaN-based light emitting diode structures.

    PubMed

    Chen, Wei-Liang; Lee, Yu-Yang; Chang, Chiao-Yun; Huang, Huei-Min; Lu, Tien-Chang; Chang, Yu-Ming

    2013-11-01

    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 A1(LO) and E2(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. PMID:24289389

  12. Detection of high-risk atherosclerotic lesions by time-resolved fluorescence spectroscopy based on the Laguerre deconvolution technique

    NASA Astrophysics Data System (ADS)

    Jo, J. A.; Fang, Q.; Papaioannou, T.; Qiao, J. H.; Fishbein, M. C.; Beseth, B.; Dorafshar, A. H.; Reil, T.; Baker, D.; Freischlag, J.; Marcu, L.

    2006-02-01

    This study introduces new methods of time-resolved laser-induced fluorescence spectroscopy (TR-LIFS) data analysis for tissue characterization. These analytical methods were applied for the detection of atherosclerotic vulnerable plaques. Upon pulsed nitrogen laser (337 nm, 1 ns) excitation, TR-LIFS measurements were obtained from carotid atherosclerotic plaque specimens (57 endarteroctomy patients) at 492 distinct areas. The emission was both spectrally- (360-600 nm range at 5 nm interval) and temporally- (0.3 ns resolution) resolved using a prototype clinically compatible fiber-optic catheter TR-LIFS apparatus. The TR-LIFS measurements were subsequently analyzed using a standard multiexponential deconvolution and a recently introduced Laguerre deconvolution technique. Based on their histopathology, the lesions were classified as early (thin intima), fibrotic (collagen-rich intima), and high-risk (thin cap over necrotic core and/or inflamed intima). Stepwise linear discriminant analysis (SLDA) was applied for lesion classification. Normalized spectral intensity values and Laguerre expansion coefficients (LEC) at discrete emission wavelengths (390, 450, 500 and 550 nm) were used as features for classification. The Laguerre based SLDA classifier provided discrimination of high-risk lesions with high sensitivity (SE>81%) and specificity (SP>95%). Based on these findings, we believe that TR-LIFS information derived from the Laguerre expansion coefficients can provide a valuable additional dimension for the diagnosis of high-risk vulnerable atherosclerotic plaques.

  13. Energy transfer in the chlorophyll f-containing cyanobacterium, Halomicronema hongdechloris, analyzed by time-resolved fluorescence spectroscopies.

    PubMed

    Akimoto, Seiji; Shinoda, Toshiyuki; Chen, Min; Allakhverdiev, Suleyman I; Tomo, Tatsuya

    2015-08-01

    We prepared thylakoid membranes from Halomicronema hongdechloris cells grown under white fluorescent light or light from far-red (740 nm) light-emitting diodes, and observed their energy-transfer processes shortly after light excitation. Excitation-relaxation processes were examined by steady-state and time-resolved fluorescence spectroscopies. Two time-resolved fluorescence techniques were used: time-correlated single photon counting and fluorescence up-conversion methods. The thylakoids from the cells grown under white light contained chlorophyll (Chl) a of different energies, but were devoid of Chl f. At room temperature, the excitation energy was equilibrated among the Chl a pools with a time constant of 6.6 ps. Conversely, the thylakoids from the cells grown under far-red light possessed both Chl a and Chl f. Two energy-transfer pathways from Chl a to Chl f were identified with time constants of 1.3 and 5.0 ps, and the excitation energy was equilibrated between the Chl a and Chl f pools at room temperature. We also examined the energy-transfer pathways from phycobilisome to the two photosystems under white-light cultivation.

  14. Quantitative measurement of cerebral blood flow in a juvenile porcine model by depth-resolved near-infrared spectroscopy

    NASA Astrophysics Data System (ADS)

    Elliott, Jonathan T.; Diop, Mamadou; Tichauer, Kenneth M.; Lee, Ting-Yim; Lawrence, Keith St.

    2010-05-01

    Nearly half a million children and young adults are affected by traumatic brain injury each year in the United States. Although adequate cerebral blood flow (CBF) is essential to recovery, complications that disrupt blood flow to the brain and exacerbate neurological injury often go undetected because no adequate bedside measure of CBF exists. In this study we validate a depth-resolved, near-infrared spectroscopy (NIRS) technique that provides quantitative CBF measurement despite significant signal contamination from skull and scalp tissue. The respiration rates of eight anesthetized pigs (weight: 16.2+/-0.5 kg, age: 1 to 2 months old) are modulated to achieve a range of CBF levels. Concomitant CBF measurements are performed with NIRS and CT perfusion. A significant correlation between CBF measurements from the two techniques is demonstrated (r2=0.714, slope=0.92, p<0.001), and the bias between the two techniques is -2.83 mL.min-1.100 g-1 (CI0.95: -19.63 mL.min-1.100 g-1-13.9 mL.min-1.100 g-1). This study demonstrates that accurate measurements of CBF can be achieved with depth-resolved NIRS despite significant signal contamination from scalp and skull. The ability to measure CBF at the bedside provides a means of detecting, and thereby preventing, secondary ischemia during neurointensive care.

  15. 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

  16. Two-Photon Absorption and Time-Resolved Stimulated Emission Depletion Spectroscopy of a New Fluorenyl Derivative

    PubMed Central

    Bondar, Mykhailo V.; Morales, Alma R.; Yue, Xiling; Luchita, Gheorghe; Przhonska, Olga V.; Kachkovsky, Olexy D.

    2012-01-01

    The synthesis, comprehensive linear photophysical characterization, two-photon absorption (2PA), steady-state and time-resolved stimulated emission depletion properties of a new fluorene derivative, (E)-1-(2-(di-p-tolylamino)-9,9-diethyl-9H-fluoren-7-yl)-3-(thiophen-2-yl)prop-2-en-1-one (1), are reported. The primary linear spectral properties, including excitation anisotropy, fluorescence lifetimes, and photostability, were investigated in a number of aprotic solvents at room temperature. The degenerate 2PA spectra of 1 were obtained with an open aperture Z-scan and two-photon induced fluorescence methods, using a 1-kHz femtosecond laser system, and maximum 2PA cross-sections of ~400–600 GM were obtained. The nature of the electronic absorption processes in 1 was investigated by DFT-based quantum chemical methods implemented in the Gaussian 09 program. The one- and two-photon stimulated emission spectra of 1 were measured over a broad spectral range using a femtosecond pump probe–based fluorescence quenching technique, while a new methodology for time-resolved fluorescence emission spectroscopy is proposed. An effective application of 1 in fluorescence bioimaging was demonstrated via one- and two-photon fluorescence microscopy images of HCT 116 cells containing the dye encapsulated micelles. PMID:22887914

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. Rotationally Resolved Spectroscopy of the Electronically Excited C and D States of {XeKr} and {XeAr}

    NASA Astrophysics Data System (ADS)

    Piticco, Lorena; Schäfer, Martin; Merkt, Frédéric

    2009-06-01

    Informations on excited electronic states of the heteronuclear rare-gas dimers XeRg (Rg=Kr, Ar) available in the literature are limited to the vibrational structure of several band systems in the VUV range of the electromagnetic spectrum. Using a near-Fourier-transform-limited vacuum-ultraviolet laser system spectra of the C ← X and D ← X band systems of several isotopomers of XeKr and XeAr were recorded at high resolution in the wavenumber range from 77 000 cm^{-1} to 77 350 cm^{-1} by resonance-enhanced two-photon ionization spectroscopy. The rotational and vibrational structures of the C ← X and D ← X band systems could be fully resolved and assigned on the basis of isotopic shifts, combination differences and the ground state microwave spectra. The orbital hyperfine structure of the C1 state could be resolved for the ^{129}Xe^{40}Ar and ^{131}Xe^{40}Ar isotopomers. Potential energy functions and a full set of spectroscopic parameters were derived for the ground and excited states. D. M. Mao, X. K. Hu, S. S. Dimov, R. H. Lipson}, J. Phys. B 29, L89 (1996). O. Zehnder, F. Merkt, Mol. Phys. 106, 1215 (2008). KrXe+ O. Zehnder, F. Merkt, J. Chem. Phys. 128, 014306 (2008). ArXe+ U. Hollenstein, H. Palm and F. Merkt, Rev. Sci. Instr. 71, 4023 (2000). W. Jäger, Y. Xu, M. C. L. Gerry, J. Chem. Phys. 99, 919 (1993).

  2. 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.

  3. 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.

  4. FOS spectroscopy of resolved structure in the nucleus of NGC 1068

    SciTech Connect

    Caganoff, S.; Kriss, G.A.; Antonucci, R.R.J.; Ford, H.C.; Hartig, G. California Univ., Santa Barbara Telescope Science Inst., Baltimore, MD )

    1991-08-01

    The results of FOS spectroscopy of the continuum peak of NGC 1068 in the wavelength range 2200-7000 A are reported. Detailed analysis reveals the emission lines to be complex in shape and to consist of a number of different velocity components. Both the Balmer lines and the strong forbidden lines have a contribution from a component with full width at half-maximum on the order of 2200 km/s. However, the broad H-beta emission observed in polarized light is not detected. This implies that the continuum peak is not the mirror which reflects light from the hidden Seyfert I nucleus. It could possibly contribute some of the reflected light, but the equivalent width of the H-beta BLR line, if present at all, is much weaker than expected from the ground-based nuclear polarized-flux spectrum. 15 refs.

  5. FOS spectroscopy of resolved structure in the nucleus of NGC 1068

    NASA Technical Reports Server (NTRS)

    Caganoff, S.; Kriss, G. A.; Antonucci, R. R. J.; Ford, H. C.; Hartig, G.

    1991-01-01

    The results of FOS spectroscopy of the continuum peak of NGC 1068 in the wavelength range 2200-7000 A are reported. Detailed analysis reveals the emission lines to be complex in shape and to consist of a number of different velocity components. Both the Balmer lines and the strong forbidden lines have a contribution from a component with full width at half-maximum on the order of 2200 km/s. However, the broad H-beta emission observed in polarized light is not detected. This implies that the continuum peak is not the mirror which reflects light from the hidden Seyfert I nucleus. It could possibly contribute some of the reflected light, but the equivalent width of the H-beta BLR line, if present at all, is much weaker than expected from the ground-based nuclear polarized-flux spectrum.

  6. AU Mic’s Debris Disk Chemistry Revealed Using Spatially Resolved Spectroscopy

    NASA Astrophysics Data System (ADS)

    Lomax, Jamie Renae; Donaldson, Jessica; Debes, John H.; Malumuth, Eliot; Roberge, Aki; Weinberger, Alycia J.; Wisniewski, John P.

    2015-01-01

    We present the first coronagraphic spectroscopy of the AU Mic debris disk system obtained with HST/STIS as part of GO-12512. Spectra of the system were taken by placing a long slit in the disk direction while blocking out the central star with an occulting bar. A naked star of similar spectral type was likewise observed for a PSF subtraction. This procedure results in a two dimensional spectrum as a function of disk position between 5200 and 10,200 angstroms for the system. We use the spectra to determine the cold dust grain composition by characterizing the system's color as a function of radial distance along the disk's midplane. This reveals the dynamical perturbations and chemical processing occurring within the disk and traces the potential composition and architecture of any planetary bodies in the system because the planetesimals that form planets produce the observed dust through collisional break up and evaporation.

