Electronic and nuclear contributions to time-resolved optical and X-ray absorption spectra of hematite and insights into photoelectrochemical performance

DOE PAGES

Hayes, Dugan; Hadt, Ryan G.; Emery, Jonathan D.; ...

2016-11-02

Ultrafast time-resolved studies of photocatalytic thin films can provide a wealth of information crucial for understanding and thereby improving the performance of these materials by directly probing electronic structure, reaction intermediates, and charge carrier dynamics. The interpretation of transient spectra, however, can be complicated by thermally induced structural distortions, which appear within the first few picoseconds following excitation due to carrier–phonon scattering. Here we present a comparison of ex situ steady-state thermal difference spectra and transient absorption spectra spanning from NIR to hard X-ray energies of hematite thin films grown by atomic layer deposition. We find that beyond the firstmore » 100 picoseconds, the transient spectra measured for all excitation wavelengths and probe energies are almost entirely due to thermal effects as the lattice expands in response to the ultrafast temperature jump and then cools to room temperature on the microsecond timescale. At earlier times, a broad excited state absorption band that is assigned to free carriers appears at 675 nm, and the lifetime and shape of this feature also appear to be mostly independent of excitation wavelength. The combined spectroscopic data, which are modeled with density functional theory and full multiple scattering calculations, support an assignment of the optical absorption spectrum of hematite that involves two LMCT bands that nearly span the visible spectrum. Lastly, our results also suggest a framework for shifting the ligand-to-metal charge transfer absorption bands of ferric oxide films from the near-UV further into the visible part of the solar spectrum to improve solar conversion efficiency.« less

Spectroscopic classification of supernova SN 2018Z by NUTS (NOT Un-biased Transient Survey)

NASA Astrophysics Data System (ADS)

Kuncarayakti, H.; Mattila, S.; Kotak, R.; Harmanen, J.; Reynolds, T.; Pastorello, A.; Benetti, S.; Stritzinger, M.; Onori, F.; Somero, A.; Kangas, T.; Lundqvist, P.; Taddia, F.; Ergon, M.

2018-01-01

The NOT Unbiased Transient Survey (NUTS; ATel #8992) collaboration reports the spectroscopic classification of supernova SN 2018Z in host galaxy SDSS J231809.76+212553.5 The observations were performed with the 2.56 m Nordic Optical Telescope equipped with ALFOSC (range 350-950 nm; resolution 1.6 nm) on 2018-01-09.9 UT. Survey Name | IAU Name | Discovery (UT) | Discovery mag | Observation (UT) | Redshift | Type | Phase | Notes PS18ao | SN 2018Z | 2018-01-01.2 | 19.96 | 2018-01-09.9 | 0.102 | Ia | post-maximum? | (1) (1) Redshift was derived from the SN and host absorption features.

Separation of distinct photoexcitation species in femtosecond transient absorption microscopy

DOE PAGES

Xiao, Kai; Ma, Ying -Zhong; Simpson, Mary Jane; ...

2016-02-03

Femtosecond transient absorption microscopy is a novel chemical imaging capability with simultaneous high spatial and temporal resolution. Although several powerful data analysis approaches have been developed and successfully applied to separate distinct chemical species in such images, the application of such analysis to distinguish different photoexcited species is rare. In this paper, we demonstrate a combined approach based on phasor and linear decomposition analysis on a microscopic level that allows us to separate the contributions of both the excitons and free charge carriers in the observed transient absorption response of a composite organometallic lead halide perovskite film. We found spatialmore » regions where the transient absorption response was predominately a result of excitons and others where it was predominately due to charge carriers, and regions consisting of signals from both contributors. Lastly, quantitative decomposition of the transient absorption response curves further enabled us to reveal the relative contribution of each photoexcitation to the measured response at spatially resolved locations in the film.« less

Exciton exciton annihilation dynamics in chromophore complexes. II. Intensity dependent transient absorption of the LH2 antenna system.

PubMed

Bruggemann, B; May, V

2004-02-01

Using the multiexciton density matrix theory of excitation energy transfer in chromophore complexes developed in a foregoing paper [J. Chem. Phys. 118, 746 (2003)], the computation of ultrafast transient absorption spectra is presented. Beside static disorder and standard mechanisms of excitation energy dissipation the theory incorporates exciton exciton annihilation (EEA) processes. To elucidate signatures of EEA in intensity dependent transient absorption data the approach is applied to the B850 ring of the LH2 found in rhodobacter sphaeroides. As main indications for two-exciton population and resulting EEA we found (i) a weakening of the dominant single-exciton bleaching structure in the transient absorption, and (ii) an intermediate suppression of long-wavelength and short-wavelength shoulders around the bleaching structure. The suppression is caused by stimulated emission from the two-exciton to the one-exciton state and the return of the shoulders follows from a depletion of two-exciton population according to EEA. The EEA-signature survives as a short-wavelength shoulder in the transient absorption if orientational and energetic disorder are taken into account. Therefore, the observation of the EEA-signatures should be possible when doing frequency resolved transient absorption experiments with a sufficiently strongly varying pump-pulse intensity. Copyright 2004 American Institute of Physics

Femtosecond transient absorption, Raman, and electrochemistry studies of tetrasulfonated copper phthalocyanine in water solutions.

PubMed

Abramczyk, H; Brozek-Płuska, B; Kurczewski, K; Kurczewska, M; Szymczyk, I; Krzyczmonik, P; Błaszczyk, T; Scholl, H; Czajkowski, W

2006-07-20

Ultrafast time-resolved electronic spectra of the primary events induced in the copper tetrasulfonated phthalocyanine Cu(tsPc)4-) in aqueous solution has been measured by femtosecond pump-probe transient absorption spectroscopy. The primary events initiated by the absorption of a photon occurring within the femtosecond time scale are discussed on the basis of the electron transfer mechanism between the adjacent phthalocyanine rings proposed recently in our laboratory. The femtosecond transient absorption results are compared with the low temperature emission spectra obtained with Raman spectroscopy and the voltammetric curves.

Photochemical synthesis and photophysical properties of coumarins bearing extended polyaromatic rings studied by emission and transient absorption measurements.

PubMed

Yamaji, Minoru; Hakoda, Yuma; Okamoto, Hideki; Tani, Fumito

2017-04-12

We prepared a variety of coumarin derivatives having expanded π-electron systems along the direction crossing the C 3 -C 4 bond of the coumarin skeleton via a photochemical cyclization process and investigated their photophysical features as a function of the number (n) of the added benzene rings based on emission and transient absorption measurements. Upon increasing n, the fluorescence quantum yields of the π-extended coumarins increased. Expanding the π-electron system on the C 3 -C 4 bond of the coumarin skeleton was found to be efficient for increasing the fluorescence ability more than that on the C 7 -C 8 bond. Introducing the methoxy group at the 7-position was also efficient for enhancing the fluorescence quantum yield and rate of the expanded coumarins. The non-radiative process from the fluorescence state was not substantially influenced by the expanded π-electron system. The competitive process with the fluorescence was found to be intersystem crossing to the triplet state based on the observations of the triplet-triplet absorption. The effects of the expanded π-electron systems on the fluorescence ability were investigated with the aid of TD-DFT calculations.

Molecular behavior of zero-dimensional perovskites

PubMed Central

Yin, Jun; Maity, Partha; De Bastiani, Michele; Dursun, Ibrahim; Bakr, Osman M.; Brédas, Jean-Luc; Mohammed, Omar F.

2017-01-01

Low-dimensional perovskites offer a rare opportunity to investigate lattice dynamics and charge carrier behavior in bulk quantum-confined solids, in addition to them being the leading materials in optoelectronic applications. In particular, zero-dimensional (0D) inorganic perovskites of the Cs4PbX6 (X = Cl, Br, or I) kind have crystal structures with isolated lead halide octahedra [PbX6]4− surrounded by Cs+ cations, allowing the 0D crystals to exhibit the intrinsic properties of an individual octahedron. Using both experimental and theoretical approaches, we studied the electronic and optical properties of the prototypical 0D perovskite Cs4PbBr6. Our results underline that this 0D perovskite behaves akin to a molecule, demonstrating low electrical conductivity and mobility as well as large polaron binding energy. Density functional theory calculations and transient absorption measurements of Cs4PbBr6 perovskite films reveal the polaron band absorption and strong polaron localization features of the material. A short polaron lifetime of ~2 ps is observed in femtosecond transient absorption experiments, which can be attributed to the fast lattice relaxation of the octahedra and the weak interactions among them. PMID:29250600

The X-ray Absorber in the X-ray Transient NLS1 WPVS 007

NASA Astrophysics Data System (ADS)

Grupe, Dirk

This proposal is for a funding request for an approved XMM-Newton observations of the X-ray transient Narrow-Line Seyfert 1 galaxy WPVS 007. The request is for 4 month of salary for the PI for one year in order to do the data analysis, publish the results, and attend an international AGN meeting. XMM will observe WPVS 007 in June 2010 simultaneously with HST, Chandra, and Swift. The goal is to establish a tight connection between the UV broad absorption line troughs found in FUSE observations and the strong partial covering absorber feature found by Swift. WPVS 007 showed a dramatic transformation into a Broad Absorption line QSO like AGN between a 1996 HST observation and a 2003 FUSE observation. Several Swift monitoring observations have suggested that the absorber may have started to disappear. Therefore it is crucial for our HST COS UV spectroscopy to know what the status of the X-ray absorber is. The XMM observation will provide a well-exposed X-ray spectrum even if WPVS 007 will be in a low flux state. This spectrum will enable us to put constraints on the absorption column density and covering fraction of the partial covering absorber.

Development of tunable high pressure CO2 laser for lidar measurements of pollutants and wind velocities, January 1976 to December 1977

NASA Technical Reports Server (NTRS)

Javan, A.

1979-01-01

A tunable multiatmospheric pulsed CO2 laser with emphasis on experimental features and supporting theoretical analyses important to differential absorption lidar and Doppler lidar measurement of pollutants and wind velocities is reported. The energy deposition and the means to produce the uniform high density plasma in the multiatmospheric medium, through UV preionization of an organic seed gas is discussed. Design features of the pulsed CO2 laser are presented. The radiative processes which are operative and prevent the laser from breaking into oscillations in a large number of modes over its broad amplification bandwidth are described. The mode competition for the transient pulsed laser oscillation in a standing wave and traveling wave ring laser configuration is discussed and contrasted with the approach to steady state oscillations. The latter findings are important to transient injection locking for production of a highly stable pulsed CO2 laser output.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

DOE PAGES

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.; ...

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

On the Non-Metallicity of 2.2 nm Au 246 (SR) 80 Nanoclusters

DOE PAGES

Zhou, Meng; Zeng, Chenjie; Song, Yongbo; ...

2017-11-22

The transition from molecular to plasmonic behaviour in metal nanoparticles with increasing size remains a central question in nanoscience. Here, we report that the giant 246-gold-atom nanocluster (2.2 nm in gold core diameter) protected by 80 thiolate ligands is surprisingly non-metallic based on UV/Vis and femtosecond transient absorption spectroscopy as well as electrochemical measurements. Specifically, the Au246 nanocluster exhibits multiple excitonic peaks in transient absorption spectra and electron dynamics independent of the pump power, which are in contrast to the behaviour of metallic gold nanoparticles. Moreover, a prominent oscillatory feature with frequency of 0.5 THz can be observed in almostmore » all the probe wavelengths. The phase and amplitude analysis of the oscillation suggests that it arises from the wavepacket motion on the ground state potential energy surface, which also indicates the presence of a small band-gap and thus non-metallic or molecular-like behaviour.« less

Layer-Dependent Ultrafast Carrier and Coherent Phonon Dynamics in Black Phosphorus.

PubMed

Miao, Xianchong; Zhang, Guowei; Wang, Fanjie; Yan, Hugen; Ji, Minbiao

2018-05-09

Black phosphorus is a layered semiconducting material, demonstrating strong layer-dependent optical and electronic properties. Probing the photophysical properties on ultrafast time scales is of central importance in understanding many-body interactions and nonequilibrium quasiparticle dynamics. Here, we applied temporally, spectrally, and spatially resolved pump-probe microscopy to study the transient optical responses of mechanically exfoliated few-layer black phosphorus, with layer numbers ranging from 2 to 9. We have observed layer-dependent resonant transient absorption spectra with both photobleaching and red-shifted photoinduced absorption features, which could be attributed to band gap renormalization of higher subband transitions. Surprisingly, coherent phonon oscillations with unprecedented intensities were observed when the probe photons were in resonance with the optical transitions, which correspond to the low-frequency layer-breathing mode. Our results reveal strong Coulomb interactions and electron-phonon couplings in photoexcited black phosphorus, providing important insights into the ultrafast optical, nanomechanical, and optoelectronic properties of this novel two-dimensional material.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zurch, Michael; Chang, Hung -Tzu; Borja, Lauren J.

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20 cm –3. Separate electron and hole relaxation times are observedmore » as a function of hot carrier energies. A first-order electron and hole decay of ~1 ps suggests a Shockley–Read–Hall recombination mechanism. Furthermore, the simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.« less

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium.

PubMed

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J; Kraus, Peter M; Cushing, Scott K; Gandman, Andrey; Kaplan, Christopher J; Oh, Myoung Hwan; Prell, James S; Prendergast, David; Pemmaraju, Chaitanya D; Neumark, Daniel M; Leone, Stephen R

2017-06-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M 4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 10 20  cm -3 . Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley-Read-Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions.

Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium

PubMed Central

Zürch, Michael; Chang, Hung-Tzu; Borja, Lauren J.; Kraus, Peter M.; Cushing, Scott K.; Gandman, Andrey; Kaplan, Christopher J.; Oh, Myoung Hwan; Prell, James S.; Prendergast, David; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Understanding excited carrier dynamics in semiconductors is crucial for the development of photovoltaics and efficient photonic devices. However, overlapping spectral features in optical pump-probe spectroscopy often render assignments of separate electron and hole carrier dynamics ambiguous. Here, ultrafast electron and hole dynamics in germanium nanocrystalline thin films are directly and simultaneously observed by ultrafast transient absorption spectroscopy in the extreme ultraviolet at the germanium M4,5 edge. We decompose the spectra into contributions of electronic state blocking and photo-induced band shifts at a carrier density of 8 × 1020 cm−3. Separate electron and hole relaxation times are observed as a function of hot carrier energies. A first-order electron and hole decay of ∼1 ps suggests a Shockley–Read–Hall recombination mechanism. The simultaneous observation of electrons and holes with extreme ultraviolet transient absorption spectroscopy paves the way for investigating few- to sub-femtosecond dynamics of both holes and electrons in complex semiconductor materials and across junctions. PMID:28569752

Attosecond transient absorption probing of electronic superpositions of bound states in neon. Detection of quantum beats

DOE PAGES

Beck, Annelise R; Bernhardt, Birgitta; Warrick, Erika R.; ...

2014-11-07

Electronic wavepackets composed of multiple bound excited states of atomic neon lying between 19.6 and 21.5 eV are launched using an isolated attosecond pulse. Individual quantum beats of the wavepacket are detected by perturbing the induced polarization of the medium with a time-delayed few-femtosecond near-infrared (NIR) pulse via coupling the individual states to multiple neighboring levels. All of the initially excited states are monitored simultaneously in the attosecond transient absorption spectrum, revealing Lorentzian to Fano lineshape spectral changes as well as quantum beats. The most prominent beating of the several that were observed was in the spin–orbit split 3d absorptionmore » features, which has a 40 femtosecond period that corresponds to the spin–orbit splitting of 0.1 eV. The few-level models and multilevel calculations confirm that the observed magnitude of oscillation depends strongly on the spectral bandwidth and tuning of the NIR pulse and on the location of possible coupling states.« less

Ultrafast carrier dynamics of titanic acid nanotubes investigated by transient absorption spectroscopy.

PubMed

Wang, Li; Zhao, Hui; Pan, Lin Yun; Weng, Yu Xiang; Nakato, Yoshihiro; Tamai, Naoto

2010-12-01

Carrier dynamics of titanic acid nanotubes (phase of H2Ti2O5.H2O) deposited on a quartz plate was examined by visible/near-IR transient absorption spectroscopy with an ultraviolet excitation. The carrier dynamics of titanic acid nanotubes follows the fast trapping process which attributed to the intrinsic tubular structure, the relaxation of shallow trapped carriers and the recombination as a second-order kinetic process. Transient absorption of titanic acid nanotubes was dominated by the absorption of surface-trapped holes in visible region around 500 nm, which was proved by the faster decay dynamics in the presence of polyvinyl alcohol as a hole-scavenger. However, the slow relaxation of free carriers was much more pronounced in the TiO2 single crystals, as compared with the transient absorption spectra of titanic acid nanotubes under the similar excitation.

Analyte-induced spectral filtering in femtosecond transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

Here, we discuss the influence of spectral filtering by samples in femtosecond transient absorption measurements. Commercial instruments for transient absorption spectroscopy (TA) have become increasingly available to scientists in recent years and TA is becoming an established technique to measure the dynamics of photoexcited systems. Furthermore, we show that absorption of the excitation pulse by the sample can severely alter the spectrum and consequently the temporal pulse shape. This “spectral self-filtering” effect can lead to systematic errors and misinterpretation of data, most notably in concentration dependent measurements. Finally, the combination of narrow absorption peaks in the sample with ultrafast broadbandmore » excitation pulses is especially prone to this effect.« less

Analyte-induced spectral filtering in femtosecond transient absorption spectroscopy

DOE PAGES

Abraham, Baxter; Nieto-Pescador, Jesus; Gundlach, Lars

2017-03-06

Here, we discuss the influence of spectral filtering by samples in femtosecond transient absorption measurements. Commercial instruments for transient absorption spectroscopy (TA) have become increasingly available to scientists in recent years and TA is becoming an established technique to measure the dynamics of photoexcited systems. Furthermore, we show that absorption of the excitation pulse by the sample can severely alter the spectrum and consequently the temporal pulse shape. This “spectral self-filtering” effect can lead to systematic errors and misinterpretation of data, most notably in concentration dependent measurements. Finally, the combination of narrow absorption peaks in the sample with ultrafast broadbandmore » excitation pulses is especially prone to this effect.« less

Probing excitons in transition metal dichalcogenides by Drude-like exciton intraband absorption.

PubMed

Zhao, Siqi; He, Dawei; He, Jiaqi; Zhang, Xinwu; Yi, Lixin; Wang, Yongsheng; Zhao, Hui

2018-05-24

Understanding excitonic dynamics in two-dimensional semiconducting transition metal dichalcogenides is important for developing their optoelectronic applications. Recently, transient absorption techniques based on resonant excitonic absorption have been used to study various aspects of excitonic dynamics in these materials. The transient absorption in such measurements originates from phase-space state filling, bandgap renormalization, or screening effects. Here we report a new method to probe excitonic dynamics based on exciton intraband absorption. In this Drude-like process, probe photons are absorbed by excitons in their intraband excitation to higher energy states, causing a transient absorption signal. Although the magnitude of the transient absorption is lower than that of the resonant techniques, the new method is less restrictive on the selection of probe wavelength, has a larger linear range, and can provide complementary information on photocarrier dynamics. Using the WS2 monolayer and bulk samples as examples, we show that the new method can probe exciton-exciton annihilation at high densities and reveal exciton formation processes. We also found that the exciton intraband absorption cross section of the WS2 monolayer is on the order of 10-18 cm2.

Non-Destructive and Discriminating Identification of Illegal Drugs by Transient Absorption Spectroscopy in the Visible and Near-IR Wavelength Range

NASA Astrophysics Data System (ADS)

Sato, Chie; Furube, Akihiro; Katoh, Ryuzi; Nonaka, Hidehiko; Inoue, Hiroyuki

2008-11-01

We have tested the possibility of identifying illegal drugs by means of nanosecond transient absorption spectroscopy with a 10-ns UV-laser pulse for the excitation light and visible-to-near-IR light for the probe light. We measured the transient absorption spectra of acetonitrile solutions of d-methamphetamine, dl-3,4-methylenedioxymethamphetamine hydrochloride (MDMA), and dl-N-methyl-1-(1,3-benzodioxol-5-yl)-2-butanamine hydrochloride (MBDB), which are illegal drugs widely consumed in Japan. Transient absorption signals of these drugs were observed between 400 and 950 nm, a range in which they are transparent in the ground state. By analyzing the spectra in terms of exponential and Gaussian functions, we could identify the drugs and discriminate them from chemical substances having similar structures. We propose that transient absorption spectroscopy will be a useful, non-destructive method of inspecting for illegal drugs, especially when they are dissolved in liquids. Such a method may even be used for drugs packed in opaque materials if it is further extended to utilize intense femtosecond laser pulses.

Note: A flexible light emitting diode-based broadband transient-absorption spectrometer

NASA Astrophysics Data System (ADS)

Gottlieb, Sean M.; Corley, Scott C.; Madsen, Dorte; Larsen, Delmar S.

2012-05-01

This Note presents a simple and flexible ns-to-ms transient absorption spectrometer based on pulsed light emitting diode (LED) technology that can be incorporated into existing ultrafast transient absorption spectrometers or operate as a stand-alone instrument with fixed-wavelength laser sources. The LED probe pulses from this instrument exhibit excellent stability (˜0.5%) and are capable of producing high signal-to-noise long-time (>100 ns) transient absorption signals either in a broadband multiplexed (spanning 250 nm) or in tunable narrowband (20 ns) operation. The utility of the instrument is demonstrated by measuring the photoinduced ns-to-ms photodynamics of the red/green absorbing fourth GMP phosphodiesterase/adenylyl cyclase/FhlA domain of the NpR6012 locus of the nitrogen-fixing cyanobacterium Nostoc punctiforme.

Do fluorescence and transient absorption probe the same intramolecular charge transfer state of 4-(dimethylamino)benzonitrile?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gustavsson, Thomas; Coto, Pedro B.; Serrano-Andres, Luis

2009-07-21

We present here the results of time-resolved absorption and emission experiments for 4-(dimethylamino)benzonitrile in solution, which suggest that the fluorescent intramolecular charge transfer (ICT) state may differ from the twisted ICT (TICT) state observed in transient absorption.

Optical and near-infrared study of the Ca-rich transient iPTF15eqv in the early phase

NASA Astrophysics Data System (ADS)

Kawahara, Naoki; Yamanaka, Masayuki; Kawabata, Koji; Nakaoka, Tatsuya; Kawabata, Miho; Maeda, Keiichi; Takaki, Katsutoshi; Akitaya, Hiroshi; Itoh, Ryosuke; Moritani, Yuki; Uemura, Makoto; Yoshida, Michitoshi

2018-01-01

Supernovae (SNe) exhibiting strong calcium features in their spectra are called Ca-rich transients. Frequently their early-phase spectra also exhibit helium absorption lines. They are mostly discovered in elliptical galaxies or at a remote location far from the host galaxy center. Well-observed samples are still too limited to clarify the explosion and progenitor properties. We present optical and near-infrared observations of a Ca-rich transient iPTF15eqv in the spiral galaxy NGC 3430. The data are obtained using 1.5-m Kanata telescope since Sep 28, 2015. While the discovery was at a post-maximum-phase, we infer the maximum date to be 30 days before the discovery date, by comparing its light curve and spectroscopic evolution to those of well-observed samples. The spectra exhibit absorption lines of He I and prominent emission lines of Ca II IR and [Ca II] from +31 to 69 d after the maximum date. We find that iPTF15eqv is more luminous than other Ca-rich transients by 1.5 to 2 mag on +31 d, and we estimate that the peak absolute magnitude in the R band is approximately -18 to -16.5 mag. The decline rate of the light curve between 30 and 60 d is similar to those of SNe Ib/c. The line velocity of the helium is similar to those of Ca-rich transients but also to SNe Ib. The ejecta properties inferred from our observations indicate that iPTF15eqv has a larger nickel mass than typical Ca-rich transients. While these properties show similarity to SNe Ib, we show that most of these properties are indeed shared by other Ca-rich transients. The properties of iPTF15eqv may thus still be regarded to be within the diversities among the Ca-rich transients.

The effects from high-altitude storm discharges in Earth atmosphere

NASA Astrophysics Data System (ADS)

Kozak, L.; Odzimek, A.; Ivchenko, V.; Kozak, P.; Gala, I.; Lapchuk, V.

2016-06-01

The regularities of appearance of transient luminous effects in Earth atmosphere and features of their ground-based observations are considered. Using video-observations obtained in the Institution of Geophysics of Poland Academy of Sciences the energy of atmospheric afterglow from these processes in visual wavelength range has been determined. Calibrating curve was plotted using unfocal images of Vega. The star spectrum,atmosphere absorption coefficient and characteristics of the observational camera were used.

Optically induced lattice deformations, electronic structure changes, and enhanced superconductivity in YBa 2Cu 3O 6.48

DOE PAGES

Mankowsky, R.; Fechner, M.; Forst, M.; ...

2017-02-28

Resonant optical excitation of apical oxygen vibrational modes in the normal state of underdoped YBa 2Cu 3O 6+x induces a transient state with optical properties similar to those of the equilibrium superconducting state. Amongst these, a divergent imaginary conductivity and a plasma edge are transiently observed in the photo-stimulated state. Femtosecond hard x-ray diffraction experiments have been used in the past to identify the transient crystal structure in this non-equilibrium state. Here, we start from these crystallographic features and theoretically predict the corresponding electronic rearrangements that accompany these structural deformations. Using density functional theory, we predict enhanced hole-doping of themore » CuO 2 planes. The empty chain Cu dy2-z2 orbital is calculated to strongly reduce in energy, which would increase c-axis transport and potentially enhance the interlayer Josephson coupling as observed in the THz-frequency response. From these results, we calculate changes in the soft x-ray absorption spectra at the Cu L-edge. As a result, femtosecond x-ray pulses from a free electron laser are used to probe changes in absorption at two photon energies along this spectrum and provide data consistent with these predictions.« less

Single and double core-hole ion emission spectroscopy of transient neon plasmas produced by ultraintense x-ray laser pulses

NASA Astrophysics Data System (ADS)

Gao, Cheng; Zeng, Jiaolong; Yuan, Jianmin

2016-05-01

Single core-hole (SCH) and double core-hole (DCH) spectroscopy is investigated systematically for neon gas in the interaction with ultraintense x-ray pulses with photon energy from 937 eV to 2000 eV. A time-dependent rate equation, implemented in the detailed level accounting approximation, is utilized to study the dynamical evolution of the level population and emission properties of the laser-produced highly transient plasmas. The plasma density effects on level populations are demonstrated with an x-ray photon energy of 2000 eV. For laser photon energy in the range of 937 - 1360 eV, resonant absorptions (RA) of 1s-np (n> = 2) transitions play important roles in time evolution of the population and DCH emission spectroscopy. For x-ray photon energy larger than 1360 eV, no RA exist and transient plasmas show different features in the DCH spectroscopy.

Exciton Absorption Spectra by Linear Response Methods:Application to Conjugated Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mosquera, Martin A.; Jackson, Nicholas E.; Fauvell, Thomas J.