  7. 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.

  8. 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

  9. Improved instrumentation for intensity-, wavelength-, temperature-, and magnetic field-resolved photoconductivity spectroscopy

    NASA Astrophysics Data System (ADS)

    Cottingham, Patrick; Morey, Jennifer R.; Lemire, Amanda; Lemire, Penny; McQueen, Tyrel M.

    2016-10-01

    We report instrumentation for photovoltage and photocurrent spectroscopy over a larger continuous range of wavelengths, temperatures, and applied magnetic fields than other instruments described in the literature: 350 nm≤λ≤1700 nm, 1.8 K≤T≤300 K, and B≤9 T. This instrument uses a modulated monochromated incoherent light source with total power<30 μW in combination with an LED in order to probe selected regions of non-linear responses while maintaining low temperatures and avoiding thermal artifacts. The instrument may also be used to measure a related property, the photomagnetoresistance. We demonstrate the importance of normalizing measured responses for variations in light power and describe a rigorous process for performing these normalizations. We discuss several circuits suited to measuring different types of samples and provide analysis for converting measured values into physically relevant properties. Uniform approaches to measurement of these photoproperties are essential for reliable quantitative comparisons between emerging new materials with energy applications.

  10. 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.

  11. 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

  12. Time-resolved Spectroscopy of Active Binary Stars: Coronal Structure and Flares (Part II)

    NASA Astrophysics Data System (ADS)

    Brown, Alexander

    EUVE has provided the first stellar coronal spectra showing individual emission lines, thereby allowing coronal modelling at a level of sophistication previously unattainable. Long EUVE observations have shown that large-scale flaring is prevalent in the coronae of active binary stars. We propose to obtain EUVE DSS spectra and photometry for 4 active binaries, one of which has never been observed by EUVE (V478 Lyr) and three EUV-bright systems that merit reobservation (Sigma CrB, Sigma Gem, Xi UMa). We shall use these observations to derive high quality quiescent coronal spectra for measuring emission measure distributions and modelling, and to obtain new flare data. We shall try to coordinate these observations with ground-based radio observations and other spacecraft, if the scheduling allows. The Sigma CrB spectra may be coordinated with AXAF GTO observations. The proposed observations will significantly increase the available EUVE spectroscopy of active binaries.

  13. 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)

  14. 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.

  15. Chiral signatures in angle-resolved valence photoelectron spectroscopy of pure glycidol enantiomers.

    PubMed

    Garcia, Gustavo A; Nahon, Laurent; Harding, Chris J; Powis, Ivan

    2008-03-28

    Photoionization of the chiral molecule glycidol has been investigated in the valence region. Photoelectron circular dichroism (PECD) curves have been obtained at various photon energies by using circularly polarized VUV synchrotron radiation and a velocity map imaging technique to record angle-resolved photoelectron spectra (PES). The measured chiral asymmetries vary dramatically with the photon energy as well as with the ionized orbital, improving the effective orbital resolution of the PECD spectrum with respect to the PES. Typical asymmetry factors of 5% are observed, but the peak values measured range up to 15%. The experimental results are interpreted by continuum multiple scattering (CMS-Xalpha) calculations for several thermally accessible glycidol conformers. We find that a nearly quantitative agreement between theory and experiments can be achieved for the ionization of several molecular orbitals. Owing to the sensitivity of PECD to molecular conformation this allows us to identify the dominant conformer. The influence of intramolecular hydrogen bond orbital polarization is found to play a small yet significant role in determining the chiral asymmetry in the electron angular distributions.

  16. Hyperfine resolved spectrum of the bromomethyl radical, CH2Br, by Fourier transform microwave spectroscopy.

    PubMed

    Ozeki, H; Okabayashi, T; Tanimoto, M; Saito, S; Bailleux, S

    2007-12-14

    Pure rotational spectra of the bromomethyl radical, CH(2)Br, were measured by using a Fourier transform microwave (FT-MW) spectrometer in order to fully resolve hyperfine structures arising from both the bromine and hydrogen nuclei. We detected a total of 124 lines for the (79)Br and (81)Br isotopomers, including K(a)=0 (ortho species) and K(a)=1 (para species). No hyperfine splitting due to the hydrogen nuclei was observed for the para species, directly confirming the planarity of the radical. We conducted a global analysis of our present FT-MW results and previous measurements in the millimeter-wave region and obtained an exhaustive list of molecular constants. The sign of the Fermi constant of the bromine nucleus was unambiguously determined to be positive, which is opposite to that found in previous work in the millimeter-wave region and in electron spin resonance experiment on this radical. The present study permitted a systematic comparison to be made of the hyperfine coupling constants of both the halogen and hydrogen nuclei for CH(2)X-type compounds, where X=F, Cl, and Br.

  17. 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.

  18. 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.

  19. Near-infrared spatially resolved spectroscopy of 136108 Haumea's multiple system

    NASA Astrophysics Data System (ADS)

    Dumas, Christophe; Gourgeot, Florian; Carry, Benoit; Lacerda, Pedro; Merlin, Frederic; Vachier, Frederic; Antonieta Barucci, Maria; Berthier, Jerome

    2015-01-01

    The trans-Neptunian 136108 Haumea is a very fast rotator (~3.9h). It also displays a highly elongated shape and hosts two small moons, all covered with crystalline water ice, similarly to their central body. Haumea is also known to be the largest member of a TNO family, itself the outcome of a catastrophic collision likely responsible for Haumea's unique characteristics.We report here on the analysis of a new set of near-infrared Laser Guide Star assisted observations of Haumea obtained with the IFU spectrograph SINFONI at the ESO-Very Large Telescope Observatory. Combined with previous data published by Dumas et al. (2011), and using photometric light curve measurements (Lacerda 2009, Lellouch et al. 2011) to associate each spectrum with Haumea's corresponding rotational phase, we were able to derive an accurate rotationally resolved spectroscopic study of the surface of this trans-neptunian. A particular region of interest was the dark-red spot identified on the surface of Haumea from multi-band light curve analysis (Lacerda et al. 2008). We will present the results of applying Hapke modeling to our data-set, and our conclusions regarding the surface heterogeneity of Haumea. Additionally, thanks to the IFU capabilities to reconstruct images from our spectral cube, we were able to obtain relative astrometric position measurements for the two satellites and constrain dynamical models for their orbital motion.

  20. 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.).

  1. Resolved Spectroscopy of the Narrow-Line Region in NGC 1068: Kinematics of the Ionized Gas.

    PubMed

    Crenshaw; Kraemer

    2000-04-01

    We have determined the radial velocities of the [O iii]-emitting gas in the inner narrow-line region of the Seyfert 2 galaxy NGC 1068, along a slit at position angle 202 degrees, from STIS observations at a spatial resolution of 0&farcs;1 and a spectral resolving power of lambda&solm0;Deltalambda approximately 1000. We use these data to investigate the kinematics of the narrow-line region within 6&arcsec; ( approximately 430 pc) of the nucleus. The emission-line knots show evidence for radial acceleration to a projected angular distance of 1&farcs;7 in most cases, followed by deceleration that approaches the systemic velocity at a projected distance of approximately 4&arcsec;. We find that a simple kinematic model of biconical radial outflow can match the general trend of observed radial velocities. In this model, the emitting material is evacuated along the bicone axis, and the axis is inclined 5 degrees out of the plane of the sky. The acceleration of the emission-line clouds provides support for dynamical models that invoke radiation and/or wind pressure. We suggest that the deceleration of the clouds is due to their collision with a patchy and anistropically distributed ambient medium.

  2. Spectroscopy and optically stimulated luminescence of Al2O3:C using time-resolved measurements

    NASA Astrophysics Data System (ADS)

    Yukihara, E. G.; McKeever, S. W. S.

    2006-10-01

    This paper reports the observation of ultraviolet (UV) emission at 335nm in the optically stimulated luminescence (OSL) of carbon-doped aluminum oxide (Al2O3:C) and presents results on the investigation of the OSL properties of this band, including its dose response, time dependence after irradiation, and dependence of the OSL signal on the type of radiation. Time-resolved OSL measurements were used to separate the UV emission band from the dominant OSL emission band of Al2O3:C, namely, the F-center luminescence at 420nm. A comparison of the OSL properties of the UV and F-center emission bands is important for various dosimetric applications because the relative contribution of the UV and F-center emissions to the OSL signal varies with readout technique and optical filters used in the readout equipment. The UV emission band is found to show an ionization density dependence that is different from the dependence observed for the F-center emission, and an increase in intensity with time elapsed after beta irradiation. These results are relevant for OSL dosimetry of radiation fields containing heavy charged particles, such as the space radiation field and the secondary fields created by interactions of matter with energetic neutrons, as well as for understanding of the basic OSL mechanism in Al2O3:C.

  3. Near-infrared time-resolved spectroscopy of the cataclysmic variable YY Draconis

    SciTech Connect

    Mateo, M.; Szkody, P.; Garnavich, P. Washington Univ., Seattle )

    1991-03-01

    Time-resolved near-infrared (8100-8600 A) spectrophotometry and Johnson B-band CCD photometry of the cataclysmic binary YY Dra are presented. The spectra show the presence of the Na I doublet in absorption from the secondary, as well as sharp and broad Ca II emission lines. The sharp Ca II emission lines appear to originate on or near the secondary star because they are visible only during superior conjunction of the secondary star, their radial velocities vary in phase with the Na I absorption lines, and their K-velocity is considerably smaller than observed for the Na I lines. The radial velocity variation of the Na I near-infrared doublet yield an orbital period for YY Dra of P = 0.164988 + or - 0.00023 days. A spectral type of dM 4 + or - 1 for the secondary star is deduced based on the strength of its near-infrared spectral features. The distance to YY Dra is 155 + or - 35 pc based on an application of Bailey's method. 56 refs.

  4. 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.

  5. 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.

  6. SPATIALLY RESOLVED SPECTROSCOPY OF EUROPA: THE DISTINCT SPECTRUM OF LARGE-SCALE CHAOS

    SciTech Connect

    Fischer, P. D.; Brown, M. E.; Hand, K. P.

    2015-11-15

    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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. 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.

  13. 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.

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

    PubMed

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

    2010-01-01

    We introduce a method for noninvasively measuring muscle contraction in vivo, based on near-infrared diffusing-wave spectroscopy (DWS). The method exploits the information about time-dependent shear motions within the contracting muscle that are contained in the temporal autocorrelation function g(1)(τ,t) of the multiply scattered light field measured as a function of lag time, τ, and time after stimulus, t. The analysis of g(1)(τ,t) measured on the human M. biceps brachii during repetitive electrical stimulation, using optical properties measured with time-resolved reflectance spectroscopy, shows that the tissue dynamics giving rise to the speckle fluctuations can be described by a combination of diffusion and shearing. The evolution of the tissue Cauchy strain e(t) shows a strong correlation with the force, indicating that a significant part of the shear observed with DWS is due to muscle contraction. The evolution of the DWS decay time shows quantitative differences between the M. biceps brachii and the M. gastrocnemius, suggesting that DWS allows to discriminate contraction of fast- and slow-twitch muscle fibers. PMID:21054123

  15. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2010-09-01

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

  17. 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.

  18. A field programmable gate array-based time-resolved scaler for collinear laser spectroscopy with bunched radioactive potassium beams.

    PubMed

    Rossi, D M; Minamisono, K; Barquest, B R; Bollen, G; Cooper, K; Davis, M; Hammerton, K; Hughes, M; Mantica, P F; Morrissey, D J; Ringle, R; Rodriguez, J A; Ryder, C A; Schwarz, S; Strum, R; Sumithrarachchi, C; Tarazona, D; Zhao, S

    2014-09-01

    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 (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(5) in resonant photon detection measurements. The hyperfine structure of (37)K and its isotope shift relative to the stable (39)K were determined using 5 × 10(4) s(-1) (37)K ions injected into the BECOLA beam line. The obtained hyperfine coupling constants A((2)S(1/2)) = 120.3(1.4) MHz, A((2)P(1/2)) = 15.2(1.1) MHz, and A((2)P(3/2)) = 1.4(8) MHz, and the isotope shift δν(39, 37) = -264(3) MHz are consistent with the previously determined values, where available. PMID:25273722

  19. A field programmable gate array-based time-resolved scaler for collinear laser spectroscopy with bunched radioactive potassium beams.

    PubMed

    Rossi, D M; Minamisono, K; Barquest, B R; Bollen, G; Cooper, K; Davis, M; Hammerton, K; Hughes, M; Mantica, P F; Morrissey, D J; Ringle, R; Rodriguez, J A; Ryder, C A; Schwarz, S; Strum, R; Sumithrarachchi, C; Tarazona, D; Zhao, S

    2014-09-01

    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 (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(5) in resonant photon detection measurements. The hyperfine structure of (37)K and its isotope shift relative to the stable (39)K were determined using 5 × 10(4) s(-1) (37)K ions injected into the BECOLA beam line. The obtained hyperfine coupling constants A((2)S(1/2)) = 120.3(1.4) MHz, A((2)P(1/2)) = 15.2(1.1) MHz, and A((2)P(3/2)) = 1.4(8) MHz, and the isotope shift δν(39, 37) = -264(3) MHz are consistent with the previously determined values, where available.

  20. A field programmable gate array-based time-resolved scaler for collinear laser spectroscopy with bunched radioactive potassium beams

    NASA Astrophysics Data System (ADS)

    Rossi, D. M.; Minamisono, K.; Barquest, B. R.; Bollen, G.; Cooper, K.; Davis, M.; Hammerton, K.; Hughes, M.; Mantica, P. F.; Morrissey, D. J.; Ringle, R.; Rodriguez, J. A.; Ryder, C. A.; Schwarz, S.; Strum, R.; Sumithrarachchi, C.; Tarazona, D.; Zhao, S.

    2014-09-01

    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 37K 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 × 105 in resonant photon detection measurements. The hyperfine structure of 37K and its isotope shift relative to the stable 39K were determined using 5 × 104 s-1 37K ions injected into the BECOLA beam line. The obtained hyperfine coupling constants A(2S1/2) = 120.3(1.4) MHz, A(2P1/2) = 15.2(1.1) MHz, and A(2P3/2) = 1.4(8) MHz, and the isotope shift δν39, 37 = -264(3) MHz are consistent with the previously determined values, where available.

  1. 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 }.

  2. 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.

  3. Time-resolved spectroscopy of charge transfer phenomena in organic solar cells

    NASA Astrophysics Data System (ADS)

    Gerhard, Marina; Arndt, Andreas; Quintilla, Aina; Rahimi-Iman, Arash; Lemmer, Uli; Koch, Martin

    2015-03-01

    Geminate recombination of photo-generated excitons represents a considerable loss mechanism in polymer solar cells. We apply time-resolved photoluminescence (TRPL) to study the radiative recombination which accompanies the process of charge generation. A streak camera is used, which is sensitive for both the photoluminescence (PL) from the initially excited singlet excitons and the weaker emission from charge transfer (CT) states. The latter are formed at internal interfaces when the polymer is blended with a fullerene acceptor. We draw a comparison between our results for two polymers, P3HT and PTB7, respectively, which were studied in blends with the fullerene derivative PCBM. In addition, pristine films were investigated, allowing for the identification of interfacial features in the blends. For both polymers, the PL of the singlet states was rapidly quenched in blends with PCBM. In P3HT, time constants of about 40 ps were recorded for the singlet exciton decay and related to exciton diffusion, whereas the PL of PTB7 was almost completely quenched within the first 3 ps. The decay rates of the emissive CT excitons were 2-3 orders of magnitude smaller than those of the singlet state. Yet, due to their slower dynamics (~ 500 ps), they could be separated from the superimposed singlet emission. The CT decay times in blends with P3HT exhibited no significant temperature dependence, indicating that thermally driven dissociation of emissive excitons is unlikely. For blends with PTB7, however, a faster decay of the CT emission was obtained at room temperature.

  4. Spatially resolved electron tunneling spectroscopy on single crystalline Rb{sub 3}C{sub 60}

    SciTech Connect

    Jess, P.; Hubler, U.; Behler, S.; Thommen-Geiser, V.; Lang, H.P.; Guentherodt, H.

    1996-03-01

    A Rb{sub 3}C{sub 60} single crystal ({ital T}{sub {ital c}}=30.5 K) is investigated in the superconducting state at 2.8 K by scanning tunneling microscopy and scanning tunneling spectroscopy (STS). STS data reveals a spatial variation of the superconducting energy gap {Delta} on a scale of 50 nm ({Delta}=2.6{endash}5.2 meV; 2{Delta}/{ital k}{sub {ital BT}}{sub {ital c}}=2.0{endash}4.0). This behavior is attributed to varying stoichiometry on the sample surface. An investigation of a Rb{sub 3}C{sub 60} facet shows that {ital I}({ital V}) characteristics even vary on molecular scale. {ital I}({ital V}) curves acquired between fullerene molecules exhibit a nonvanishing slope at zero bias whereas {ital I}({ital V}) characteristics measured above molecules exhibit vanishing slope at zero bias. {copyright} {ital 1996 American Vacuum Society}

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Time-resolved spectroscopy of the singlet excited state of betanin in aqueous and alcoholic solutions.

    PubMed

    Wendel, Monika; Nizinski, Stanislaw; Tuwalska, Dorota; Starzak, Karolina; Szot, Dominika; Prukala, Dorota; Sikorski, Marek; Wybraniec, Slawomir; Burdzinski, Gotard

    2015-07-21

    The photophysical properties of betanin in aqueous and alcoholic solutions were determined at room temperature using ultrafast UV-vis-NIR transient absorption spectroscopy (λexc = 535 nm). Its S1 → Sn (n > 1) absorption bands appear with maxima at about λ ∼ 450 and 1220 nm. The short betanin S1 state lifetime (6.4 ps in water) is mainly determined by the efficient S1 → S0 radiationless relaxation, probably requiring a strong change in geometry, since the S1 lifetime grows to 27 ps in the more viscous ethylene glycol. The fluorescence quantum yield is very low (Φf ∼ 0.0007 in water), therefore this deactivation path is of minor importance. Other processes, such as S1 → T1 intersystem crossing or photoproduct formation, are virtually absent, since full S0 ← S1 ground state recovery is observed within tens of picoseconds after photoexcitation. The observed fast light-to-heat conversion in the absence of triplet excited state formation supports the idea that betanin is a photoprotector in vivo.

  10. Direct Visualization of Excited-State Symmetry Breaking Using Ultrafast Time-Resolved Infrared Spectroscopy.

    PubMed

    Dereka, Bogdan; Rosspeintner, Arnulf; Li, Zhiquan; Liska, Robert; Vauthey, Eric

    2016-04-01

    Most symmetric quadrupolar molecules designed for two-photon absorption behave as dipolar molecules in the S1 electronic excited state. This is usually explained by a breakup of the symmetry in the excited state. However, the origin of this process and its dynamics are still not fully understood. Here, excited-state symmetry breaking in a quadrupolar molecule with a D-π-A-π-D motif, where D and A are electron donating and accepting units, is observed in real time using ultrafast transient infrared absorption spectroscopy. The nature of the relaxed S1 state was found to strongly depend on the solvent polarity: (1) in nonpolar solvents, it is symmetric and quadrupolar; (2) in weakly polar media, the quadrupolar state observed directly after excitation transforms to a symmetry broken S1 state with one arm bearing more excitation than the other; and (3) in highly polar solvents, the excited state evolves further to a purely dipolar S1 state with the excitation localized entirely on one arm. The time scales associated with the transitions between these states coincide with those of solvation dynamics, indicating that symmetry breaking is governed by solvent fluctuations.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Absolute calibration method for nanosecond-resolved, time-streaked, fiber optic light collection, spectroscopy systems.

    PubMed

    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/cm(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. PMID:22938275

  16. Spatially resolved force spectroscopy of bacterial surfaces using force-volume imaging.

    PubMed

    Gaboriaud, Fabien; Parcha, Bhargava S; Gee, Michelle L; Holden, James A; Strugnell, Richard A

    2008-04-01

    Force spectroscopy using the atomic force microscope (AFM) is a powerful technique for measuring physical properties and interaction forces at microbial cell surfaces. Typically for such a study, the point at which a force measurement will be made is located by first imaging the cell using AFM in contact mode. In this study, we image the bacterial cell Shewanella putrefaciens for subsequent force measurements using AFM in force-volume mode and compare this to contact-mode images. It is known that contact-mode imaging does not accurately locate the apical surface and periphery of the cell since, in contact mode, a component of the applied load laterally deforms the cell during the raster scan. Here, we illustrate that contact-mode imaging does not accurately locate the apical surface and periphery of the cell since, in contact mode, a component of the applied load laterally deforms the cell during the raster scan. This is an artifact due to the deformability and high degree of curvature of bacterial cells. We further show that force-volume mode imaging avoids the artifacts associated with contact-mode imaging due to surface deformation since it involves the measurement of a grid of individual force profiles. The topographic image is subsequently reconstructed from the zero-force height (the contact distance between the AFM tip and the surface) at each point on the cell surface. We also show how force-volume measurements yield applied load versus indentation data from which mechanical properties of the cell such as Young's modulus, cell turgor pressure and elastic and plastic energies can be extracted.

  17. 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

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

    NASA Astrophysics Data System (ADS)

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

    2009-02-01

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

  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

    NASA Astrophysics Data System (ADS)

    Blake, Thomas A.; Sharpe, Steven W.; Xantheas, Sotiris S.

    2000-07-01

    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 Au symmetry. Ninety-five ground state combination differences were fit to a symmetric top Hamiltonian to give the following ground state rotational constants: B″=0.132 081(7) cm-1, DJ″=7.1(7)×10-7 cm-1, DJK″=-9(2)×10-7 cm-1, HJJJ″=6(2)×10-10 cm-1, HJJK″=9(7)×10-10 cm-1, HJKK″=-1.3(8)×10-10 cm-1. A total of 190 transitions were fit to determine the upper state spectroscopic constants: v4=714.7849(1) cm-1, B'=0.129 634(5) cm-1, Δ(C-B)=0.001 344 cm-1, DJ'=6.4(5)×10-7 cm-1, DJK'=-4.5(6)×10-7 cm-1, ΔDK=2.92(8)×10-6 cm-1, HJJJ'=3(1)×10-10 cm-1, HJKK'=-1.55(6)×10-8 cm-1; ΔHKKK=-4.65(6)×10-8 cm-1. Furthermore, a perpendicular band centered at 752.7 cm-1 was observed. The band has a rotational line spacing that gives an approximate B″ value of 0.132 cm-1; it has been assigned as the Eu symmetry, H-F in-plane libration fundamental of the HF tetramer. Finally, a parallel band was observed at 741.0 cm-1 with B″=0.076 cm-1 and has been assigned as the A″ 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, the first reported for the tetramer at this level of theory. Based on our results, we suggest "best estimates" of RFF=2.51 Å, rHF=0.947 Å, and θHFF=9.7° for the structural parameters and a range for De of 27.4 to 28.1 kcal/mol (D0=19.7 to 20.4 kcal/mol) for the parameters and for the energy of the tetramer dissociating into four

  1. 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

  2. Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy.