The theoretical description of the timeevolution of excitons requires, as an initial step, the calculation of their spectra, which has been inaccessible to most users due to the high computational scaling of conventional algorithms and accuracy issues caused by common density functionals. Previously (J. Chem. Phys. 2016, 144, 204105), we developed a simple method that resolves these issues. Our scheme is based on a two-step calculation in which a linear-response TDDFT calculation is used to generate orbitals perturbed by the excitonic state, and then a second linear-response TDDFT calculation is used to determine the spectrum of excitations relative to themore » excitonic state. Herein, we apply this theory to study near-infrared absorption spectra of excitons in oligomers of the ubiquitous conjugated polymers poly(3-hexylthiophene) (P3HT), poly(2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene) (MEH-PPV), and poly(benzodithiophene-thieno[3,4-b]thiophene) (PTB7). For P3HT and MEH-PPV oligomers, the calculated intense absorption bands converge at the longest wavelengths for 10 monomer units, and show strong consistency with experimental measurements. The calculations confirm that the exciton spectral features in MEH-PPV overlap with those of the bipolaron formation. In addition, our calculations identify the exciton absorption bands in transient absorption spectra measured by our group for oligomers (1, 2, and 3 units) of PTB7. For all of the cases studied, we report the dominant orbital excitations contributing to the optically active excited state-excited state transitions, and suggest a simple rule to identify absorption peaks at the longest wavelengths. We suggest our methodology could be considered for further evelopments in theoretical transient spectroscopy to include nonadiabatic effects, coherences, and to describe the formation of species such as charge-transfer states and polaron pairs.« less

Nonconjugated Acyloxy Group Deactivates the Intramolecular Charge-Transfer State in the Carotenoid Fucoxanthin.

PubMed

Staleva-Musto, Hristina; Kuznetsova, Valentyna; West, Robert G; Keşan, Gürkan; Minofar, Babak; Fuciman, Marcel; Bína, David; Litvín, Radek; Polívka, Tomáš

2018-03-22

We used ultrafast transient absorption spectroscopy to study excited-state dynamics of the keto-carotenoid fucoxanthin (Fx) and its two derivatives: 19'-butanoyloxyfucoxanthin (bFx) and 19'-hexanoyloxyfucoxanthin (hFx). These derivatives occur in some light-harvesting systems of photosynthetic microorganisms, and their presence is typically related to stress conditions. Even though the hexanoyl (butanoyl) moiety is not a part of the conjugated system of hFx (bFx), their absorption spectra in polar solvents exhibit more pronounced vibrational bands of the S 2 state than for Fx. The effect of the nonconjugated acyloxy moiety is further observed in transient absorption spectra, which for Fx exhibit characteristic features of an intramolecular charge transfer (ICT) state in all polar solvents. For bFx and hFx, however, much weaker ICT features are detected in methanol, and the spectral markers of the ICT state disappear completely in polar, but aprotic acetonitrile. The presence of the acyloxy moiety also alters the lifetimes of the S 1 /ICT state. For Fx, the lifetimes are 60, 30, and 20 ps in n-hexane, acetonitrile, and methanol, whereas for bFx and hFx, these lifetimes yield 60, 60, and 40 ps, respectively. Testing the S 1 /ICT state lifetimes of hFx in other solvents revealed that some ICT features can be induced only in polar, protic solvents (methanol, ethanol, and ethylene glycol). Thus, bFx and hFx represent a rather rare example of a system in which a nonconjugated functional group significantly alters excited-state dynamics. By comparison with other carotenoids, we show that a keto group at the acyloxy tail, even though it is not in conjugation, affects the electron distribution along the conjugated backbone, resulting in the observed decrease of the ICT character of the S 1 /ICT state of bFx and hFx.

Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in Novel Donor-Acceptor Core-Shell Nanostructures for Organic Photovoltaics

NASA Astrophysics Data System (ADS)

Strain, Jacob; Jamhawi, Abdelqader; Abeywickrama, Thulitha M.; Loomis, Wendy; Rathnayake, Hemali; Liu, Jinjun

2016-06-01

Novel donor-acceptor nanostructures were synthesized via covalent synthesis and/or UV cross-linking method. Their photoinduced dynamics were investigated with ultrafast transient absorption (TA) spectroscopy. These new nanostructures are made with the strategy in mind to reduce manufacturing steps in the process of fabricating an organic photovoltaic cell. By imitating the heterojunction interface within a fixed particle domain, several fabrication steps can be bypassed reducing cost and giving more applicability to other film deposition methods. Such applications include aerosol deposition and ink-jet printing. The systems that were studied by TA spectroscopy include PDIB core, PDIB-P3HT core-shell, and PDIB-PANT core-shell which range in size from 60 to 130 nm. Within the experimentally accessible spectra range there resides a region of ground state bleaching, stimulated emission, and excited-state absorption of both neutrals and anions. Control experiments have been carried out to assign these features. At high pump fluences the TA spectra of PDIB core alone also indicate an intramolecular charge separation. The TA spectroscopy results thus far suggest that the core-shells resemble the photoinduced dynamics of a standard film although the particles are dispersed in solution, which indicates the desired outcome of the work.

Photophysical properties of C60 colloids suspended in water with Triton X-100 surfactant: excited-state properties with femtosecond resolution.

PubMed

Clements, Andrew F; Haley, Joy E; Urbas, Augustine M; Kost, Alan; Rauh, R David; Bertone, Jane F; Wang, Fei; Wiers, Brian M; Gao, De; Stefanik, Todd S; Mott, Andrew G; Mackie, David M

2009-06-11

We examine the photophysics of a colloidal suspension of C(60) particles in a micellar solution of Triton X-100 and water, prepared via a new synthesis which allows high-concentration suspensions. The particle sizes are characterized by transmission electron microscopy and dynamic light scattering and found to be somewhat polydisperse in the range of 10-100 nm. The suspension is characterized optically by UV-vis spectroscopy, femtosecond transient absorption spectroscopy, laser flash photolysis, and z-scan. The ground-state absorbance spectrum shows a broad absorbance feature centered near 450 nm which is indicative of colloidal C(60). The transient absorption dynamics, presented for the first time with femtosecond resolution, are very similar to that of thin films of C(60) and indicate a strong quenching of the singlet excited state on short time scales and evidence of little intersystem crossing to a triplet excited state. Laser flash photolysis reveals that a triplet excited-state absorption spectrum, which is essentially identical in shape to that of molecular C(60) solutions, does indeed arise, but with much lower magnitude and somewhat shorter lifetime. Z-scan analysis confirms that the optical response of this material is dominated by nonlinear scattering.

Correlation-driven charge migration following double ionization and attosecond transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hollstein, Maximilian; Santra, Robin; Pfannkuche, Daniela

2017-05-01

We theoretically investigate charge migration following prompt double ionization. Thereby, we extend the concept of correlation-driven charge migration, which was introduced by Cederbaum and coworkers for single ionization [Chem. Phys. Lett. 307, 205 (1999), 10.1016/S0009-2614(99)00508-4], to doubly ionized molecules. This allows us to demonstrate that compared to singly ionized molecules, in multiply ionized molecules, electron dynamics originating from electronic relaxation and correlation are particularly prominent. In addition, we also discuss how these correlation-driven electron dynamics might be evidenced and traced experimentally using attosecond transient absorption spectroscopy. For this purpose, we determine the time-resolved absorption cross section and find that the correlated electron dynamics discussed are reflected in it with exceptionally great detail. Strikingly, we find that features in the cross section can be traced back to electron hole populations and time-dependent partial charges and hence, can be interpreted with surprising ease. By taking advantage of element-specific core-to-valence transitions even atomic spatial resolution can be achieved. Thus, with the theoretical considerations presented, not only do we predict particularly diverse and correlated electron dynamics in molecules to follow prompt multiple ionization but we also identify a promising route towards their experimental investigation.

Excitation of photosystem I by 760 nm femtosecond laser pulses: transient absorption spectra and intermediates

NASA Astrophysics Data System (ADS)

Cherepanov, Dmitry A.; Shelaev, Ivan V.; Gostev, Fedor E.; Mamedov, Mahir D.; Petrova, Anastasia A.; Aybush, Arseniy V.; Shuvalov, Vladimir A.; Semenov, Alexey Yu; Nadtochenko, Victor A.

2017-09-01

Excitation of photosystem I (PS I) by a femtosecond 760 nm pump leads to one- and two-photon absorption. The one-photon excitation produces intermediates with transient absorption spectra similar to the spectra of the primary [{{{P}}700}+{{{A}}0}-{{A}}1] and secondary [{{{P}}700}+{{A}}0{{{A}}1}-] ion-radical pairs in the PS I reaction center. The two-photon absorption generates the upper level excited states of chlorophyll (Chl) and carotenoid molecules in the antenna. These excited states are converted into the long-lived intermediates and can be tentatively attributed to the excited and charge-transfer ion-radical states of Chl molecules and to the excited states of carotenoids in the antenna. The transient spectra of intermediates generated by two-photon excitation differ from the transient one-photon spectra of the primary and secondary ion-radical pairs.

Absorption dynamics and delay time in complex potentials

NASA Astrophysics Data System (ADS)

Villavicencio, Jorge; Romo, Roberto; Hernández-Maldonado, Alberto

2018-05-01

The dynamics of absorption is analyzed by using an exactly solvable model that deals with an analytical solution to Schrödinger’s equation for cutoff initial plane waves incident on a complex absorbing potential. A dynamical absorption coefficient which allows us to explore the dynamical loss of particles from the transient to the stationary regime is derived. We find that the absorption process is characterized by the emission of a series of damped periodic pulses in time domain, associated with damped Rabi-type oscillations with a characteristic frequency, ω = (E + ε)/ℏ, where E is the energy of the incident waves and ‑ε is energy of the quasidiscrete state of the system induced by the absorptive part of the Hamiltonian; the width γ of this resonance governs the amplitude of the pulses. The resemblance of the time-dependent absorption coefficient with a real decay process is discussed, in particular the transition from exponential to nonexponential regimes, a well-known feature of quantum decay. We have also analyzed the effect of the absorptive part of the potential on the dynamical delay time, which behaves differently from the one observed in attractive real delta potentials, exhibiting two regimes: time advance and time delay.

Hot spots of Io

NASA Technical Reports Server (NTRS)

Pearl, J. C.; Sinton, W. M.

1982-01-01

The size and temperature, morphology and distribution, variability, possible absorption features, and processes of hot spots on Io are discussed, and an estimate of the global heat flux is made. Size and temperature information is deconvolved to obtain equivalent radius and temperature of hot spots, and simultaneously obtained Voyager thermal and imaging data is used to match hot sources with specific geologic features. In addition to their thermal output, it is possible that hot spots are also characterized by production of various gases and particulate materials; the spectral signature of SO2 has been seen. Origins for relatively stable, low temperature sources, transient high temperature sources, and relatively stable, high-tmperature sources are discussed.

BATSE gamma-ray burst line search. 2: Bayesian consistency methodology

NASA Technical Reports Server (NTRS)

Band, D. L.; Ford, L. A.; Matteson, J. L.; Briggs, M.; Paciesas, W.; Pendleton, G.; Preece, R.; Palmer, D.; Teegarden, B.; Schaefer, B.

1994-01-01

We describe a Bayesian methodology to evaluate the consistency between the reported Ginga and Burst and Transient Source Experiment (BATSE) detections of absorption features in gamma-ray burst spectra. Currently no features have been detected by BATSE, but this methodology will still be applicable if and when such features are discovered. The Bayesian methodology permits the comparison of hypotheses regarding the two detectors' observations and makes explicit the subjective aspects of our analysis (e.g., the quantification of our confidence in detector performance). We also present non-Bayesian consistency statistics. Based on preliminary calculations of line detectability, we find that both the Bayesian and non-Bayesian techniques show that the BATSE and Ginga observations are consistent given our understanding of these detectors.

Direct observation of ring-opening dynamics in strong-field ionized selenophene using femtosecond inner-shell absorption spectroscopy

DOE PAGES

Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.; ...

2016-12-21

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C 4H 4Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field inducedmore » ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ 1 = 80 ± 30 fs into a transient molecular species, which then gives rise to the emergence of bare Se + and ring-open cations within an additional τ 2 = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

Trivalent cerium coped crystals as tunable laser systems: two bad apples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hamilton, D.S.

1985-01-01

The 5d-4f transitions of trivalent doped crystals have broad emission bands with large oscillator strengths and near unity quantum efficiency. These characteristics make cerium systems strong candidates for tunable solid state lasers. However, two such cerium crystals will probably never lase. The first is Ce/sup 3 +/:YAG where a strong excited state absorption quenches the lasing transition. Our recent measurements have indicated that the excited state absorption terminates in the YAG conduction band with a peak cross section of 1.0 x 10/sup -17/ cm/sup 2/ at 700 nm. Some of the general features of impurity ion to band spectra aremore » discussed. The second system is Ce/sup 3 +/:CaF/sub 2/ where a uv pump induced photochromic center is produced following excitation of the cerium ions. The initial measurements of cerium related transient absorptions in Ce/sup 3 +/:YLF are also presented.« less

Carrier-Specific Femtosecond XUV Transient Absorption of PbI 2 Reveals Ultrafast Nonradiative Recombination

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Ming-Fu; Verkamp, Max A.; Leveillee, Joshua

Femtosecond carrier recombination in PbI 2 is measured using tabletop high-harmonic extreme ultraviolet (XUV) transient absorption spectroscopy and ultrafast electron diffraction. XUV absorption from 45 eV to 62 eV measures transitions from the iodine 4d core level to the conduction band density of states. Photoexcitation at 400 nm creates separate and distinct transient absorption signals for holes and electrons, separated in energy by the 2.4 eV band gap of the semiconductor. The shape of the conduction band and therefore the XUV absorption spectrum is temperature dependent, and nonradiative recombination converts the initial electronic excitation to thermal excitation within picoseconds. Ultrafastmore » electron diffraction (UED) is used to measure the lattice temperature and confirm the recombination mechanism. Lastly, the XUV and UED results support a 2nd-order recombination model with a rate constant of 2.5x10 -9 cm 3/s.« less

Carrier-Specific Femtosecond XUV Transient Absorption of PbI 2 Reveals Ultrafast Nonradiative Recombination

DOE PAGES

Lin, Ming-Fu; Verkamp, Max A.; Leveillee, Joshua; ...

2017-11-30

Femtosecond carrier recombination in PbI 2 is measured using tabletop high-harmonic extreme ultraviolet (XUV) transient absorption spectroscopy and ultrafast electron diffraction. XUV absorption from 45 eV to 62 eV measures transitions from the iodine 4d core level to the conduction band density of states. Photoexcitation at 400 nm creates separate and distinct transient absorption signals for holes and electrons, separated in energy by the 2.4 eV band gap of the semiconductor. The shape of the conduction band and therefore the XUV absorption spectrum is temperature dependent, and nonradiative recombination converts the initial electronic excitation to thermal excitation within picoseconds. Ultrafastmore » electron diffraction (UED) is used to measure the lattice temperature and confirm the recombination mechanism. Lastly, the XUV and UED results support a 2nd-order recombination model with a rate constant of 2.5x10 -9 cm 3/s.« less

Exploring exciton relaxation and multiexciton generation in PbSe nanocrystals using hyperspectral near-IR probing.

PubMed

Gdor, Itay; Sachs, Hanan; Roitblat, Avishy; Strasfeld, David B; Bawendi, Moungi G; Ruhman, Sanford

2012-04-24

Hyperspectral femtosecond transient absorption spectroscopy is employed to record exciton relaxation and recombination in colloidal lead selenide (PbSe) nanocrystals in unprecedented detail. Results obtained with different pump wavelengths and fluences are scrutinized with regard to three issues: (1) early subpicosecond spectral features due to "hot" excitons are analyzed in terms of suggested underlying mechanisms; (2) global kinetic analysis facilitates separation of the transient difference spectra into single, double, and triple exciton state contributions, from which individual band assignments can be tested; and (3) the transient spectra are screened for signatures of multiexciton generation (MEG) by comparing experiments with excitation pulses both below and well above the theoretical threshold for multiplication. For the latter, a recently devised ultrafast pump-probe spectroscopic approach is employed. Scaling sample concentrations and pump pulse intensities inversely with the extinction coefficient at each excitation wavelength overcomes ambiguities due to direct multiphoton excitation, uncertainties of absolute absorption cross sections, and low signal levels. As observed in a recent application of this method to InAs core/shell/shell nanodots, no sign of MEG was detected in this sample up to photon energy 3.7 times the band gap. Accordingly, numerous reports of efficient MEG in other samples of PbSe suggest that the efficiency of this process varies from sample to sample and depends on factors yet to be determined.

Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters

NASA Astrophysics Data System (ADS)

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; Nobusada, Katsuyuki; Jin, Rongchao

2016-03-01

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications. Electronic supplementary information (ESI) available: The pump dependent transient absorption spectra and the corresponding global analysis results. See DOI: 10.1039/c6nr01008c

Photoisomerization pathways and Raman activity of 1,1'-difluorostilbene

NASA Astrophysics Data System (ADS)

Dobryakov, A. L.; Quick, M.; Richter, C.; Knie, C.; Ioffe, I. N.; Granovsky, A. A.; Mahrwald, R.; Ernsting, N. P.; Kovalenko, S. A.

2017-01-01

The photoisomerization of 1,1'-difluorostilbene, following S0→S1 optical excitation in solution, was studied with femtosecond broadband transient absorption and stimulated Raman spectroscopy, and by quantum-chemical calculations. In n-hexane, trans-to-cis (t →c ) isomerization starts with Franck-Condon relaxation (τ1 t = 0.07 ps) followed by nearly barrierless torsion around the ethylenic bond (τ2 t ≈ 0.3 ps) to a perpendicular conformation P. About 50% of the excited molecules are trapped in P, while others reach the S1(cis) conformation adiabatically. For the opposite cis-to-trans (c →t ) path, the dynamics in n-hexane (τ1 c = 0.04 ps, τ2 c = 0.7 ps) suggest a 5 kJ/mol barrier between the relaxed S1(cis) and P states. The subsequent P decay with τ3 = 0.4 ps is followed by much slower ground-state recovery (τ4 ≈ 3 ps), indicating an intermediate state X. The t →P and c →P torsion depend on solvent viscosity and polarity, whereas the P →X →S0 relaxation and residual torsion is viscosity-independent but still polarity-dependent. Photoisomerization yields are derived from the transient absorption data and compared to those from actinometric measurements. Low-frequency oscillations in the transient signal are assigned to nuclei motions. Transient and stationary stimulated Raman spectra are compared to calculations. Early Franck-Condon Raman spectra differ from those of the quasistationary trans or cis S1 state. The photoisomerization behavior of stilbene and vinyl-substituted derivatives is compared and the general features are discussed.

Fast spectroscopic variations on rapidly-rotating, cool dwarfs. 3: Masses of circumstellar absorbing clouds on AB Doradus

NASA Technical Reports Server (NTRS)

Cameron, A. Collier; Duncan, D. K.; Ehrenfreund, P.; Foing, B. H.; Kuntz, K. D.; Penston, M. V.; Robinson, R. D.; Soderblom, D. R.

1989-01-01

New time-resolved H alpha, Ca II H and K and Mg II h and k spectra of the rapidly-rotating K0 dwarf star AB Doradus (= HD 36705). The transient absorption features seen in the H alpha line are also present in the Ca II and Mg II resonance lines. New techniques are developed for measuring the average strength of the line absorption along lines of sight intersecting the cloud. These techniques also give a measure of the projected cloud area. The strength of the resonance line absorption provides useful new constraints on the column densities, projected surface areas, temperatures and internal turbulent velocity dispersions of the circumstellar clouds producing the absorption features. At any given time the star appears to be surrounded by at least 6 to 10 clouds with masses in the range 2 to 6 x 10(exp 17) g. The clouds appear to have turbulent internal velocity dispersions of order 3 to 20 km/s, comparable with the random velocities of discrete filamentary structures in solar quiescent prominences. Night-to-night changes in the amount of Ca II resonance line absorption can be explained by changes in the amplitude of turbulent motions in the clouds. The corresponding changes in the total energy of the internal motions are of order 10(exp 29) erg per cloud. Changes of this magnitude could easily be activated by the frequent energetic (approximately 10(exp 34) erg) x ray flares seen on this star.

Triplet exciton dissociation and electron extraction in graphene-templated pentacene observed with ultrafast spectroscopy.

PubMed

McDonough, Thomas J; Zhang, Lushuai; Roy, Susmit Singha; Kearns, Nicholas M; Arnold, Michael S; Zanni, Martin T; Andrew, Trisha L

2017-02-08

We compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. Pentacene grown on graphene is interesting because it forms large crystals with the long axis of the molecules "lying-down" (parallel to the surface). At low excitation fluence, spectra for pentacene on graphene contain triplet absorptions at 507 and 545 nm and no bleaching at 630 nm, which we show is due to the orientation of the pentacene molecules. We perform the first transient absorption anisotropy measurements on pentacene, observing negative anisotropy of the 507 and 545 nm peaks, consistent with triplet absorption. A broad feature at 853 nm, observed on both glass and graphene, is isotropic, suggesting hole absorption. At high fluence, there are additional features, whose kinetics and anisotropies are not explained by heating, that we assign to charge generation; we propose a polaron pair absorption at 614 nm. The lifetimes are shorter at high fluence for both pentacene on glass and graphene, indicative of triplet-triplet annihilation that likely enhances charge generation. The anisotropy decays more slowly for pentacene on graphene than on glass, in keeping with the smaller domain size observed via atomic force microscopy. Coherent acoustic phonons are observed for pentacene on graphene, which is a consequence of more homogeneous domains. Measuring the ultrafast dynamics of pentacene as a function of molecular orientation, fluence, and polarization provides new insight to previous spectral assignments.

Ultrafast transient absorption studies of hematite nanoparticles: the effect of particle shape on exciton dynamics.

PubMed

Fitzmorris, Bob C; Patete, Jonathan M; Smith, Jacqueline; Mascorro, Xiomara; Adams, Staci; Wong, Stanislaus S; Zhang, Jin Z

2013-10-01

Much progress has been made in using hematite (α-Fe2 O3 ) as a potentially practical and sustainable material for applications such as solar-energy conversion and photoelectrochemical (PEC) water splitting; however, recent studies have shown that the performance can be limited by a very short charge-carrier diffusion length or exciton lifetime. In this study, we performed ultrafast studies on hematite nanoparticles of different shapes to determine the possible influence of particle shape on the exciton dynamics. Nanorice, multifaceted spheroidal nanoparticles, faceted nanocubes, and faceted nanorhombohedra were synthesized and characterized by using SEM and XRD techniques. Their exciton dynamics were investigated by using femtosecond transient absorption (TA) spectroscopy. Although the TA spectral features differ for the four samples studied, their decay profiles are similar, which can be fitted with time constants of 1-3 ps, approximately 25 ps, and a slow nanosecond component extending beyond the experimental time window that was measured (2 ns). The results indicate that the overall exciton lifetime is weakly dependent on the shape of the hematite nanoparticles, even though the overall optical absorption and scattering are influenced by the particle shape. This study suggests that other strategies need to be developed to increase the exciton lifetime or to lengthen the exciton diffusion length in hematite nanostructures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mapping CTTS dynamics of Na- in tetrahydrofurane with ultrafast multichannel pump-probe spectroscopy.

PubMed

Shoshana, O; Pérez Lustres, J L; Ernsting, N P; Ruhman, S

2006-06-14

Using multichannel femtosecond spectroscopy we have followed Na- charge transfer to solvent (CTTS) dynamics in THF solution. Absorption of the primary photoproducts in the visible, resolved here for the first time, consists of an asymmetric triplet centered at 595 nm, which we assign to a metastable incompletely solvated neutral atomic sodium species. Decay of this feature within approximately 1 ps to a broad and structureless solvated neutral is accompanied by broadening and loss of spectral detail. Kinetic analysis shows that both the spectral structure and the decay of this band are independent of the excitation photon frequency in the range 400-800 nm. With different pump-probe polarizations the anisotropy in transient transmission has been charted and its variation with excitation wavelength surveyed. The anisotropies are assigned to the reactant bleach, indicating that due to solvent-induced symmetry breaking, the CTTS absorption band of Na- is made up of discreet orthogonally polarized sub bands. None of the anisotropy in transient absorption could be associated with the photoproduct triplet band even at the earliest measurable time delays. Along with the documented differences in the spatial distribution of ejected electrons across the tested excitation wavelength range, these results lead us to conclude that photoejection is extremely rapid, and that loss of correlations between the departing electron and its neutral core is faster than our time resolution of approximately 60 fs.

Anomalous photoluminescence in InP1−xBix

PubMed Central

Wu, Xiaoyan; Chen, Xiren; Pan, Wenwu; Wang, Peng; Zhang, Liyao; Li, Yaoyao; Wang, Hailong; Wang, Kai; Shao, Jun; Wang, Shumin

2016-01-01

Low temperature photoluminescence (PL) from InP1−xBix thin films with Bi concentrations in the 0–2.49% range reveals anomalous spectral features with strong and very broad (linewidth of 700 nm) PL signals compared to other bismide alloys. Multiple transitions are observed and their energy levels are found much smaller than the band-gap measured from absorption measurements. These transitions are related to deep levels confirmed by deep level transient spectroscopy, which effectively trap free holes and enhance radiative recombination. The broad luminescence feature is beneficial for making super-luminescence diodes, which can theoretically enhance spatial resolution beyond 1 μm in optical coherent tomography (OCT). PMID:27291823

Discovery of an Ultraviolet Counterpart to an Ultrafast X-Ray Outflow in the Quasar PG 1211+143

NASA Astrophysics Data System (ADS)

Kriss, Gerard A.; Lee, Julia C.; Danehkar, Ashkbiz; Nowak, Michael A.; Fang, Taotao; Hardcastle, Martin J.; Neilsen, Joseph; Young, Andrew

2018-02-01

We observed the quasar PG 1211+143 using the Cosmic Origins Spectrograph on the Hubble Space Telescope in 2015 April as part of a joint campaign with the Chandra X-ray Observatory and the Jansky Very Large Array. Our ultraviolet spectra cover the wavelength range 912–2100 Å. We find a broad absorption feature (∼ 1080 {km} {{{s}}}-1) at an observed wavelength of 1240 Å. Interpreting this as H I Lyα, in the rest frame of PG 1211+143 (z = 0.0809), this corresponds to an outflow velocity of ‑16,980 {km} {{{s}}}-1 (outflow redshift {z}{out}∼ -0.0551), matching the moderate ionization X-ray absorption system detected in our Chandra observation and reported previously by Pounds et al. With a minimum H I column density of {log} {N}{{H}{{I}}}> 14.5, and no absorption in other UV resonance lines, this Lyα absorber is consistent with arising in the same ultrafast outflow as the X-ray absorbing gas. The Lyα feature is weak or absent in archival ultraviolet spectra of PG 1211+143, strongly suggesting that this absorption is transient, and intrinsic to PG 1211+143. Such a simultaneous detection in two independent wavebands for the first time gives strong confirmation of the reality of an ultrafast outflow in an active galactic nucleus.

[Study on transient absorption spectrum of tungsten nanoparticle with HepG2 tumor cell].

PubMed

Cao, Lin; Shu, Xiao-Ning; Liang, Dong; Wang, Cong

2014-07-01

Significance of this study lies in tungsten nano materials can be used as a preliminary innovative medicines applied basic research. This paper investigated the inhibition of tungsten nanoparticles which effected on human hepatoma HepG2 cells by MTT. The authors use transient absorption spectroscopy (TAS) technology absorption and emission spectra characterization of charge transfer between nanoparticles and tumor cell. The authors discussed the role of the tungsten nanoparticles in the tumor early detection of the disease and its anti-tumor properties. In the HepG2 experiments system, 100-150 microg x mL(-1) is the best drug concentration of anti-tumor activity which recact violently within 6 hours and basically completed in 24 hours. The results showed that transient absorption spectroscopy can be used as tumor detection methods and characterization of charge transfer between nano-biosensors and tumor cells. Tungsten nanoparticles have potential applications as anticancer drugs.

S193: another non-eclipsing SW Sex star

NASA Astrophysics Data System (ADS)

Martínez-Pais, I. G.; Rodríguez-Gil, P.; Casares, J.

1999-05-01

We present time-resolved optical spectroscopy of the cataclysmic variable S193. The emission lines are remarkably similar to those of V795 Her and exhibit high-velocity S-waves and complex absorptions that are modulated with the orbital period. Evidence for transient anomalous spectral features is seen during the first two nights of our run. We propose that S193 and V795 Her are non-eclipsing SW Sex stars. Finally, we show that the `disc overflow' model fails to explain the Balmer line orbital behaviour in these low-inclination systems.