    PubMed

    Wilkinson, Iain; Boguslavskiy, Andrey E; Mikosch, Jochen; Bertrand, Julien B; Wörner, Hans Jakob; Villeneuve, David M; Spanner, Michael; Patchkovskii, Serguei; Stolow, Albert

    2014-05-28

    The excited state dynamics of isolated sulfur dioxide molecules have been investigated using the time-resolved photoelectron spectroscopy and time-resolved photoelectron-photoion coincidence techniques. Excited state wavepackets were prepared in the spectroscopically complex, electronically mixed (B̃)(1)B1/(Ã)(1)A2, Clements manifold following broadband excitation at a range of photon energies between 4.03 eV and 4.28 eV (308 nm and 290 nm, respectively). The resulting wavepacket dynamics were monitored using a multiphoton ionisation probe. The extensive literature associated with the Clements bands has been summarised and a detailed time domain description of the ultrafast relaxation pathways occurring from the optically bright (B̃)(1)B1 diabatic state is presented. Signatures of the oscillatory motion on the (B̃)(1)B1/(Ã)(1)A2 lower adiabatic surface responsible for the Clements band structure were observed. The recorded spectra also indicate that a component of the excited state wavepacket undergoes intersystem crossing from the Clements manifold to the underlying triplet states on a sub-picosecond time scale. Photoelectron signal growth time constants have been predominantly associated with intersystem crossing to the (c̃)(3)B2 state and were measured to vary between 750 and 150 fs over the implemented pump photon energy range. Additionally, pump beam intensity studies were performed. These experiments highlighted parallel relaxation processes that occurred at the one- and two-pump-photon levels of excitation on similar time scales, obscuring the Clements band dynamics when high pump beam intensities were implemented. Hence, the Clements band dynamics may be difficult to disentangle from higher order processes when ultrashort laser pulses and less-differential probe techniques are implemented.

  3. 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.

  4. Spatio-temporally resolved diagnostics of the barrier discharge by cross-correlation spectroscopy in air at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Wagner, Hans-Erich

    2002-10-01

    The technique of spatially resolved cross-correlation spectroscopy (CCS) is used to carry out diagnostic measurements of the barrier discharge (BD) in air at atmospheric pressure.(Kozlov K V, Wagner H-E, Brandenburg R, Michel P 2001 J. Phys. D: Appl. Phys. 34 3164-3176.) (Kozlov K V, Dobryakov V V, Monyakin A P, Samoilovich V G, Shepeliuk O S, and Wagner H-E, Brandenburg R, Michel P 2002 in: Selected Research Papers on Spectroscopy of Nonequilibrium Plasma at Elevated Pressures, Vladimir N. Ochkin, Editor, Proceedings of SPIE vol. 4460, 165-176 Washington (USA).) Quantitative estimates for the electric field strength E(x,t) and for relative electron density n_e(x,t)/ne max are derived from the experimentally determined spatio-temporal distributions of the luminosity for the spectral bands of the 00 transitions of the second positive system of N2 (λ =337.1 nm) and the first negative system of N_2^+ (λ =391.5 nm). All the measurements and calculations have been performed for a BD with the symmetrical electrode arrangement (glass - glass), discharge gap width of 1.2 mm, in flowing synthetic air (80 % N2 + 20 % O_2) at atmospheric pressure. It is shown that the streamer starts directly from the surface of the anode and crosses the gap with an increasing velocity that reaches 10^6 m/s. The reduced electric field of the streamer grows from 120 Td at the anode to 240 Td at the cathode, respectively. The influence of the spatio-temporal structure of the discharge on the chemical kinetics of ozone synthesis is studied within the frame of the kinetic model based on the results of spatially resolved CCS measurements. It is demonstrated that the properties of the plasma in the region near the anode (where the electric field is lower but electron density is higher than near the cathode), favor dissociation of molecular oxygen by direct electron impact. In the case of the excitation of triplet nitrogen states, the contributions of both regions to this process appear to be

  5. 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

  6. Laser double-resonance studies of electronic spectroscopy and state-resolved collisional relaxation in highly vibrationally excited acetylene

    SciTech Connect

    Tobiason, J.D.

    1992-01-01

    Vibrational overtone excitation combined with laser-induced fluorescence detection of acetylene molecules permits rotation-selected spectroscopy of the ([tilde A][sup 1]A[sub u]) electronic state and direct, state-resolved measurements of collisional energy transfer in the highly vibrationally excited ground electronic state. The author assigns energies of 1,045 transitions to previously unobserved ungerade vibrational states 2800-4500 cm[sup [minus]1] above the [tilde A] state origin. An analysis yields frequencies of 2856.4 and 3894.3 cm[sup [minus]1] for [nu][sub v][prime] and [nu][sub 3][prime] + [nu][sub 5][prime]. The author performs the first normal coordinate analysis of [tilde A] state acetylene based only on directly observed fundamentals. The spectroscopy measurements enable double-resonance experiments on the collisional dynamics of highly vibrationally excited acetylene. The quenching rate for single rotational states is twice the Lennard-Jones gas kinetic rate and fairly independent of vibrational energy level. Collision-induced detection of vibrational overtone excitation under single collision conditions allows direct measurements of state-of-state rotational and vibrational energy transfer. A collision-induced spectrum obtained by this new technique immediately identifies transfer channels and the [Delta]J and [Delta]E dependence of the transfer rates. The author observes changes of [vert bar][Delta]J[vert bar] and [Delta]E [approx] 3kT in a single collision. Directly measured rates for one set of vibrational relaxation pathways account for [approximately]3% of the total relaxation rate. The author also observes other vibrational relaxation pathways. The available pathways suggest that vibrational relaxation accounts for the rest of the total relaxation. Changes of [vert bar]J[vert bar] = 18 and [vert bar][Delta]E[vert bar] [approximately] 500 cm[sup [minus]1] in a single collision are observed.

  7. 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.

  8. Resolving voltage-dependent structural changes of a membrane photoreceptor by surface-enhanced IR difference spectroscopy.

    PubMed

    Jiang, X; Zaitseva, E; Schmidt, M; Siebert, F; Engelhard, M; Schlesinger, R; Ataka, K; Vogel, R; Heberle, J

    2008-08-26

    Membrane proteins are molecular machines that transport ions, solutes, or information across the cell membrane. Electrophysiological techniques have unraveled many functional aspects of ion channels but suffer from the lack of structural sensitivity. Here, we present spectroelectrochemical data on vibrational changes of membrane proteins derived from a single monolayer. For the seven-helical transmembrane protein sensory rhodopsin II, structural changes of the protein backbone and the retinal cofactor as well as single ion transfer events are resolved by surface-enhanced IR difference absorption spectroscopy (SEIDAS). Angular changes of bonds versus the membrane normal have been determined because SEIDAS monitors only those vibrations whose dipole moment are oriented perpendicular to the solid surface. The application of negative membrane potentials (DeltaV = -0.3 V) leads to the selective halt of the light-induced proton transfer at the stage of D75, the counter ion of the retinal Schiff base. It is inferred that the voltage raises the energy barrier of this particular proton-transfer reaction, rendering the energy deposited in the retinal by light excitation insufficient for charge transfer to occur. The other structural rearrangements that accompany light-induced activity of the membrane protein, are essentially unaffected by the transmembrane electric field. Our results demonstrate that SEIDAS is a generic approach to study processes that depend on the membrane potential, like those in voltage-gated ion channels and transporters, to elucidate the mechanism of ion transfer with unprecedented spatial sensitivity and temporal resolution.

  9. 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.

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

    NASA Astrophysics Data System (ADS)

    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 ṡ 1010 photons/s (at 5 kHz) in the 29th harmonic, after the monochromator. The XUV pulse duration is measured to be <25 fs after monochromatization.

  11. Viscosity heterogeneity inside lipid bilayers of single-component phosphatidylcholine liposomes observed with picosecond time-resolved fluorescence spectroscopy.

    PubMed

    Nojima, Yuki; Iwata, Koichi

    2014-07-24

    A number of biochemical reactions proceed inside biomembranes. Because the rate of a chemical reaction is influenced by chemical properties of the reaction field, it is important to examine the chemical properties inside the biomembranes, or lipid bilayer membranes, for understanding biochemical reactions. In this study, we estimate viscosity inside the lipid bilayers of liposomes with picosecond time-resolved fluorescence spectroscopy. trans-Stilbene is solubilized in the lipid bilayers formed by phosphatidylcholines, DSPC, DOPC, DPPC, DMPC, and DLPC, with 18, 18, 16, 14, and 12 carbon atoms in their alkyl chains, respectively, and egg-PC. Viscosity inside the lipid bilayer is estimated from the photoisomerization rate constant and from the rotational relaxation time of the first excited singlet state of trans-stilbene. The effect of the hydrocarbon chain length and temperature on viscosity is examined. The presence of two solvation environments within the lipid bilayer is indicated from the two independent estimations. One environment is 30 to 290 times more viscous than the other. Even single-component lipid bilayers are likely to have heterogeneous structures.

  12. 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.

  13. Two-photon resonances in femtosecond time-resolved four-wave mixing spectroscopy: β-carotene

    NASA Astrophysics Data System (ADS)

    Namboodiri, V.; Namboodiri, M.; Flachenecker, G.; Materny, A.

    2010-08-01

    Femtosecond time-resolved pump-degenerate four-wave mixing (pump-DFWM) spectroscopy has been used to study the ultrafast dynamics of β-carotene involving several electronic and vibrational states. An initial pump pulse, resonant with the S0-to-S2 transition, excites the molecular system and a DFWM process, resonant with the S1-to-Sn 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 S1 state, nonresonant DFWM signal of the ground S0 state and vibrational hot S0∗ state, and the two-photon resonant DFWM signal of the ground S0 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 β-carotene. For comparison, a two-pulse pump-probe experiment was performed measuring the transient absorption at the wavelength of the DFWM experiment.

  14. 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.

  15. Spatially and spectrally resolved particle swarm optimization for precise optical property estimation using diffuse-reflectance spectroscopy.

    PubMed

    Kholodtsova, Maria N; Daul, Christian; Loschenov, Victor B; Blondel, Walter C P M

    2016-06-13

    This paper presents a new approach to estimate optical properties (absorption and scattering coefficients µa and µs) of biological tissues from spatially-resolved spectroscopy measurements. A Particle Swarm Optimization (PSO)-based algorithm was implemented and firstly modified to deal with spatial and spectral resolutions of the data, and to solve the corresponding inverse problem. Secondly, the optimization was improved by fitting exponential decays to the two best points among all clusters of the "particles" randomly distributed all over the parameter space (µs, µa) of possible solutions. The consequent acceleration of all the groups of particles to the "best" curve leads to significant error decrease in the optical property estimation. The study analyzes the estimated optical property error as a function of the various PSO parameter combinations, and several performance criteria such as the cost-function error and the number of iterations in the algorithms proposed. The final one led to error values between ground truth and estimated values of µs and µa less than 6%. PMID:27410289

  16. 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.