Femtosecond time-resolved X-ray absorption spectroscopy of anatase TiO2 nanoparticles using XFEL

PubMed Central

Obara, Yuki; Ito, Hironori; Ito, Terumasa; Kurahashi, Naoya; Thürmer, Stephan; Tanaka, Hiroki; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yamamoto, Yo-ichi; Karashima, Shutaro; Nishitani, Junichi; Yabashi, Makina; Suzuki, Toshinori; Misawa, Kazuhiko

2017-01-01

The charge-carrier dynamics of anatase TiO2 nanoparticles in an aqueous solution were studied by femtosecond time-resolved X-ray absorption spectroscopy using an X-ray free electron laser in combination with a synchronized ultraviolet femtosecond laser (268 nm). Using an arrival time monitor for the X-ray pulses, we obtained a temporal resolution of 170 fs. The transient X-ray absorption spectra revealed an ultrafast Ti K-edge shift and a subsequent growth of a pre-edge structure. The edge shift occurred in ca. 100 fs and is ascribed to reduction of Ti by localization of generated conduction band electrons into shallow traps of self-trapped polarons or deep traps at penta-coordinate Ti sites. Growth of the pre-edge feature and reduction of the above-edge peak intensity occur with similar time constants of 300–400 fs, which we assign to the structural distortion dynamics near the surface. PMID:28713842

Picosecond flash spectroscopic studies on ultraviolet stabilizers and stabilized polymers

NASA Technical Reports Server (NTRS)

Scott, G. W.

1982-01-01

Spectroscopic and excited state decay kinetics are reported for monomeric and polymeric forms of ultraviolet stabilizers in the 2-(2'-hydroxyphenyl)-benzotriazole and 2-hydroxybenzophenone classes. For some of these molecules in various solvents at room temperature, (1) ground state absorption spectra, (2) emission spectra, (3) picosecond time-resolved transient absorption spectra, (4) ground state absorption recovery kinetics, (5) emission kinetics, and (6) transient absorption kinetics are reported. In the solid state at low temperatures, emission spectra and their temperature dependent kinetics up to approximately 200K as well as, in one case, the 12K excitation spectra of the observed dual emission are also reported.

Black Box Real-Time Transient Absorption Spectroscopy and Electron Correlation

NASA Astrophysics Data System (ADS)

Parkhill, John

2017-06-01

We introduce an atomistic, all-electron, black-box electronic structure code to simulate transient absorption (TA) spectra and apply it to simulate pyrazole and a GFP- chromophore derivative1. The method is an application of OSCF2, our dissipative exten- sion of time-dependent density-functional theory. We compare our simulated spectra directly with recent ultra-fast spectroscopic experiments. We identify features in the TA spectra to Pauli-blocking which may be missed without a first-principles model. An important ingredient in this method is the stationary-TDDFT correction scheme recently put forwards by Fischer, Govind, and Cramer which allows us to overcome a limitation of adiabatic TDDFT. We demonstrate that OSCF2 is able to reproduce the energies of bleaches and induced absorptions, as well as the decay of the transient spectrum, with only the molecular structure as input. We show that the treatment of electron correlation is the biggest hurdle for TA simulations, which motivates the second half of the talk a new method for realtime electron correlation. We continue to derive and propagate self-consistent electronic dynamics. Extending our derivation of OSCF2 to include electron correlation we obtain a non-linear correlated one-body equation of motion which corrects TDHF. Similar equations are known in quantum kinetic theory, but rare in electronic structure. We introduce approximations that stabilize the theory and reduce its computational cost. We compare the resulting dynamics with well-known exact and approximate theories showing improvements over TDHF. When propagated EE2 changes occupation numbers like exact theory, an important feature missing from TDHF or TDDFT. We introduce a rotating wave approximation to reduce the scaling of the model to O(N^4), and enable propagation on realistically large systems. The equation-of-motion does not rely on a pure-state model for the electronic state, and could be used to study the relationship between electron correlation and relaxation/dephasing or as a non-adiabatic kernel for TDDFT. We show that a quasi-thermal Fermi-Dirac population of one-particle states is a stationary state of the method reached as the endpoint of propagation in some limits. We discuss this 'thermalization' of an isolated quantum many-body system in the context of the eigenstate thermalization hypothesis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lackner, Florian; Chatterley, Adam S.; Pemmaraju, C. D.

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C 4H 4Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field inducedmore » ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ 1 = 80 ± 30 fs into a transient molecular species, which then gives rise to the emergence of bare Se + and ring-open cations within an additional τ 2 = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

Transient-Absorption Spectroscopy of Cis-Trans Isomerization of N,N-dimethyl-4,4'-Azodianiline with 3D-Printed Temperature-Controlled Sample Holder

ERIC Educational Resources Information Center

Kosenkov, Dmytro; Shaw, James; Zuczek, Jennifer; Kholod, Yana

2016-01-01

The laboratory unit demonstrates a project based approach to teaching physical chemistry laboratory where upper-division undergraduates carry out a transient-absorption experiment investigating the kinetics of cis-trans isomerization of N,N-dimethyl-4,4'-azodianiline. Students participate in modification of a standard flash-photolysis spectrometer…

Ultrafast Transient Absorption Spectroscopy Investigation of Photoinduced Dynamics in POLY(3-HEXYLTHIOPHENE)-BLOCK-OLIGO(ANTHRACENE-9,10-DIYL)

NASA Astrophysics Data System (ADS)

Strain, Jacob; Rathnayake, Hemali; Liu, Jinjun

2017-06-01

Semiconducting polymer nanostructures featuring bulk heterojunction (BHJ) architecture are promising light harvesters in photovoltaic (PV) devices because they allow control of individual domain sizes, internal structure and ordering, as well as well-defined contact between the electron donor and acceptor. Power conversion efficiency (PCE) of PV devices strongly depends on photoinduced dynamics. Understanding and optimizing photoinduced charge transfer processes in BHJ's hence help improve the performance of PV devices and increase their PCE in particular. We have investigated the photoinduced dynamics of a block polymer containing moieties of poly-3-hexylthiophene (P3HT) and polyanthracene (PANT) in solution and in solid state with femtosecond transient absorption (TA) spectroscopy. The dynamics of the polymer PANT alone are also studied as a control. The TA spectra of PANT includes a strong excited state absorption centered at 610 (nm) along with a stimulated emission signal stretching past the detection limit into the UV region which is absent in the monomer's spectra in the detection window. The block polymer's TA spectra strongly resembles that of P3HT but a noticeable positive pull on P3HT's stimulated emission signal residing at 575-620 (nm) is indicative of the excited state absorption of PANT in the adjacent spectral region. The doubling of the lifetime exciton delocalization on the block polymer versus P3HT alone have alluded that the lifetime of P3HT is extended by the covalent addition of PANT. The current spectroscopic investigation represents an interesting example of photoinduced processes in systems with complex energy level structure. Studies of dependence of change generation and separation on composition, dimension, and morphology of the heterojunctions are in process.

Carrier lifetime in exfoliated few-layer graphene determined from intersubband optical transitions.

PubMed

Limmer, Thomas; Feldmann, Jochen; Da Como, Enrico

2013-05-24

We report a femtosecond transient spectroscopy study in the near to middle infrared range, 0.8-0.35 eV photon energy, on graphene and few layer graphene single flakes. The spectra show an evolving structure of photoinduced absorption bands superimposed on the bleaching caused by Pauli blocking of the interband optically coupled states. Supported by tight-binding model calculations, we assign the photoinduced absorption features to intersubband transitions as the number of layers is increased. Interestingly, the intersubband photoinduced resonances show a longer dynamics than the interband bleaching, because of their independence from the absolute energy of the carriers with respect to the Dirac point. The dynamic of these intersubband transitions reflects the lifetime of the hot carriers and provides an elegant method to access it in this important class of semimetals.

Carrier Lifetime in Exfoliated Few-Layer Graphene Determined from Intersubband Optical Transitions

NASA Astrophysics Data System (ADS)

Limmer, Thomas; Feldmann, Jochen; Da Como, Enrico

2013-05-01

We report a femtosecond transient spectroscopy study in the near to middle infrared range, 0.8-0.35 eV photon energy, on graphene and few layer graphene single flakes. The spectra show an evolving structure of photoinduced absorption bands superimposed on the bleaching caused by Pauli blocking of the interband optically coupled states. Supported by tight-binding model calculations, we assign the photoinduced absorption features to intersubband transitions as the number of layers is increased. Interestingly, the intersubband photoinduced resonances show a longer dynamics than the interband bleaching, because of their independence from the absolute energy of the carriers with respect to the Dirac point. The dynamic of these intersubband transitions reflects the lifetime of the hot carriers and provides an elegant method to access it in this important class of semimetals.

Gas exchange in fruits related to skin condition and fruit ripening studied with diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Huang, Jing; Zhang, Hao; Lin, Huiying; Li, Tianqi; Mei, Liang; Svanberg, Katarina; Svanberg, Sune

2016-12-01

The concentration of the biologically active molecular oxygen gas is of crucial importance for fruits in the metabolic respiration, maturation, and ripening processes. In our study, oxygen content and oxygen transport in fruits, exemplified by apples and guavas, were studied noninvasively by gas in scattering media absorption spectroscopy. The technique is based on the fact that free gases typically have 10,000 times narrower absorption features than the bulk material. The technique was demonstrated in studies of the influence of the fruit skin in regulating the internal oxygen balance, by observing the signal response of the internal oxygen gas to a transient change in the ambient gas concentration on peeled and unpeeled fruits. In addition, the gas exchange rate at different ripening stages was also studied in intact guavas.

Gas exchange in fruits related to skin condition and fruit ripening studied with diode laser spectroscopy.

PubMed

Huang, Jing; Zhang, Hao; Lin, Huiying; Li, Tianqi; Mei, Liang; Svanberg, Katarina; Svanberg, Sune

2016-12-01

The concentration of the biologically active molecular oxygen gas is of crucial importance for fruits in the metabolic respiration, maturation, and ripening processes. In our study, oxygen content and oxygen transport in fruits, exemplified by apples and guavas, were studied noninvasively by gas in scattering media absorption spectroscopy. The technique is based on the fact that free gases typically have 10,000 times narrower absorption features than the bulk material. The technique was demonstrated in studies of the influence of the fruit skin in regulating the internal oxygen balance, by observing the signal response of the internal oxygen gas to a transient change in the ambient gas concentration on peeled and unpeeled fruits. In addition, the gas exchange rate at different ripening stages was also studied in intact guavas.

The chromospheric association of the metric type 3 bursts - implications concerning the acceleration of solar electrons and the active streamers

NASA Technical Reports Server (NTRS)

Axisa, F.; Martres, M. J.; Pick, M.; Soru-Escaut, I.

1973-01-01

In two recent papers it was shown that the metric type 3 emission is closely related to a transient perturbation seen in absorption in the H alpha line. In addition, this perturbation sometimes triggers a flare, sometimes not. This can explain why the type 3 have a poor H alpha flare correlation rate and still are a typical flash phase emission when flare-associated. The characteristics are summarized of the new association proposed. It is assumed that 10 to 100 keV electrons are accelerated in connection with a particular kind of transient H alpha absorbing feature. For as yet undetermined reasons, this process would often, but not always, result in a more efficient acceleration coincident with the early phase of the optical flare. The possibilities that this process could lead occasionally to long lasting subrelativistic particle emissive region are explored.

Photophysical studies of chromium sensitizers designed for excited state hole transfer to semiconductors and sequential hole/electron transfers from photoexcited cadmium sulfide nanorods to mononuclear ruthenium water-oxidation catalysts

NASA Astrophysics Data System (ADS)

Tseng, Huan-Wei

This dissertation describes three research projects related to solar cells and solar water splitting with a goal of utilizing solar energy, a renewable energy source. The first project is focused on photophysical studies of four newly-synthesized Cr(III) tris-bipyridyl complexes featuring the 4-dmcbpy (dimethyl 2,2'-bipyridine-4,4'-dicarboxylate) ligand. Static and time-resolved emission results suggest that the complexes store ˜1.7 eV of energy for multiple microseconds. Using cyclic voltammetry, it is found that the inclusion of 4-dmcbpy shifts the E1/2 of CrIII/II by +0.2 V from the homoleptic parent complexes without 4-dmcbpy. All four complexes have excited state potentials of CrIII*/II between +1.8 and +2.0 V vs. NHE, placing them among the most powerful photooxidants reported and making them candidates for hole-injection sensitizers. The second project continues with Cr(III) complexes, but using iminopyridine Schiff base ligands. Two complexes feature hexadentate ligands and the other two are their tris-bidentate analogues. One of each pair contains methyl ester groups for attachment to semiconductors. Cyclic voltammograms show that the hexadentate and tris-bidentate analogues have almost identical reduction potentials, but the addition of ester substituents shifts the reduction potentials by +0.2 V. The absorption spectra of the hexadentate complexes show improved absorption of visible light compared to the tris-bidentate analogues. For freshly prepared sample solutions in CH3CN, time-resolved emission and transient absorption measurements for the Cr(III) tris-bidentate ester complex show a doublet excited state with a 17-19 microsecond lifetime at room temperature, while no emission or transient absorption signals from the doublet states are observed for the hexadentate analogue under the same conditions. The dramatic difference is due to the presence of a nonligated bridgehead nitrogen atom. The third project features charge transfer interactions between a photoexcited cadmium sulfide nanorod and [Ru(diethyl 2,2'-bipyridine-4,4'-dicarboxylate)(2,2':6',2"-terpyridine)Cl] +, a mononuclear water-oxidation catalyst. Upon photoexcitation, hole transfer from the cadmium sulfide nanorod oxidizes the catalyst (Ru 2+ → Ru3+) on a 100 ps to 1 ns timescale. This is followed by electron transfer (10-100 ns) from the nanorod to reduce the Ru3+ center. The relatively slow electron transfer dynamics may provide opportunities for the accumulation of multiple holes at the catalyst, which is required for water oxidation.

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.

Photooxidation of Diimine Dithiolate Platinium(II) Complexes Induced by Charge Transfer to Diimine Excitation.

PubMed

Zhang, Yin; Ley, Kevin D.; Schanze, Kirk S.

1996-11-20

A photochemical and photophysical investigation was carried out on (tbubpy)Pt(II)(dpdt) and (tbubpy)Pt(II)(edt) (1 and 2, respectively, where tbubpy = 4,4'-di-tert-butyl-2,2'-bipyridine, dpdt = meso-1,2-diphenyl-1,2-ethanedithiolate and edt = 1,2-ethanedithiolate). Luminescence and transient absorption studies reveal that these complexes feature a lowest excited state with Pt(S)(2) --> tbubpy charge transfer to diimine character. Both complexes are photostable in deoxygenated solution; however, photolysis into the visible charge transfer band in air-saturated solution induces moderately efficient photooxidation. Photooxidation of 1 produces the dehydrogenation product (tbubpy)Pt(II)(1,2-diphenyl-1,2-ethenedithiolate) (4). By contrast, photooxidation of 2 produces S-oxygenated complexes in which one or both thiolate ligands are converted to sulfinate (-SO(2)R) ligands. Mechanistic photochemical studies and transient absorption spectroscopy reveal that photooxidation occurs by (1) energy transfer from the charge transfer to diimine excited state of 1 to (3)O(2) to produce (1)O(2) and (2) reaction between (1)O(2) and the ground state 1. Kinetic data indicates that excited state 1 produces (1)O(2) efficiently and that reaction between ground state 1 and (1)O(2) occurs with k approximately 3 x 10(8) M(-)(1) s(-)(1).

Polarization-controlled optimal scatter suppression in transient absorption spectroscopy

PubMed Central

Malý, Pavel; Ravensbergen, Janneke; Kennis, John T. M.; van Grondelle, Rienk; Croce, Roberta; Mančal, Tomáš; van Oort, Bart

2017-01-01

Ultrafast transient absorption spectroscopy is a powerful technique to study fast photo-induced processes, such as electron, proton and energy transfer, isomerization and molecular dynamics, in a diverse range of samples, including solid state materials and proteins. Many such experiments suffer from signal distortion by scattered excitation light, in particular close to the excitation (pump) frequency. Scattered light can be effectively suppressed by a polarizer oriented perpendicular to the excitation polarization and positioned behind the sample in the optical path of the probe beam. However, this introduces anisotropic polarization contributions into the recorded signal. We present an approach based on setting specific polarizations of the pump and probe pulses, combined with a polarizer behind the sample. Together, this controls the signal-to-scatter ratio (SSR), while maintaining isotropic signal. We present SSR for the full range of polarizations and analytically derive the optimal configuration at angles of 40.5° between probe and pump and of 66.9° between polarizer and pump polarizations. This improves SSR by (or compared to polarizer parallel to probe). The calculations are validated by transient absorption experiments on the common fluorescent dye Rhodamine B. This approach provides a simple method to considerably improve the SSR in transient absorption spectroscopy. PMID:28262765

Interdye Hole Transport Accelerates Recombination in Dye Sensitized Mesoporous Films.

PubMed

Moia, Davide; Szumska, Anna; Vaissier, Valérie; Planells, Miquel; Robertson, Neil; O'Regan, Brian C; Nelson, Jenny; Barnes, Piers R F

2016-10-12

Charge recombination between oxidized dyes attached to mesoporous TiO 2 and electrons in the TiO 2 was studied in inert electrolytes using transient absorption spectroscopy. Simultaneously, hole transport within the dye monolayers was monitored by transient absorption anisotropy. The rate of recombination decreased when hole transport was inhibited selectively, either by decreasing the dye surface coverage or by changing the electrolyte environment. From Monte Carlo simulations of electron and hole diffusion in a particle, modeled as a cubic structure, we identify the conditions under which hole lifetime depends on the hole diffusion coefficient for the case of normal (disorder free) diffusion. From simulations of transient absorption and transient absorption anisotropy, we find that the rate and the dispersive character of hole transport in the dye monolayer observed spectroscopically can be explained by incomplete coverage and disorder in the monolayer. We show that dispersive transport in the dye monolayer combined with inhomogeneity in the TiO 2 surface reactivity can contribute to the observed stretched electron-hole recombination dynamics and electron density dependence of hole lifetimes. Our experimental and computational analysis of lateral processes at interfaces can be applied to investigate and optimize charge transport and recombination in solar energy conversion devices using electrodes functionalized with molecular light absorbers and catalysts.

Femtosecond transient absorption dynamics of close-packed gold nanocrystal monolayer arrays*1

NASA Astrophysics Data System (ADS)

Eah, Sang-Kee; Jaeger, Heinrich M.; Scherer, Norbert F.; Lin, Xiao-Min; Wiederrecht, Gary P.

2004-03-01

Femtosecond transient absorption spectroscopy is used to investigate hot electron dynamics of close-packed 6 nm gold nanocrystal monolayers. Morphology changes of the monolayer caused by the laser pump pulse are monitored by transmission electron microscopy. At low pump power, the monolayer maintains its structural integrity. Hot electrons induced by the pump pulse decay through electron-phonon (e-ph) coupling inside the nanocrystals with a decay constant that is similar to the value for bulk films. At high pump power, irreversible particle aggregation and sintering occur in the nanocrystal monolayer, which cause damping and peak shifting of the transient bleach signal.

Time-domain calculations of the polarized Raman spectra, the transient infrared absorption anisotropy, and the extent of delocalization of the OH stretching mode of liquid water.

PubMed

Torii, Hajime

2006-08-03

The polarized Raman spectrum and the time dependence of the transient infrared (TRIR) absorption anisotropy are calculated for the OH stretching mode of liquid water (neat liquid H2O) by using time-domain formulations, which include the effects of both the diagonal frequency modulations (of individual oscillators) induced by the interactions between the dipole derivatives and the intermolecular electric field, and the off-diagonal (intermolecular) vibrational coupling described by the transition dipole coupling (TDC) mechanism. The IR spectrum of neat liquid H2O and the TRIR anisotropy of a liquid mixture of H2O/HDO/D2O are also calculated. It is shown that the calculated features of these optical signals, including the temperature dependence of the polarized Raman and IR spectra, are in reasonable agreement with the experimental results, indicating that the frequency separation between the isotropic and anisotropic components of the polarized Raman spectrum and the rapid decay (approximately 0.1 ps) of the TRIR anisotropy of the OH stretching mode of neat liquid H2O are mainly controlled by the resonant intermolecular vibrational coupling described by the TDC mechanism. Comparing with the time evolution of vibrational excitations, it is suggested that the TRIR anisotropy decays in the time needed for the initially localized vibrational excitations to delocalize over a few oscillators. It is also shown that the enhancement of the dipole derivatives by the interactions with surrounding molecules is an important factor in generating the spectral profiles of the OH stretching Raman band. The time-domain behavior of the molecular motions that affect the spectroscopic features is discussed.

Acceptor and Excitation Density Dependence of the Ultrafast Polaron Absorption Signal in Donor-Acceptor Organic Solar Cell Blends.

PubMed

Zarrabi, Nasim; Burn, Paul L; Meredith, Paul; Shaw, Paul E

2016-07-21

Transient absorption spectroscopy on organic semiconductor blends for solar cells typically shows efficient charge generation within ∼100 fs, accounting for the majority of the charge carriers. In this Letter, we show using transient absorption spectroscopy on blends containing a broad range of acceptor content (0.01-50% by weight) that the rise of the polaron signal is dependent on the acceptor concentration. For low acceptor content (<10% by weight), the polaron signal rises gradually over ∼1 ps with most polarons generated after 200 fs, while for higher acceptor concentrations (>10%) most polarons are generated within 200 fs. The rise time in blends with low acceptor content was also found to be sensitive to the pump fluence, decreasing with increasing excitation density. These results indicate that the sub-100 fs rise of the polaron signal is a natural consequence of both the high acceptor concentrations in many donor-acceptor blends and the high excitation densities needed for transient absorption spectroscopy, which results in a short average distance between the exciton and the donor-acceptor interface.

Light, Molecules, Action: Broadband UV-visible transient absorption studies of excited state dynamics in photoactive molecules

NASA Astrophysics Data System (ADS)

Sension, Roseanne

2015-03-01

Broadband UV-visible transient absorption spectroscopy provides a powerful tool for the investigation of the dynamics of electronically excited molecules in the condensed phase. It is now possible to obtain transient spectra on a routine basis spanning the range from <300 nm to >800 nm with femtosecond time resolution. We have used this method to study the excited state dynamics and internal conversion of a range of molecular systems with potential application as optically powered molecular devices. The cyclohexadiene ring-opening reaction is the basis of a class of important optical switches and of the biological synthesis of previtamin D3. The ring-opening reaction is ultrafast, occurring on a picosecond to subpicosecond times scale depending on the substituents around the ring. These have a significant influence on the dynamics and electronic structure of the electronically excited molecule. The results of a series of transient absorption studies as a function of chromophore substitution and environment will be presented. The cis-trans isomerization of polyene molecules, especially substituted stilbenes, provides another important class of functional molecular transformations. Again the excited state dynamics can be ultrafast with photochemistry controlled by details of the curve crossings and conical intersections. Finally the photochemistry of the even more complex set of cobalamin chromophores with a photoalabile C-Co bond has been proposed as a tool for spatio-temporal control of molecule delivery including drug delivery. Broadband transient absorption spectroscopy has been used to investigate the ultrafast electronic dynamics of a range of cobalamin compounds with comparison to detailed theoretical calculations. The results of these studies will be presented.

Flash photolysis and pulse radiolysis studies on collagen Type I in acetic acid solution.

PubMed

Sionkowska, Alina

2006-07-03

An investigation of the photochemical properties of collagen Type I in acetic acid solution was carried out using nanosecond laser irradiation. The transient spectra of collagen solution excited at 266 nm show two bands. One of them with maximum at 295 nm and the second one with maximum at 400 nm. The peak at 400 nm is assigned to tyrosyl radicals. The first peak of the transient absorption spectra at 295 nm is probably due to photoionisation producing collagen radical cation. The transient for collagen solution in acetic acid at 640 nm was not observed. It is evidence that there is no hydrated electron in the irradiated collagen solution. The reactions of hydrated electrons and (*)OH radicals with collagen have been studied by pulse radiolysis. In the absorption spectra of products resulting from the reaction of collagen with e(aq)(-) no characteristic maximum absorption in UV and visible light region has been observed. In the absorption spectra of products resulting from the reaction of the hydroxyl radicals with collagen two bands have been observed. The first one at 320 nm and the second one at 405 nm. Reaction of (*)OH radicals with tyrosine residues in collagen chains gives rise to Tyr phenoxyl radicals (absorption at 400 nm).

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

PubMed

Koch, Marius; Letrun, Romain; Vauthey, Eric

2014-03-12

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

Excited-state dynamics of pentacene derivatives with stable radical substituents.

PubMed

Ito, Akitaka; Shimizu, Akihiro; Kishida, Noriaki; Kawanaka, Yusuke; Kosumi, Daisuke; Hashimoto, Hideki; Teki, Yoshio

2014-06-23

The excited-state dynamics of pentacene derivatives with stable radical substituents were evaluated in detail through transient absorption measurements. The derivatives showed ultrafast formation of triplet excited state(s) in the pentacene moiety from a photoexcited singlet state through the contributions of enhanced intersystem crossing and singlet fission. Detailed kinetic analyses for the transient absorption data were conducted to quantify the excited-state characteristics of the derivatives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy.

PubMed

Chatterley, Adam S; Lackner, Florian; Neumark, Daniel M; Leone, Stephen R; Gessner, Oliver

2016-06-07

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10(13) and 2.2 × 10(14) W cm(-2). The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br(++). However, the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br(+), and Br(++), respectively. Transient molecular ion features assigned to DBE(+) and DBE(++) are observed, with dynamics linked to the production of Br(+) products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE(+) ions on a shallow potential energy surface. The appearance of Br(+) ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE(+) ionic species. Dicationic Br(++) products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.

Tracking dissociation dynamics of strong-field ionized 1,2-dibromoethane with femtosecond XUV transient absorption spectroscopy

DOE PAGES

Chatterley, Adam S.; Lackner, Florian; Neumark, Daniel M.; ...

2016-05-11

Using femtosecond time-resolved extreme ultraviolet absorption spectroscopy, the dissociation dynamics of the haloalkane 1,2-dibromoethane (DBE) have been explored following strong field ionization by femtosecond near infrared pulses at intensities between 7.5 × 10 13 and 2.2 × 10 14 W cm -2. The major elimination products are bromine atoms in charge states of 0, +1, and +2. The charge state distribution is strongly dependent on the incident NIR intensity. While the yield of neutral fragments is essentially constant for all measurements, charged fragment yields grow rapidly with increasing NIR intensities with the most pronounced effect observed for Br ++. However,more » the appearance times of all bromine fragments are independent of the incident field strength; these are found to be 320 fs, 70 fs, and 30 fs for Br˙, Br +, and Br ++, respectively. Transient molecular ion features assigned to DBE + and DBE ++ are observed, with dynamics linked to the production of Br + products. Neutral Br˙ atoms are produced on a timescale consistent with dissociation of DBE + ions on a shallow potential energy surface. The appearance of Br + ions by dissociative ionization is also seen, as evidenced by the simultaneous decay of a DBE + ionic species. Dicationic Br ++ products emerge within the instrument response time, presumably from Coulomb explosion of triply charged DBE.« less

Slow Organic-to-Inorganic Sub-Lattice Thermalization in Methylammonium Lead Halide Perovskites Observed by Ultrafast Photoluminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Angela Y.; Cho, Yi-Ju; Chen, Kuan-Chen

2016-05-31

Carrier dynamics in methylammonium lead halide (CH3NH3PbI3-xClx) perovskite thin films, of differing crystal morphology, are examined as functions of temperature and excitation wavelength. At room temperature, long-lived (> nanosecond) transient absorption signals indicate negligible carrier trapping. However, in measurements of ultrafast photoluminescence excited at 400 nm, a heretofore unexplained, large amplitude (50%-60%), 45 ps decay process is observed. This feature persists for temperatures down to the orthorhombic phase transition. Varying pump photon energy reveals that the fast, band-edge photoluminescence (PL) decay only appears for excitation >= 2.38 eV (520 nm), with larger amplitudes for higher pump energies. Lower photon-energy excitationmore » yields slow dynamics consistent with negligible carrier trapping. Further, sub-bandgap two-photon pumping yields identical PL dynamics as direct absorption, signifying sensitivity to the total deposited energy and insensitivity to interfacial effects. Together with first principles electronic structure and ab initio molecular dynamics calculations, the results suggest the fast PL decay stems from excitation of high energy phonon modes associated with the organic sub-lattice that temporarily enhance wavefunction overlap within the inorganic component owing to atomic displacement, thereby transiently changing the PL radiative rate during thermalization. Hence, the fast PL decay relates a characteristic organic-to-inorganic sub-lattice equilibration timescale at optoelectronic-relevant excitation energies.« less

Quantum state-resolved probing of strong-field-ionized xenon atoms using femtosecond high-order harmonic transient absorption spectroscopy.