  17. 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.

  18. Optical studies of the X-ray transient XTE J2123-058 - II. Phase-resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Hynes, R. I.; Charles, P. A.; Haswell, C. A.; Casares, J.; Zurita, C.; Serra-Ricart, M.

    2001-06-01

    We present time-resolved spectroscopy of the soft X-ray transient XTEJ2123-058 in outburst. A useful spectral coverage of 3700-6700Å was achieved spanning two orbits of the binary, with single-epoch coverage extending to ~9000Å. The optical spectrum approximates a steep blue power law, consistent with emission on the Rayleigh-Jeans tail of a hot blackbody spectrum. The strongest spectral lines are Heii 4686Å and Ciii/Niii 4640Å (Bowen blend) in emission. Their relative strengths suggest that XTEJ2123-058 was formed in the Galactic plane, not in the halo. Other weak emission lines of Heii and Civ are present, and Balmer lines show a complex structure, blended with Heii. Heii 4686-Å profiles show a complex multiple S-wave structure, with the strongest component appearing at low velocities in the lower-left quadrant of a Doppler tomogram. Hα shows transient absorption between phases 0.35 and 0.55. Both of these effects appear to be analogous to similar behaviour in SW Sex type cataclysmic variables. We therefore consider whether the spectral line behaviour of XTEJ2123-058 can be explained by the same models invoked for those systems.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

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

  1. 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.

  2. in situ studied correlated oxide LaNiO3 ultra thin film by angle resolved photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Yoo, H. K.; Chang, Y. J.; Kim, K. S.; Moreschini, L.; Jeong, D. W.; Kim, Y. S.; Bostwick, A.; Rotenberg, E.; Noh, T. W.

    2012-02-01

    Recently, RNiO3 (R: rare earth) attracted increasing attention due to the possible realization of the electronic band structure similar to the high-temperature superconductor cuprates. Among them, LaNiO3 based heterostructures have shown various fascinating physical properties such as dimensionality controlled electronic phase transitions. Theoretical works on confined LaNiO3 through heterostructuring predicted cuprate-like band structure and magnetic properties. Here, we reports in-situ angle resolved photoemission spectroscopy results on the LaNiO3 films grown by pulsed laser deposition method. We carefully controlled the thickness of LaNiO3 films from one to 30 unit cells and measured the thickness dependent band dispersions. First, we will discuss the strong electronic correlation effect in bulk-like band structure of thick LaNiO3 films comparing to the previously reported LDA+DMFT calculation. Moreover, we will discuss the thickness dependent band structure. As decreasing the film thickness, we observed the charge redistribution of two Ni eg orbitals at the Fermi surface. The origins of thickness dependent electronic structure will be discussed.

  3. Proton Transfer of Guanine Radical Cations Studied by Time-Resolved Resonance Raman Spectroscopy Combined with Pulse Radiolysis.

    PubMed

    Choi, Jungkweon; Yang, Cheolhee; Fujitsuka, Mamoru; Tojo, Sachiko; Ihee, Hyocherl; Majima, Tetsuro

    2015-12-17

    The oxidation of guanine (G) is studied by using transient absorption and time-resolved resonance Raman spectroscopies combined with pulse radiolysis. The transient absorption spectral change demonstrates that the neutral radical of G (G(•)(-H(+))), generated by the deprotonation of G radical cation (G(•+)), is rapidly converted to other G radical species. The formation of this species shows the pH dependence, suggesting that it is the G radical cation (G(•+))' formed from the protonation at the N7 of G(•)(-H(+)). On one hand, most Raman bands of (G(•+))' are up-shifted relative to those of G, indicating the increase in the bonding order of pyrimidine (Pyr) and imidazole rings. The (G(•+))' exhibits the characteristic CO stretching mode at ∼1266 cm(-1) corresponding to a C-O single bond, indicating that the unpaired electron in (G(•+))' is localized on the oxygen of the Pyr ring. PMID:26632994

  4. 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.

  5. Experimental Investigation of Coronal Plasma Conditions in Direct-Drive ICF Using Time-Resolved X-Ray Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sawada, H.; Regan, S. P.; Goncharov, V. N.; Knauer, J. P.; Epstein, R.; Craxton, R. S.; Delettrez, J. A.; Marshall, F. J.; Yaakobi, B.; Meyerhofer, D. D.; Radha, P. B.; Sangster, T. C.; Seka, W.

    2003-10-01

    The ne and Te of planar plasmas generated with six beams of the OMEGA laser are diagnosed with time-resolved K-shell spectroscopy of microdot tracer layers. Plastic foils (125 μm thick) with buried microdots (Al, KCl) were irradiated with a high-intensity, 100-ps Gaussian pulse (5 × 10^14 W/cm^2) or a low-intensity (3 × 10^13 W/cm^2), 1-ns square pulse, corresponding to the initial stages of direct-drive implosions with and without a short, high-intensity picket at the beginning of the drive pulse. The microdot buried depth was varied (0.1 to 0.5 μm) to probe the plasma at different times. Simulated spectra generated by post-processing hydrocode output (1-D LILAC, 2-D SAGE) with the FLY atomic physics code will be compared with the measured spectra. This work was supported by the U.S. Department of Energy Office of Inertial Confinement Fusion under Cooperative Agreement No. DE-FC03-92SF19460.

  6. 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.

  7. Short-term light adaptation of a cyanobacterium, Synechocystis sp. PCC 6803, probed by time-resolved fluorescence spectroscopy.

    PubMed

    Akimoto, Seiji; Yokono, Makio; Yokono, Erina; Aikawa, Shimpei; Kondo, Akihiko

    2014-08-01

    In photosynthetic organisms, the interactions among pigment-protein complexes change in response to light conditions. In the present study, we analyzed the transfer of excitation energy from the phycobilisome (PBS) and photosystem (PS) II to PSI in the cyanobacterium Synechocystis sp. PCC 6803. After 20 min of dark adaptation, Synechocystis cells were illuminated for 5 min with strong light with different spectral profiles, blue, green, two kinds of red, and white light. After illumination, the energy-transfer characteristics were evaluated using steady-state fluorescence and picosecond time-resolved fluorescence spectroscopy techniques. The fluorescence rise and decay curves were analyzed by global analysis to obtain fluorescence decay-associated spectra, followed by spectral component analysis. Under illumination with strong light, the contribution of the energy transfer from the PSII to PSI (spillover) became greater, and that of the energy transfer from the PBS to PSI decreased; the former change was larger than the latter. The energy transfer pathway to PSI was sensitive to red light. We discuss the short-term adaptation of energy-transfer processes in Synechocystis under strong-light conditions.

  8. 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

  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. 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

  11. Time-Resolved Frequency Comb Spectroscopy for Studying the Kinetics and Branching Ratio of OD+CO

    NASA Astrophysics Data System (ADS)

    Bui, Thinh Quoc; Bjork, Bryce J.; Heckl, Oliver H.; Changala, Bryan; Spaun, Ben; Okumura, Mitchio; Ye, Jun

    2016-06-01

    The chemical kinetics of the OH+CO reaction plays important roles in combustion and atmospheric processes. OH+CO has two product channels, H+CO_2 and the stabilized HOCO intermediate, with a branching ratio that is highly pressure dependent. Therefore, establishing an accurate kinetic model for this chemical system requires knowledge of the reaction rates and product yields, and the lifetimes of all molecules along a particular reaction pathway. We report the application of time-resolved frequency comb spectroscopy (TRFCS) in the mid-infrared (3.7 μm) spectral region to address the complex reaction kinetics of OD+CO at room temperature. We use the deuterated forms to avoid atmospheric water interference. This technique allows us to detect the lowest energy conformer trans-DOCO intermediate with high time-resolution and sensitivity while also permitting the direct determination of rotational state distributions of all relevant molecules. We simultaneously observe the time-dependent concentrations of trans-DOCO, OD, and D_2O which are used in conjunction with kinetics modeling to obtain the pressure- and collision partner-dependent branching ratio of OD+CO.

  12. Time-Resolved Frequency Comb Spectroscopy of Transient Free Radicals in the Mid-Infrared Spectral Region

    NASA Astrophysics Data System (ADS)

    Bjork, Bryce J.; Fleisher, Adam J.; Changala, Bryan; Bui, Thinh Quoc; Cossel, Kevin; Okumura, Mitchio; Ye, Jun

    2014-06-01

    The chemical kinetics of transient free radicals, such as HOCO and Criegee intermediates, play important roles in combustion and atmospheric processes. Establishing accurate kinetics models for these complex systems require knowledge of the reaction rates and lifetimes of all molecules along a particular reaction pathway. However, standard spectroscopic techniques lack a combination of sensitivity, frequency resolution, and adequate temporal resolution to survey these reactions on the μs timescale. To answer this challenge, we have developed time-resolved frequency comb spectroscopy (TRFCS). This novel technique allows for the detection of transient intermediates with high time-resolution and sensitivity while also permitting the direct determination of rotational state distributions of all relevant molecules. We demonstrate this technique in the mid-infrared spectral region, at 3.7 μm, by studying the photolysis of deuterated acrylic acid. We simultaneously observe the time-dependent concentrations of photoproducts trans-DOCO, HOD, and D_2O, identified through their unique rovibrational structure, with 5 × 1010 molecules cm-3 sensitivity, and with a time resolution of 25 μs. We aim to apply this technique to detect directly the formation of the DOCO intermediate in the OD + CO chemical reaction at atmospherically relevant pressures, in order to validate statistical rate models of this reaction.

  13. 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

  14. The primary photophysics of the Avena sativa phototropin 1 LOV2 domain observed with time-resolved emission spectroscopy.

    PubMed

    van Stokkum, Ivo H M; Gauden, Magdalena; Crosson, Sean; van Grondelle, Rienk; Moffat, Keith; Kennis, John T M

    2011-01-01

    The phototropins are blue-light receptors that base their light-dependent action on the reversible formation of a covalent bond between a flavin mononucleotide (FMN) cofactor and a conserved cysteine in light, oxygen or voltage (LOV) domains. The primary reactions of the Avena sativa phototropin 1 LOV2 domain were investigated by means of time-resolved and low-temperature fluorescence spectroscopy. Synchroscan streak camera experiments revealed a fluorescence lifetime of 2.2 ns in LOV2. A weak long-lived component with emission intensity from 600 to 650 nm was assigned to phosphorescence from the reactive FMN triplet state. This observation allowed determination of the LOV2 triplet state energy level at physiological temperature at 16600 cm(-1). FMN dissolved in aqueous solution showed pH-dependent fluorescence lifetimes of 2.7 ns at pH 2 and 3.9-4.1 ns at pH 3-8. Here, too, a weak phosphorescence band was observed. The fluorescence quantum yield of LOV2 increased from 0.13 to 0.41 upon cooling the sample from 293 to 77 K. A pronounced phosphorescence emission around 600 nm was observed in the LOV2 domain between 77 and 120 K in the steady-state emission.

  15. Spatially resolved bimodal spectroscopy for classification/evaluation of mouse skin inflammatory and pre-cancerous stages

    NASA Astrophysics Data System (ADS)

    Díaz-Ayil, Gilberto; Amouroux, Marine; Clanché, Fabien; Granjon, Yves; Blondel, Walter C. P. M.

    2009-07-01

    Spatially-resolved bimodal spectroscopy (multiple AutoFluorescence AF excitation and Diffuse Reflectance DR), was used in vivo to discriminate various healthy and precancerous skin stages in a pre-clinical model (UV-irradiated mouse): Compensatory Hyperplasia CH, Atypical Hyperplasia AH and Dysplasia D. A specific data preprocessing scheme was applied to intensity spectra (filtering, spectral correction and intensity normalization), and several sets of spectral characteristics were automatically extracted and selected based on their discrimination power, statistically tested for every pair-wise comparison of histological classes. Data reduction with Principal Components Analysis (PCA) was performed and 3 classification methods were implemented (k-NN, LDA and SVM), in order to compare diagnostic performance of each method. Diagnostic performance was studied and assessed in terms of Sensibility (Se) and Specificity (Sp) as a function of the selected features, of the combinations of 3 different inter-fibres distances and of the numbers of principal components, such that: Se and Sp ~ 100% when discriminating CH vs. others; Sp ~ 100% and Se > 95% when discriminating Healthy vs. AH or D; Sp ~ 74% and Se ~ 63% for AH vs. D.

  16. SmB6 electron-phonon coupling constant from time- and angle-resolved photoelectron spectroscopy

    NASA Astrophysics Data System (ADS)

    Sterzi, A.; Crepaldi, A.; Cilento, F.; Manzoni, G.; Frantzeskakis, E.; Zacchigna, M.; van Heumen, E.; Huang, Y. K.; Golden, M. S.; Parmigiani, F.

    2016-08-01

    SmB6 is a mixed valence Kondo system resulting from the hybridization between localized f electrons and delocalized d electrons. We have investigated its out-of-equilibrium electron dynamics by means of time- and angle-resolved photoelectron spectroscopy. The transient electronic population above the Fermi level can be described by a time-dependent Fermi-Dirac distribution. By solving a two-temperature model that well reproduces the relaxation dynamics of the effective electronic temperature, we estimate the electron-phonon coupling constant λ to range from 0.13 ±0.03 to 0.04 ±0.01 . These extremes are obtained assuming a coupling of the electrons with either a phonon mode at 10 or 19 meV. A realistic value of the average phonon energy will give an actual value of λ within this range. Our results provide an experimental report on the material electron-phonon coupling, contributing to both the electronic transport and the macroscopic thermodynamic properties of SmB6.

  17. 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.

  18. Angle-resolved photoemission spectroscopy with a femtosecond high harmonic light source using a two-dimensional imaging electron analyzer

    NASA Astrophysics Data System (ADS)

    Mathias, S.; Miaja-Avila, L.; Murnane, M. M.; Kapteyn, H.; Aeschlimann, M.; Bauer, M.

    2007-08-01

    An experimental setup for time- and angle-resolved photoemission spectroscopy using a femtosecond 1kHz high harmonic light source and a two-dimensional electron analyzer for parallel energy and momentum detection is presented. A selection of the 27th harmonic (41.85eV) from the harmonic spectrum of the light source is achieved with a multilayer Mo /Si double mirror monochromator. The extinction efficiency of the monochromator in selecting this harmonic is shown to be better than 7:1, while the transmitted bandwidth of the selected harmonic is capable of supporting temporal pulse widths as short as 3fs. The recorded E(k ) photoelectron spectrum from a Cu(111) surface demonstrates an angular resolution of better than 0.6° (=0.03Å-1 at Ekin ,e=36eV). Used in a pump-probe configuration, the described experimental setup represents a powerful experimental tool for studying the femtosecond dynamics of ultrafast surface processes in real time.

  19. PMAS optical integral field spectroscopy of luminous infrared galaxies. II. Spatially resolved stellar populations and excitation conditions

    NASA Astrophysics Data System (ADS)

    Alonso-Herrero, A.; García-Marín, M.; Rodríguez Zaurín, J.; Monreal-Ibero, A.; Colina, L.; Arribas, S.

    2010-11-01

    Context. The general properties (e.g., activity class, star formation rates, metallicities, extinctions, average ages, etc.) of luminous (LIRGs) and ultraluminous infrared galaxies (ULIRGs) in the local universe are well known because large samples of these objects have been the subject of numerous spectroscopic works over the past three decades. There are, however, relatively few studies of the spatially-resolved spectroscopic properties of large samples of LIRGs and ULIRGs using integral field spectroscopy (IFS). Aims: We are carrying out an IFS survey of local (z<0.26) samples of LIRGs and ULIRGs to characterize their two-dimensional spectroscopic properties. The main goal of this paper is to study the spatially resolved properties of the stellar populations and the excitation conditions in a sample of LIRGs. Methods: We analyze optical (3800-7200 Å) IFS data taken with the Potsdam Multi-Aperture Spectrophotometer (PMAS) of the central few kiloparsecs of eleven LIRGs. To study these stellar populations, we fit the optical stellar continuum and the hydrogen recombination lines of selected regions in the galaxies. We analyzed the excitation conditions of the gas using the spatially resolved properties of the brightest optical emission lines. We complemented the PMAS observations with existing HST/NICMOS near-infrared continuum and Paα imaging. Results: The optical continua of selected regions in our LIRGs are well fitted with a combination of an evolved (~0.7-10 Gyr) stellar population with an ionizing stellar population (1-20 Myr). The latter population is more obscured than the evolved population, and has visual extinctions in good agreement with those obtained from the Balmer decrement. Except for NGC 7771, we find no clear that there is an important contribution to the optical light from an intermediate-aged stellar population (~100-500 Myr). Even after correcting for the presence of stellar absorption, a large number of spaxels with low observed equivalent

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. 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

  5. The Super-Star Cluster NGC 1569-A Resolved on Subparsec Scales with Hubble Space Telescope Spectroscopy

    NASA Astrophysics Data System (ADS)

    Maoz, Dan; Ho, Luis C.; Sternberg, Amiel

    2001-06-01

    We present 3000-10000 Å Hubble Space Telescope (HST)/Space Telescope Imaging Spectrograph long-slit spectroscopy of the bright super-star cluster A (SSC-A) in the dwarf starburst galaxy NGC 1569. The 0.05" HST angular resolution allows us, for the first time, to probe for spatial variations in the stellar population of an ~106 Msolar SSC. Integrated ground-based spectra of SSC-A have previously revealed young Wolf-Rayet (W-R) signatures that coexist with features from supposedly older, red supergiant (RSG) populations. We find that the W-R emission complexes come solely from the subcluster A2, identified in previous HST imaging, and are absent from the main cluster A1, thus resolving the question of whether the W-R and RSG features arise in a single or distinct clusters. The equivalent widths of the W-R features in A2-including the C IV λ5808 complex that we detect in this object for the first time-are larger than previously observed in other W-R galaxies. Models with subsolar metallicity, as inferred from the nebular emission lines of this galaxy, predict much lower equivalent widths. On the ``clean'' side of A1, opposite to A2, we find no evidence for radial gradients in the observed stellar population at 0.05"

  6. 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.

  7. Design, simulation and application of a new micromixing device for time resolved infrared spectroscopy of chemical reactions in solution.

    PubMed

    Hinsmann, P; Frank, J; Svasek, P; Harasek, M; Lendl, B

    2001-09-01

    We present a novel micromachined fast diffusion based mixing unit for the study of rapid chemical reactions in solution with stopped-flow time resolved Fourier transform infrared spectroscopy (TR-FTIR). The presented approach is based on a chip for achieving lamination of two liquid sheets of 10 microm thickness and approximately 1 mm width on top of each other and operation in the stopped-flow mode. The microstructure is made on infrared transmitting calcium fluoride discs and built up with two epoxy negative photoresist layers and one silver layer in between. Due to the highly laminar flow conditions and the short residence time in the mixer there is hardly any mixing when the two liquid streamlines pass through the mixing unit, which allows one to record a mid-IR transmission spectrum of the analytes prior to reaction. When the flow is stopped, the reactant streams are arrested in the flow-cell and rapidly mixed by diffusion due to the reduced interstream distances and the reaction can be directly followed with hardly any dead time. On the basis of two model reactions-neutralisation of acetic acid with sodium hydroxide as well as saponification of methyl monochloroacetate-the performance of the mixing device was tested revealing proper functioning of the device with a time for complete mixing of less than 100 ms. The experimental results were supported by numerical simulations using computational fluid dynamics (CFD), which allowed a reliable, quantitative analysis of concentration, pressure and flow profiles in the course of the mixing process.

  8. 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.

  9. 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

  10. 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.

  11. Visualizing chemical states and defects induced magnetism of graphene oxide by spatially-resolved-X-ray microscopy and spectroscopy.

    PubMed

    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

    2015-10-20

    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.

  12. 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

  13. 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

  14. 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

  15. Photoexcited State Properties of H2-Porphyrin/C60-Based Rotaxanes as Studied by Time-Resolved EPR Spectroscopy

    PubMed Central

    Jakob, Manuela; Berg, Alexander; Levanon, Haim; Schuster, David I.; Megiatto, Jackson D.

    2011-01-01

    Light-driven intramolecular electron transfer (ET) and energy transfer (EnT) processes in two rotaxanes, the first containing two free base porphyrins and C60 fullerene moieties incorporated around a Cu(I)bisphenanthroline core ((H2P)2-Cu(I)(phen)2-C60) and a second rotaxane lacking the fullerene moiety ((H2P)2-Cu(I)(phen)2) were studied by X-band (9.5 GHz) time-resolved electron paramagnetic resonance (TREPR) spectroscopy. The experiments were performed in a frozen toluene and ethanol, and different phases of the nematic liquid crystal (E-7). It is demonstrated that the ET and EnT processes in the (H2P)2-Cu(I)(phen)2-C60 rotaxane in different media result in formation of the same charge separated state, namely (H2P)2•+-Cu(I)(phen)2•−-C60, while photoexcitation of the (H2P)2-Cu(I)(phen)2 rotaxane does not induce noticeable transfer processes in these matrices. The results are discussed in terms of the high conformational mobility of the rotaxanes, which enables changes in the molecular topography and resultant modification of the rates and routes of photoinduced processes occurring in these systems. The parameters of the transfer processes are compared with those obtained in our previous study of (ZnP)2-Cu(I)(phen)2-C60 and (ZnP)2-Cu(I)(phen) rotaxanes under the same experimental conditions. PMID:21528881

  16. Metal binding properties of fluorescent analogues of trichogin GA IV: a conformational study by time-resolved spectroscopy and molecular mechanics investigations.

    PubMed

    Venanzi, Mariano; Bocchinfuso, Gianfranco; Gatto, Emanuela; Palleschi, Antonio; Stella, Lorenzo; Formaggio, Fernando; Toniolo, Claudio

    2009-01-01

    The metal ion binding properties of two fluorescent analogues of trichogin GA IV, which is a natural undecapeptide showing significant antimicrobial activity, were studied by circular dichroism, time-resolved optical spectroscopy, and molecular mechanics calculations. Binding of Ca(II) and Gd(III) to the peptides investigated was shown to promote a structural transition from highly helical conformations to folded structures characterized by formation of a loop that embedded the metal ion. Time-resolved spectroscopy revealed that peptide dynamics is also remarkably affected by ion binding: peptide-backbone motions slowed down to the microsecond time scale. Finally, molecular mechanics calculations emphasized the role of the central Gly5-Gly6 motif, which allowed for the twisting of the peptide segment that gave rise to the formation of the binding cavity.