PubMed

Loh, Zhi-Heng; Khalil, Munira; Correa, Raoul E; Santra, Robin; Buth, Christian; Leone, Stephen R

2007-04-06

Femtosecond high-order harmonic transient absorption spectroscopy is used to resolve the complete |j,m quantum state distribution of Xe+ produced by optical strong-field ionization of Xe atoms at 800 nm. Probing at the Xe N4/5 edge yields a population distribution rhoj,|m| of rho3/2,1/2ratiorho1/2,1/2ratiorho3/2,3/2=75+/-6 :12+/-3 :13+/-6%. The result is compared to a tunnel ionization calculation with the inclusion of spin-orbit coupling, revealing nonadiabatic ionization behavior. The sub-50-fs time resolution paves the way for tabletop extreme ultraviolet absorption probing of ultrafast dynamics.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, L. X.; Zhang, X.; Lockard, J. V.

Transient molecular structures along chemical reaction pathways are important for predicting molecular reactivity, understanding reaction mechanisms, as well as controlling reaction pathways. During the past decade, X-ray transient absorption spectroscopy (XTA, or LITR-XAS, laser-initiated X-ray absorption spectroscopy), analogous to the commonly used optical transient absorption spectroscopy, has been developed. XTA uses a laser pulse to trigger a fundamental chemical process, and an X-ray pulse(s) to probe transient structures as a function of the time delay between the pump and probe pulses. Using X-ray pulses with high photon flux from synchrotron sources, transient electronic and molecular structures of metal complexes havemore » been studied in disordered media from homogeneous solutions to heterogeneous solution-solid interfaces. Several examples from the studies at the Advanced Photon Source in Argonne National Laboratory are summarized, including excited-state metalloporphyrins, metal-to-ligand charge transfer (MLCT) states of transition metal complexes, and charge transfer states of metal complexes at the interface with semiconductor nanoparticles. Recent developments of the method are briefly described followed by a future prospective of XTA. It is envisioned that concurrent developments in X-ray free-electron lasers and synchrotron X-ray facilities as well as other table-top laser-driven femtosecond X-ray sources will make many breakthroughs and realise dreams of visualizing molecular movies and snapshots, which ultimately enable chemical reaction pathways to be controlled.« less

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE PAGES

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.; ...

2017-02-20

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

Light-induced radical formation and isomerization of an aromatic thiol in solution followed by time-resolved x-ray absorption spectroscopy at the sulfur K-edge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ochmann, Miguel; von Ahnen, Inga; Cordones, Amy A.

Here, we applied time-resolved sulfur-1s absorption spectroscopy to a model aromatic thiol system as a promising method for tracking chemical reactions in solution. Sulfur-1s absorption spectroscopy allows tracking multiple sulfur species with a time resolution of ~70 ps at synchrotron radiation facilities. Experimental transient spectra combined with high-level electronic structure theory allow identification of a radical and two thione isomers, which are generated upon illumination with 267 nm radiation. Moreover, the regioselectivity of the thione isomerization is explained by the resulting radical frontier orbitals. This work demonstrates the usefulness and potential of time-resolved sulfur-1s absorption spectroscopy for tracking multiple chemicalmore » reaction pathways and transient products of sulfur-containing molecules in solution.« less

RAPIDLY RISING TRANSIENTS IN THE SUPERNOVA—SUPERLUMINOUS SUPERNOVA GAP

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arcavi, Iair; Howell, D. Andrew; Wolf, William M.

2016-03-01

We present observations of four rapidly rising (t{sub rise} ≈ 10 days) transients with peak luminosities between those of supernovae (SNe) and superluminous SNe (M{sub peak} ≈ −20)—one discovered and followed by the Palomar Transient Factory (PTF) and three by the Supernova Legacy Survey. The light curves resemble those of SN 2011kl, recently shown to be associated with an ultra-long-duration gamma-ray burst (GRB), though no GRB was seen to accompany our SNe. The rapid rise to a luminous peak places these events in a unique part of SN phase space, challenging standard SN emission mechanisms. Spectra of the PTF event formallymore » classify it as an SN II due to broad Hα emission, but an unusual absorption feature, which can be interpreted as either high velocity Hα (though deeper than in previously known cases) or Si ii (as seen in SNe Ia), is also observed. We find that existing models of white dwarf detonations, CSM interaction, shock breakout in a wind (or steeper CSM), and magnetar spin down cannot readily explain the observations. We consider the possibility that a “Type 1.5 SN” scenario could be the origin of our events. More detailed models for these kinds of transients and more constraining observations of future such events should help to better determine their nature.« less

Rapidly Rising Transients in the Supernova - Superluminous Supernova Gap

NASA Technical Reports Server (NTRS)

Arcavi, Iair; Wolf, William M.; Howell, D. Andrew; Bildsten, Lars; Leloudas, Giorgos; Hardin, Delphine; Prajs, Szymon; Perley, Daniel A.; Svirski, Gilad; Cenko, S. Bradley

2016-01-01

We present observations of four rapidly rising (t(sub rise) approximately equals 10 days) transients with peak luminosities between those of supernovae (SNe) and superluminous SNe (M(sub peak) approximately equals -20) - one discovered and followed by the PalomarTransient Factory (PTF) and three by the Supernova Legacy Survey. The light curves resemble those of SN 2011kl, recently shown to be associated with an ultra-long-duration gamma-ray burst (GRB), though no GRB was seen to accompany our SNe. The rapid rise to a luminous peak places these events in a unique part of SN phase space, challenging standard SN emission mechanisms. Spectra of the PTF event formally classify it as an SN II due to broad H alpha emission, but an unusual absorption feature, which can be interpreted as either high velocity H alpha (though deeper than in previously known cases) or Si II (as seen in SNe Ia), is also observed. We find that existing models of white dwarf detonations, CSM interaction, shock breakout in a wind (or steeper CSM), and magnetar spin down cannot readily explain the observations. We consider the possibility that a Type 1.5 SN scenario could be the origin of our events. More detailed models for these kinds of transients and more constraining observations of future such events should help to better determine their nature.

NuSTAR + XMM-Newton monitoring of the neutron star transient AX J1745.6-2901

NASA Astrophysics Data System (ADS)

Ponti, G.; Bianchi, S.; Muñoz-Darias, T.; Mori, K.; De, K.; Rau, A.; De Marco, B.; Hailey, C.; Tomsick, J.; Madsen, K. K.; Clavel, M.; Rahoui, F.; Lal, D. V.; Roy, S.; Stern, D.

2018-01-01

AX J1745.6-2901 is a high-inclination (eclipsing) transient neutron star (NS) low-mass X-ray binary showcasing intense ionized Fe K absorption. We present here the analysis of 11 XMM-Newton and 15 NuSTAR new data sets (obtained between 2013 and 2016), therefore tripling the number of observations of AX J1745.6-2901 in outburst. Thanks to simultaneous XMM-Newton and NuSTAR spectra, we greatly improve on the fitting of the X-ray continuum. During the soft state, the emission can be described by a disc blackbody (kT ∼ 1.1-1.2 keV and inner disc radius rDBB ∼ 14 km), plus hot (kT ∼ 2.2-3.0 keV) blackbody radiation with a small emitting radius (rBB ∼ 0.5 - 0.8 km) likely associated with the boundary layer or NS surface, plus a faint Comptonization component. Imprinted on the spectra are clear absorption features created by both neutral and ionized matter. Additionally, positive residuals suggestive of an emission Fe K α disc line and consistent with relativistic ionized reflection are present during the soft state, while such residuals are not significant during the hard state. The hard-state spectra are characterized by a hard (Γ ∼ 1.9-2.1) power law, showing no evidence for a high energy cut-off (kTe > 60-140 keV) and implying a small optical depth (τ < 1.6). The new observations confirm the previously witnessed trend of exhibiting strong Fe K absorption in the soft state that significantly weakens during the hard state. Optical (GROND) and radio (GMRT) observations suggest for AX J1745.6-2901 a standard broad-band spectral energy distribution as typically observed in accreting NSs.

The joy of transient chaos.

PubMed

Tél, Tamás

2015-09-01

We intend to show that transient chaos is a very appealing, but still not widely appreciated, subfield of nonlinear dynamics. Besides flashing its basic properties and giving a brief overview of the many applications, a few recent transient-chaos-related subjects are introduced in some detail. These include the dynamics of decision making, dispersion, and sedimentation of volcanic ash, doubly transient chaos of undriven autonomous mechanical systems, and a dynamical systems approach to energy absorption or explosion.

New photocycle intermediates in the photoactive yellow protein from Ectothiorhodospira halophila: picosecond transient absorption spectroscopy.

PubMed

Ujj, L; Devanathan, S; Meyer, T E; Cusanovich, M A; Tollin, G; Atkinson, G H

1998-07-01

Previous studies have shown that the room temperature photocycle of the photoactive yellow protein (PYP) from Ectothiorhodospira halophila involves at least two intermediate species: I1, which forms in <10 ns and decays with a 200-micros lifetime to I2, which itself subsequently returns to the ground state with a 140-ms time constant at pH 7 (Genick et al. 1997. Biochemistry. 36:8-14). Picosecond transient absorption spectroscopy has been used here to reveal a photophysical relaxation process (stimulated emission) and photochemical intermediates in the PYP photocycle that have not been reported previously. The first new intermediate (I0) exhibits maximum absorption at approximately 510 nm and appears in

Broadband transient absorption spectroscopy with 1- and 2-photon excitations: Relaxation paths and cross sections of a triphenylamine dye in solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moreno, J.; Dobryakov, A. L.; Hecht, S., E-mail: sh@chemie.hu-berlin.de, E-mail: skovale@chemie.hu-berlin.de

2015-07-14

1-photon (382 nm) and 2-photon (752 nm) excitations to the S{sub 1} state are applied to record and compare transient absorption spectra of a push-pull triphenylamine (TrP) dye in solution. After 1-photon excitation, ultrafast vibrational and structural molecular relaxations are detected on a 0.1 ps time scale in nonpolar hexane, while in polar acetonitrile, the spectral evolution is dominated by dipolar solvation. Upon 2-photon excitation, transient spectra in hexane reveal an unexpected growth of stimulated emission (SE) and excited-state absorption (ESA) bands. The behavior is explained by strong population transfer S{sub 1} → S{sub n} due to resonant absorption ofmore » a third pump photon. Subsequent S{sub n} → S{sub 1} internal conversion (with τ{sub 1} = 1 ps) prepares a very hot S{sub 1} state which cools down with τ{sub 2} = 13 ps. The pump pulse energy dependence proves the 2-photon origin of the bleach signal. At the same time, SE and ESA are strongly affected by higher-order pump absorptions that should be taken into account in nonlinear fluorescence applications. The 2-photon excitation cross sections σ{sup (2)} = 32 ⋅ 10{sup −50} cm{sup 4} s at 752 nm are evaluated from the bleach signal.« less

Charge Transfer from Carbon Nanotubes to Silicon in Flexible Carbon Nanotube/Silicon Solar Cells

DOE PAGES

Li, Xiaokai; Mariano, Marina; McMillon-Brown, Lyndsey; ...

2017-11-10

Mechanical fragility and insufficient light absorption are two major challenges for thin flexible crystalline Si-based solar cells. Flexible hybrid single-walled carbon nanotube (SWNT)/Si solar cells are demonstrated by applying scalable room-temperature processes for the fabrication of solar-cell components (e.g., preparation of SWNT thin films and SWNT/Si p–n junctions). The flexible SWNT/Si solar cells present an intrinsic efficiency ≈7.5% without any additional light-trapping structures. By using these solar cells as model systems, the charge transport mechanisms at the SWNT/Si interface are investigated using femtosecond transient absorption. Although primary photon absorption occurs in Si, transient absorption measurements show that SWNTs also generatemore » and inject excited charge carriers to Si. Such effects can be tuned by controlling the thickness of the SWNTs. Thus, findings from this study could open a new pathway for designing and improving the efficiency of photocarrier generation and absorption for high-performance ultrathin hybrid SWNT/Si solar cells.« less

Charge Transfer from Carbon Nanotubes to Silicon in Flexible Carbon Nanotube/Silicon Solar Cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Xiaokai; Mariano, Marina; McMillon-Brown, Lyndsey

Mechanical fragility and insufficient light absorption are two major challenges for thin flexible crystalline Si-based solar cells. Flexible hybrid single-walled carbon nanotube (SWNT)/Si solar cells are demonstrated by applying scalable room-temperature processes for the fabrication of solar-cell components (e.g., preparation of SWNT thin films and SWNT/Si p–n junctions). The flexible SWNT/Si solar cells present an intrinsic efficiency ≈7.5% without any additional light-trapping structures. By using these solar cells as model systems, the charge transport mechanisms at the SWNT/Si interface are investigated using femtosecond transient absorption. Although primary photon absorption occurs in Si, transient absorption measurements show that SWNTs also generatemore » and inject excited charge carriers to Si. Such effects can be tuned by controlling the thickness of the SWNTs. Thus, findings from this study could open a new pathway for designing and improving the efficiency of photocarrier generation and absorption for high-performance ultrathin hybrid SWNT/Si solar cells.« less

Transient absorption study of two-photon excitation mechanism in the LH2 complex from purple bacterium Rhodobacter sphaeroides.