  17. 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.

  18. 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

  19. 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.

  20. Phase-resolved spectroscopy and Kepler photometry of the ultracompact AM CVn binary SDSS J190817.07+394036.4

    NASA Astrophysics Data System (ADS)

    Kupfer, T.; Groot, P. J.; Bloemen, S.; Levitan, D.; Steeghs, D.; Marsh, T. R.; Rutten, R. G. M.; Nelemans, G.; Prince, T. A.; Fürst, F.; Geier, S.

    2015-10-01

    Kepler satellite photometry and phase-resolved spectroscopy of the ultracompact AM CVn type binary SDSS J190817.07+394036.4 are presented. The average spectra reveal a variety of weak metal lines of different species, including silicon, sulphur and magnesium as well as many lines of nitrogen, beside the strong absorption lines of neutral helium. The phase-folded spectra and the Doppler tomograms reveal an S-wave in emission in the core of the He I 4471 Å absorption line at a period of Porb = 1085.7 ± 2.8 s identifying this as the orbital period of the system. The Si II, Mg II and the core of some He I lines show an S-wave in absorption with a phase offset of 170° ± 15° compared to the S-wave in emission. The N II, Si III and some helium lines do not show any phase variability at all. The spectroscopic orbital period is in excellent agreement with a period at Porb = 1085.108(9) s detected in the 3 yr Kepler light curve. A Fourier analysis of the Q6-Q17 short-cadence data obtained by Kepler revealed a large number of frequencies above the noise level where the majority shows a large variability in frequency and amplitude. In an Observed-minus-computed analysis, we measured a \\vert dot{P}\\vert ˜ 1.0 × 10-8 s s-1 for some of the strongest variations and set a limit for the orbital period to be \\vert dot{P}\\vert <10^{-10} s s-1. The shape of the phase-folded light curve on the orbital period indicates the motion of the bright-spot. Models of the system were constructed to see whether the phases of the radial velocity curves and the light-curve variation can be combined to a coherent picture. However, from the measured phases neither the absorption nor the emission can be explained to originate in the bright-spot.

  1. Spatially Localized Two-Dimensional J-Resolved NMR Spectroscopy via Intermolecular Double-Quantum Coherences for Biological Samples at 7 T

    PubMed Central

    Tan, Chunhua; Cai, Shuhui; Huang, Yuqing

    2015-01-01

    Background and Purpose Magnetic resonance spectroscopy (MRS) constitutes a mainstream technique for characterizing biological samples. Benefiting from the separation of chemical shifts and J couplings, spatially localized two-dimensional (2D) J-resolved spectroscopy (JPRESS) shows better identification of complex metabolite resonances than one-dimensional MRS does and facilitates the extraction of J coupling information. However, due to variations of macroscopic magnetic susceptibility in biological samples, conventional JPRESS spectra generally suffer from the influence of field inhomogeneity. In this paper, we investigated the implementation of the localized 2D J-resolved spectroscopy based on intermolecular double-quantum coherences (iDQCs) on a 7 T MRI scanner. Materials and Methods A γ-aminobutyric acid (GABA) aqueous solution, an intact pig brain tissue, and a whole fish (Harpadon nehereus) were explored by using the localized iDQC J-resolved spectroscopy (iDQCJRES) method, and the results were compared to those obtained by using the conventional 2D JPRESS method. Results Inhomogeneous line broadening, caused by the variations of macroscopic magnetic susceptibility in the detected biological samples (the intact pig brain tissue and the whole fish), degrades the quality of 2D JPRESS spectra, particularly when a large voxel is selected and some strongly structured components are included (such as the fish spinal cord). By contrast, high-resolution 2D J-resolved information satisfactory for metabolite analyses can be obtained from localized 2D iDQCJRES spectra without voxel size limitation and field shimming. From the contrastive experiments, it is obvious that the spectral information observed in the localized iDQCJRES spectra acquired from large voxels without field shimming procedure (i.e. in inhomogeneous fields) is similar to that provided by the JPRESS spectra acquired from small voxels after field shimming procedure (i.e. in relatively homogeneous fields

  2. 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.

  3. Rapid high-resolution spin- and angle-resolved photoemission spectroscopy with pulsed laser source and time-of-flight spectrometer.

    PubMed

    Gotlieb, K; Hussain, Z; Bostwick, A; Lanzara, A; Jozwiak, C

    2013-09-01

    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(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. PMID:24089838

  4. Rapid high-resolution spin- and angle-resolved photoemission spectroscopy with pulsed laser source and time-of-flight spectrometer

    NASA Astrophysics Data System (ADS)

    Gotlieb, K.; Hussain, Z.; Bostwick, A.; Lanzara, A.; Jozwiak, C.

    2013-09-01

    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-EF 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.

  5. Rapid high-resolution spin- and angle-resolved photoemission spectroscopy with pulsed laser source and time-of-flight spectrometer.

    PubMed

    Gotlieb, K; Hussain, Z; Bostwick, A; Lanzara, A; Jozwiak, C

    2013-09-01

    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(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.

  6. 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.

  7. Chemical-shift-resolved ¹⁹F NMR spectroscopy between 13.5 and 135 MHz: Overhauser-DNP-enhanced diagonal suppressed correlation spectroscopy.

    PubMed

    George, Christy; Chandrakumar, Narayanan

    2014-08-01

    Overhauser-DNP-enhanced homonuclear 2D (19)F correlation spectroscopy with diagonal suppression is presented for small molecules in the solution state at moderate fields. Multi-frequency, multi-radical studies demonstrate that these relatively low-field experiments may be operated with sensitivity rivalling that of standard 200-1000 MHz NMR spectroscopy. Structural information is accessible without a sensitivity penalty, and diagonal suppressed 2D NMR correlations emerge despite the general lack of multiplet resolution in the 1D ODNP spectra. This powerful general approach avoids the rather stiff excitation, detection, and other special requirements of high-field (19)F NMR spectroscopy.

  8. Microfluidic space-domain time-resolved emission spectroscopy of terbium(III) and europium(III) chelates with pyridine-2,6-dicarboxylate.

    PubMed

    Nuñez, Vicente; Upadhyayula, Srigokul; Millare, Brent; Larsen, Jillian M; Hadian, Ali; Shin, Sanghoon; Vandrangi, Prashanthi; Gupta, Sharad; Xu, Hong; Lin, Adam P; Georgiev, Georgi Y; Vullev, Valentine I

    2013-05-01

    This article describes the utilization of laminar microflows for time-resolved emission measurements with steady-state excitation and detection. Passing a laminar flow through a short illuminated section of a microchannel provided a means for pulsed-like photoexcitation of the moieties carried by the fluid. Imaging the microchannel flows carrying thus photoexcited chelates of lanthanide ions allowed us to extract their excited-state lifetimes from the spatial distribution of the changes in the emission intensity. The lifetime values obtained using this space-domain approach agreed well with the lifetimes from time-domain measurements. This validated space-domain microfluidic approach reveals a means for miniaturization of time-resolved emission spectroscopy.

  9. 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

  10. 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.

  11. Image potential states in monolayer, bilayer, and trilayer epitaxial graphene studied with time- and angle-resolved two-photon photoemission spectroscopy

    NASA Astrophysics Data System (ADS)

    Takahashi, Kazutoshi; Imamura, Masaki; Yamamoto, Isamu; Azuma, Junpei; Kamada, Masao

    2014-04-01

    Image potential states (IPSs) on monolayer, bilayer, and trilayer graphene epitaxially grown on SiC(0001) have been studied by time- and angle-resolved two-photon photoemission (2PPE) spectroscopy. The free-electron-like dispersions of even and odd symmetry IPSs with a quantum number of n = 1+, 1-, 2, 3 were observed. All observed IPSs showed the dispersions with effective masses of m*=1.0±0.1me. The 2PPE intensity of the lowest IPS (n = 1+) was attenuated with an increasing number of graphene layers. The time-resolved 2PPE measurements revealed that these IPSs have significantly shorter lifetimes, suggesting a coupling of IPSs with electronic states in the buffer layer and the SiC substrate.

  12. Time-resolved K α spectroscopy measurements of hot-electron equilibration dynamics in thin-foil solid targets: collisional and collective effects

    NASA Astrophysics Data System (ADS)

    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.

    2015-11-01

    Time-resolved K α spectroscopy measurements from high-intensity laser interactions with thin-foil solid targets are reviewed. Thin Cu foils were irradiated with 1-10 J, 1 ps pulses at focused intensities from 1018 to 1019 W cm-2. The experimental data show K α -emission pulse widths from 3 to 6 ps, increasing with laser intensity. The time-resolved K α -emission data are compared to a hot-electron transport and K α -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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. Momentum-Dependent Charge Transfer Excitations in Sr2CuO 2Cl2 Angle-Resolved Electron Energy Loss Spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Y. Y.; Zhang, F. C.; Dravid, V. P.; Ng, K. K.; Klein, M. V.; Schnatterly, S. E.; Miller, L. L.

    1996-08-01

    Electron-hole pair excitations in the insulating cuprates Sr2CuO2Cl2 were investigated by angle-resolved electron energy loss spectroscopy. The optically allowed and optically forbidden transitions were observed to be strongly anisotropic in Cu-O2 plane. The former show a large energy dispersion ~1.5 eV along [110], and the latter appear at a higher energy position (~4.5 eV) only along [100], but not along [110]. We interpret these results as transitions involving excitons. A small exciton model is examined to explain both the observed features.

  18. Probing Electronic and Vibrational Dynamics in Molecules by Time-Resolved Photoelectron, Auger-Electron, and X-ray Photon Scattering Spectroscopy

    PubMed Central

    Bennett, Kochise; Kowalewski, Markus; Mukamel, Shaul

    2015-01-01

    We present a unified description for time-resolved electron and photon scattering spectroscopies from molecules prepared in nonstationary states. Signals are expressed in terms of superoperator Green’s functions and a systematic procedure for treating various degrees of freedom consistently at different levels of theory is developed. The standard Fermi Golden Rule expressions for photelectron spectra, which are limited to broad, slowly-varying signals, are obtained as a limiting case of our more general theory that applies to broader parameter regimes. PMID:25730500

  19. 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.

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. 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

  5. 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

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

    PubMed

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

    2015-02-25

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

  7. 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.

  8. 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.

  9. 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

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

    PubMed

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

    2015-05-01

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

  11. 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.

  12. 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

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

    PubMed

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

    2015-05-01

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

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1994-07-01

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

  16. Nanosecond time-resolved emission spectroscopy of a fluorescence probe adsorbed to L-alpha-egg lecithin vesicles.

    PubMed Central

    Easter, J H; DeToma, R P; Brand, L

    1976-01-01

    Nanosecond time-resolved emission spectra (TRES) are fluorescence emission spectra obtained at discrete times during the fluorescence decay. The complete data-set obtainable is a surface representing the intensity at all wavelengths and times during the emission decay time. When 2-p-toluidinonaphthalene-6-sulfonate (2,6 p-TNS) is adsorbed to egg lecithin vesicles, an excited-state reaction associated with energetic changes of the emitting species occurs on the nanosecond time scale. Convolution of the fluorescence decay with the excitation response introduces an artifact in the time-dependent spectra. A precedure is described by which this artifact can be eliminated. The data for the generation of time-resolved emission spectra are obtained with a computer-interfaced instrument based on the single-photon counting method. PMID:945086

  17. 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.

  18. 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.

  19. Molecular-level investigation of the structure, transformation, and bioactivity of single living fission yeast cells by time- and space-resolved Raman spectroscopy.

    PubMed

    Huang, Yu-San; Karashima, Takeshi; Yamamoto, Masayuki; Hamaguchi, Hiro-o

    2005-08-01

    The structure, transformation, and bioactivity of single living Schizosaccharomyces pombe cells at the molecular level have been studied in vivo by time- and space-resolved Raman spectroscopy. A time resolution of 100 s and a space resolution of 250 nm have been achieved with the use of a confocal Raman microspectrometer. The space-resolved Raman spectra of living S. pombe cells at different cell cycle stages were recorded in an effort to elucidate the molecular compositions of organelles, including nuclei, cytoplasm, mitochondria, and septa. The time- and space-resolved measurement of the central part of a dividing yeast cell showed continuous spectral evolution from that of the nucleus to those of the cytoplasm and mitochondria and finally to that of the septum, in accordance with the transformation during the cell cycle. A strong Raman band was observed at 1602 cm(-)(1) only when cells were under good nutrient conditions. The effect of a respiration inhibitor, KCN, on a living yeast cell was studied by measuring the Raman spectra of its mitochondria. A sudden disappearance of the 1602 cm(-)(1) band followed by the change in the shape and intensity of the phospholipid bands was observed, indicating a strong relationship between the cell activity and the intensity of this band. We therefore call this band "the Raman spectroscopic signature of life". The Raman mapping of a living yeast cell was also carried out. Not only the distributions of molecular species but also those of active mitochondria in the cell were successfully visualized in vivo.

  20. 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.

  1. 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.

  2. Quantitative time-resolved vibrational sum frequency generation spectroscopy as a tool for thin film kinetic studies: new insights into oleic acid monolayer oxidation.

    PubMed

    Kleber, Joscha; Laß, Kristian; Friedrichs, Gernot

    2013-08-22

    Environmental air-water interfaces are often covered by thin films of surface-active organic substances that play an important role for air-sea gas exchange and aerosol aging. Surface-sensitive vibrational sum frequency generation (VSFG) spectroscopy has been widely used to study the static structure of organic monolayers serving as simple model systems of such films. Probably due to the difficulties to correlate the SFG signal intensity with the surface concentration, corresponding time-resolved studies of surface reactions are scarce. In this study, quantitative time-resolved measurements have been performed on the oleic acid monolayer ozonolysis, which is considered a benchmark system for investigating the reactivity and fate of unsaturated natural organics. Surface concentration calibration data have been obtained by combining the pressure-area isotherm and VSFG spectra acquisition such that the 2D phase behavior of the oleic acid film could be properly taken into account. In contrast to literature reports, surface-active oxidation products were found to be negligible and do not interfere with the VSFG measurements. A pseudo-first-order kinetic analysis of the time-resolved data yielded a bimolecular rate constant of k2(oleic acid + O3 → products) = (1.65 ± 0.64) × 10(-16) cm(3) molecules(-1) s(-1), corresponding to an uptake coefficient of γ = (4.7 ± 1.8) × 10(-6). This result is in very good agreement with most recent monolayer measurements based on alternative methods and underlines the reliability of the time-resolved VSFG approach.

  3. Highly resolved two-dimensional ¹H spectroscopy of the human brain using ISIS CT-PRESS with resolution enhancement.

    PubMed

    Watanabe, Hidehiro; Takaya, Nobuhiro; Mitsumori, Fumiyuki

    2012-01-01

    In constant time (CT) point-resolved spectroscopy (PRESS), echo centers shift with the fast decay of short T₂* on two-dimensional (2D) time domain (TD) data under inhomogeneous B₀ field like in vivo conditions. Though ¹H decoupling along the F₁ direction is a feature of this method, the tilted and broadened peak pattern on the F₁-F₂ plane after reconstruction causes the peaks to overlap. To enhance resolution to achieve highly resolved 2D CT-PRESS spectra in the human brain, we propose a 2-part window function that comprises an enhancement part for shifting echoes with fast decay and a conventional part, such as Lorentzian, Gaussian, or sine-bell function. We obtained 2D spectra from human brains at 4.7T. The 3 diagonal peaks of C4H of glutamate (Glu C4H) at 2.35 ppm, C2H of γ-amino butyric acid (GABA C2H) at 2.28 ppm, and C4H of glutamine (Gln C4H) at 2.44 ppm-overlapped on the spectra processed with the conventional window but clearly resolved on the spectra using the proposed enhancement window. The signal-to-noise ratio per unit measurement time of Glu C4H on a CT-PRESS spectrum of the human brain was 1.7 times higher than that on a spectrum obtained by CT-correlation spectroscopic (COSY). In conclusion, 2D CT-PRESS spectra processed with the proposed window function to enhance resolution can resolve peaks of coupled ¹H spins with higher accuracy and sensitivity.

  4. 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

  5. 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.

  6. Comparison of TiO₂ and ZnO solar cells sensitized with an indoline dye: time-resolved laser spectroscopy studies of partial charge separation processes.

    PubMed

    Sobuś, Jan; Burdziński, Gotard; Karolczak, Jerzy; Idígoras, Jesús; Anta, Juan A; Ziółek, Marcin

    2014-03-11

    Time-resolved laser spectroscopy techniques in the time range from femtoseconds to seconds were applied to investigate the charge separation processes in complete dye-sensitized solar cells (DSC) made with iodide/iodine liquid electrolyte and indoline dye D149 interacting with TiO2 or ZnO nanoparticles. The aim of the studies was to explain the differences in the photocurrents of the cells (3-4 times higher for TiO2 than for ZnO ones). Electrochemical impedance spectroscopy and nanosecond flash photolysis studies revealed that the better performance of TiO2 samples is not due to the charge collection and dye regeneration processes. Femtosecond transient absorption results indicated that after first 100 ps the number of photoinduced electrons in the semiconductor is 3 times higher for TiO2 than for ZnO solar cells. Picosecond emission studies showed that the lifetime of the D149 excited state is about 3 times longer for ZnO than for TiO2 samples. Therefore, the results indicate that lower performance of ZnO solar cells is likely due to slower electron injection. The studies show how to correlate the laser spectroscopy methodology with global parameters of the solar cells and should help in better understanding of the behavior of alternative materials for porous electrodes for DSC and related devices.

  7. 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.

  8. 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 %.

  9. 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.

  10. Time-resolved in situ investigations of reactive sputtering processes by grazing incidence X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Lützenkirchen-Hecht, Dirk; Frahm, Ronald

    2006-09-01

    We have applied the time-resolved grazing incidence X-ray absorption fine structure technique to study in situ the atomic short range order and the electronic structure of reactively sputter deposited thin films. Results obtained during the reactive deposition of amorphous Ta-pentoxide thin films deposited in oxygen containing atmospheres will be presented. A new calculation scheme for a detailed reflection mode EXAFS data analysis giving bond distances, coordination numbers and Debye-Waller factors is presented. The atomic short range structure of the amorphous Ta 2O 5 thin films is compared to that of crystalline β-Ta 2O 5.

  11. 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

  12. A theoretical analysis of the spin dynamics of magnetic adatoms traced by time-resolved scanning tunneling spectroscopy

    NASA Astrophysics Data System (ADS)

    Schüler, M.; Pavlyukh, Y.; Berakdar, J.

    2012-04-01

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

  13. 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.

  14. 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.

  15. Fast Spatially Resolved Exhaust Gas Recirculation (EGR) Distribution Measurements in an Internal Combustion Engine Using Absorption Spectroscopy

    DOE PAGESBeta

    Yoo, Jihyung; Prikhodko, Vitaly; Parks, James E.; Perfetto, Anthony; Geckler, Sam; Partridge, William P.

    2015-09-01

    One effective method of reducing NOx emissions while improving efficiency is exhaust gas recirculation (EGR) in internal combustion engines. But, insufficient mixing between fresh air and exhaust gas can lead to cycle-to-cycle and cylinder-to-cylinder nonuniform charge gas mixtures of a multi-cylinder engine, which can in turn reduce engine performance and efficiency. Furthermore, 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 themore » intake manifold. Our 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.« less

  16. Fast Spatially Resolved Exhaust Gas Recirculation (EGR) Distribution Measurements in an Internal Combustion Engine Using Absorption Spectroscopy

    SciTech Connect

    Yoo, Jihyung; Prikhodko, Vitaly; Parks, James E.; Perfetto, Anthony; Geckler, Sam; Partridge, William P.

    2015-09-01

    One effective method of reducing NOx emissions while improving efficiency is exhaust gas recirculation (EGR) in internal combustion engines. But, insufficient mixing between fresh air and exhaust gas can lead to cycle-to-cycle and cylinder-to-cylinder nonuniform charge gas mixtures of a multi-cylinder engine, which can in turn reduce engine performance and efficiency. Furthermore, 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. Our 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.

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

    PubMed

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

    2015-05-01

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

  18. Deep and surface hemodynamic signal from functional time resolved transcranial near infrared spectroscopy compared to skin flowmotion.

    PubMed

    Aletti, Federico; Re, Rebecca; Pace, Vincenzo; Contini, Davide; Molteni, Erika; Cerutti, Sergio; Maria Bianchi, Anna; Torricelli, Alessandro; Spinelli, Lorenzo; Cubeddu, Rinaldo; Baselli, Giuseppe

    2012-03-01

    The potential disturbance in the prefrontal cortex hemodynamic signal measured by functional near infrared spectroscopy (NIRS), due to forehead skin flowmotion, detected by laser Doppler flowmetry, was investigated by a standard protocol of hemodynamic challenge by Valsalva maneuver, aimed at assessing and disentangling local regulatory responses in skin vasomotion and in cerebral perfusion in presence of a strong systemic drive, and to quantify the common information in the two signals. The deep cortical NIRS signal did not appear to be affected by surface vasomotor activity, and autoregulation dynamics were dominant with respect to autonomic control of circulation.

  19. Time-resolved postdischarge absolute silicon monoxide density measurement by resonant absorption spectroscopy in a nonthermal atmospheric plasma

    SciTech Connect

    Motret, Olivier; Coursimault, Fabien; Pouvesle, Jean-Michel

    2006-11-01

    In this study we present the technique of resonant absorption spectroscopy diagnostic developed to estimate the density of silicon monoxide (SiO) molecules during the postdischarge of an atmospheric dielectric barrier discharge plasma. The ultraviolet (0,0) rovibrational band of the SiO(A {sup 1}{pi}-X {sup 1}{sigma}{sup +}) electronic transition was investigated. Effective values of absorption coefficient and absorption cross section for the rotational transitions under consideration were calculated. The SiO concentration was estimated by comparison between experimental and computed spectra. The self-absorption in the probe reactor was taken into account in the computed spectra.

  20. 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