PubMed

Stepanenko, Ilya; Kompanetz, Viktor; Makhneva, Zoya; Chekalin, Sergey; Moskalenko, Andrei; Razjivin, Andrei

2012-03-08

The mechanism of two-photon excitation of a peripheral light-harvesting complex LH2 (B800-850) from purple bacterium Rhodobacter sphaeroides was explained on the basis of femtosecond transient absorption data. Fast bleaching of the B850 absorption band was measured under two-photon excitation by 1350 nm femtosecond pulses, showing fast subpicosecond arrival of excitation energy to B850 circular aggregates. Any spectral changes connected with the B800 absorption band of B800-BChl molecules were absent. A similar picture was observed under one-photon excitation of the LH2 complex by 675 nm femtosecond pulses. We believe these effects may be attributed to direct excitation of high-energy excitonic states of a B850 circular aggregate or its vibrational manifold in accordance with the model of Abe [Chem. Phys. 2001, 264, 355-363].

A nonstationary Markov transition model for computing the relative risk of dementia before death

PubMed Central

Yu, Lei; Griffith, William S.; Tyas, Suzanne L.; Snowdon, David A.; Kryscio, Richard J.

2010-01-01

This paper investigates the long-term behavior of the k-step transition probability matrix for a nonstationary discrete time Markov chain in the context of modeling transitions from intact cognition to dementia with mild cognitive impairment (MCI) and global impairment (GI) as intervening cognitive states. The authors derive formulas for the following absorption statistics: (1) the relative risk of absorption between competing absorbing states, and (2) the mean and variance of the number of visits among the transient states before absorption. Since absorption is not guaranteed, sufficient conditions are discussed to ensure that the substochastic matrix associated with transitions among transient states converges to zero in limit. Results are illustrated with an application to the Nun Study, a cohort of 678 participants, 75 to 107 years of age, followed longitudinally with up to ten cognitive assessments over a fifteen-year period. PMID:20087848

Ultrafast relaxation dynamics of amine-substituted bipyridyl ruthenium(II) complexes

NASA Astrophysics Data System (ADS)

Song, Hongwei; Wang, Xian; Yang, WenWen; He, Guiying; Kuang, Zhuoran; Li, Yang; Xia, Andong; Zhong, Yu-Wu; Kong, Fan'ao

2017-09-01

The excited state properties of a series of ruthenium(II) amine-substituted bipyridyl complexes, [Ru(bpy)n(NNbpy)3-n]2+, were investigated by steady-state and transient absorption spectroscopy, as well as quantum chemical calculations. The steady-state absorption spectra of these complexes in CH3CN show a distinct red-shift of the 1MLCT absorption with increasing numbers of amine substituent, whereas the emission spectra indicate an energy gap order of [Ru(bpy)3]2+ > [Ru(bpy)2(NNbpy)]2+ > [Ru(NNbpy)3]2+ > [Ru(bpy)(NNbpy)2]2+. Nanosecond, femtosecond transient absorption and electrochemical measurements suggest that NNbpy ligand has a strong influence on the electronic and emission properties of these complexes, due to electron-rich amine substituent. We illustrate how the numbers of amine substituent modulate the spectroscopic properties of transition metal complexes, which is related to the design of new electro-active systems with novel photoelectrochemical properties.

The Photo-Physics of Polythiophene Nanoparticles for Biological Applications.

PubMed

Bargigia, Ilaria; Zucchetti, Elena; Srimath Kandada, Ajay Ram; Moreira, Miguel; Bossio, Caterina; Wong, Walter; Miranda, Paulo; Decuzzi, Paolo; Soci, Cesare; D'Andrea, Cosimo; Lanzani, Guglielmo

2018-05-01

In this work the photo-physics of poly(3-hexyltiophene) nanoparticles (NPs) is investigated in the context of their biological applications. The NPs made as colloidal suspensions in aqueous buffers present a distinct absorption band in the low energy region. Based on systematic analysis of absorption and transient absorption spectra taken under different pH conditions, this band is associated to charge transfer states generated by the polarization of loosely bound polymer chains and originated from complexes formed with electron withdrawing species. Importantly, the ground state depletion of these states upon photo-excitation is active even in the microsecond timescales, suggesting that they act as precursor states for long-living polarons which could be beneficial for cellular stimulation. Preliminary results of transient absorption microscopy of NPs internalized within the cells reveal the presence of long-living species, further substantiating their relevance in bio-interfaces. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE R&D Accomplishments Database

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

1995-06-01

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

Excitation Dynamics in Phycoerythrin 545: Modeling of Steady-State Spectra and Transient Absorption with Modified Redfield Theory

PubMed Central

Novoderezhkin, Vladimir I.; Doust, Alexander B.; Curutchet, Carles; Scholes, Gregory D.; van Grondelle, Rienk

2010-01-01

Abstract We model the spectra and excitation dynamics in the phycobiliprotein antenna complex PE545 isolated from the unicellular photosynthetic cryptophyte algae Rhodomonas CS24. The excitonic couplings between the eight bilins are calculated using the CIS/6-31G method. The site energies are extracted from a simultaneous fit of the absorption, circular dichroism, fluorescence, and excitation anisotropy spectra together with the transient absorption kinetics using the modified Redfield approach. Quantitative fit of the data enables us to assign the eight exciton components of the spectra and build up the energy transfer picture including pathways and timescales of energy relaxation, thus allowing a visualization of excitation dynamics within the complex. PMID:20643051

Development of picosecond time-resolved X-ray absorption spectroscopy by high-repetition-rate laser pump/X-ray probe at Beijing Synchrotron Radiation Facility.

PubMed

Wang, Hao; Yu, Can; Wei, Xu; Gao, Zhenhua; Xu, Guang Lei; Sun, Da Rui; Li, Zhenjie; Zhou, Yangfan; Li, Qiu Ju; Zhang, Bing Bing; Xu, Jin Qiang; Wang, Lin; Zhang, Yan; Tan, Ying Lei; Tao, Ye

2017-05-01

A new setup and commissioning of transient X-ray absorption spectroscopy are described, based on the high-repetition-rate laser pump/X-ray probe method, at the 1W2B wiggler beamline at the Beijing Synchrotron Radiation Facility. A high-repetition-rate and high-power laser is incorporated into the setup with in-house-built avalanche photodiodes as detectors. A simple acquisition scheme was applied to obtain laser-on and laser-off signals simultaneously. The capability of picosecond transient X-ray absorption spectroscopy measurement was demonstrated for a photo-induced spin-crossover iron complex in 6 mM solution with 155 kHz repetition rate.

SYNCHROTRON HEATING BY A FAST RADIO BURST IN A SELF-ABSORBED SYNCHROTRON NEBULA AND ITS OBSERVATIONAL SIGNATURE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yuan-Pei; Dai, Zi-Gao; Zhang, Bing, E-mail: zhang@physics.unlv.edu

Fast radio bursts (FRBs) are mysterious transient sources. If extragalactic, as suggested by their relative large dispersion measures, their brightness temperatures must be extremely high. Some FRB models (e.g., young pulsar model, magnetar giant flare model, or supra-massive neutron star collapse model) suggest that they may be associated with a synchrotron nebula. Here we study a synchrotron-heating process by an FRB in a self-absorbed synchrotron nebula. If the FRB frequency is below the synchrotron self-absorption frequency of the nebula, electrons in the nebula would absorb FRB photons, leading to a harder electron spectrum and enhanced self-absorbed synchrotron emission. In themore » meantime, the FRB flux is absorbed by the nebula electrons. We calculate the spectra of FRB-heated synchrotron nebulae, and show that the nebula spectra would show a significant hump in several decades near the self-absorption frequency. Identifying such a spectral feature would reveal an embedded FRB in a synchrotron nebula.« less

Room-Temperature Coherent Optical Phonon in 2D Electronic Spectra of CH 3NH 3PbI 3 Perovskite as a Possible Cooling Bottleneck

DOE Office of Scientific and Technical Information (OSTI.GOV)

Monahan, Daniele M.; Guo, Liang; Lin, Jia

2017-06-29

A hot phonon bottleneck may be responsible for slow hot carrier cooling in methylammonium lead iodide hybrid perovskite, creating the potential for more efficient hot carrier photovoltaics. In room-temperature 2D electronic spectra near the band edge, we observe in this paper amplitude oscillations due to a remarkably long lived 0.9 THz coherent phonon population at room temperature. This phonon (or set of phonons) is assigned to angular distortions of the Pb–I lattice, not coupled to cation rotations. The strong coupling between the electronic transition and the 0.9 THz mode(s), together with relative isolation from other phonon modes, makes it likelymore » to cause a phonon bottleneck. Finally, the pump frequency resolution of the 2D spectra also enables independent observation of photoinduced absorptions and bleaches independently and confirms that features due to band gap renormalization are longer-lived than in transient absorption spectra.« less

Novel laser gain and time-resolved FTIR studies of photochemistry

NASA Technical Reports Server (NTRS)

Leone, Stephen R.

1990-01-01

Several techniques are discussed which can be used to explore laboratory photochemical processes and kinetics relevant to planetary atmospheres; these include time-resolved laser gain-versus-absorption spectroscopy and time-resolved Fourier transform infrared (FTIR) emission studies. The laser gain-versus-absorption method employed tunable diode and F-center lasers to determine the yields of excited photofragments and their kinetics. The time-resolved FTIR technique synchronizes the sweep of a commercial FTIR with a pulsed source of light to obtain emission spectra of novel transient species in the infrared. These methods are presently being employed to investigate molecular photodissociation, the yields of excited states of fragments, their subsequent reaction kinetics, Doppler velocity distributions, and velocity-changing collisions of translationally fast atoms. Such techniques may be employed in future investigations of planetary atmospheres, for example to study polycyclic aromatic hydrocarbons related to cometary emissions, to analyze acetylene decomposition products and reactions, and to determine spectral features in the near infrared and infrared wavelength regions for planetary molecules and clusters.

Probing Exciton and Charge Dynamics in Organic Thin Films and Photovoltaics with Nonlinear Spectroscopy

NASA Astrophysics Data System (ADS)

McDonough, Thomas J.

Emerging organic solar cell technologies offer unique advantages over silicon solar cells, such as solution processability and the use of flexible substrates, but the efficiencies of these devices do not yet match the efficiency of silicon. Ultrafast nonlinear spectroscopies can probe the fates of photoexcited species on timescales in which these species are lost to channels that do not result in electric current. In the first study, I compare the ultrafast dynamics of singlet fission and charge generation in pentacene films grown on glass and graphene. The molecular orientation is different on the two substrates: the long axis of the pentacene molecules are "standing-up" (normal to the surface) on glass and "lying-down" (parallel to the surface) on graphene. By studying the fluence and polarization dependence of the transient absorption of pentacene on these two substrates, I am able to clarify previous spectral assignments. I identify a broad, isotropic absorption at 853 nm as due in significant part to hole absorption, in contrast to this feature's typical assignment to T1-T2 absorption. At high fluence, additional peaks at 614 and 688 (on glass) nm appear, whose kinetics and anisotropies are not explained by heating, which I assign to charge generation. In the second study, I utilize two-dimensional white-light spectroscopy to study the morphology dependence of exciton diffusion in semiconducting carbon nanotubes. I analyze the spectral diffusion of the S 1-S1 2D-WL lineshape via the center line slope method to separate the homogeneous and inhomogeneous contributions to the lineshape in each sample. I determine a morphology independent homogeneous linewidth of 10 meV, but I find that the inhomogeneous linewidth is sensitive to the particular sample environment. I model our experimental spectra with kinetic Monte Carlo simulations of exciton diffusion in a 1D potential. I also present preliminary bias-dependent transient absorption and 2D-WL measurements of carbon nanotube solar cell devices. I observe increasing positive trion absorption with increasing forward bias. The kinetics in the device are much different than the kinetics in the thin film, and there is an interesting change in kinetics with bias voltage that requires further investigation.

Evaluating the Nature of So-Called S*-State Feature in Transient Absorption of Carotenoids in Light-Harvesting Complex 2 (LH2) from Purple Photosynthetic Bacteria.

PubMed

Niedzwiedzki, Dariusz M; Hunter, C Neil; Blankenship, Robert E

2016-11-03

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S* state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation-bacteriochlorophyll anion pair. These findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.

On transient events in the upper atmosphere generated away of thunderstorm regions

NASA Astrophysics Data System (ADS)

Morozenko, V.; Garipov, G.; Khrenov, B.; Klimov, P.; Panasyuk, M.; Sharakin, S.; Zotov, M.

2011-12-01

Experimental data on transient events in UV and Red-IR ranges obtained in the MSU missions "Unversitetsky-Tatiana" (wavelengths 300-400 nm) and "Unversitetsky-Tatiana-2" (wavelengths 300-400 nm and 600-800 nm), published by Garipov et al, in 2010 at COSPAR session http://www.cospar2010.org, at TEPA conference http://www.aragats.am/Conferences/tepa2010 and in 2011 by Sadovnichy et al, Solar System Research, 45, #1, 3-29 (2011); Vedenkin et al, JETP, v. 140, issue 3(9), 1-11 (2011) demonstrated existence of transients at large distances (up to thousands km) away of cloud thunderstorm regions. Those "remote" transients are short (1-5 msec) and are less luminous than the transients above thunderstorm regions. The ratio of Red-IR to UV photon numbers in those transients indicates high altitude of their origin (~70 km). Important observation facts are also: 1. a change of the exponent in transient distribution on luminosity Q ("-1" for photon numbers Q=1020 -1023 to "-2" for Q>1023), 2. a change of global distribution of transient with their luminosity (transients with Q>1023 are concentrated in equatorial range above continents, while transients with low luminosity are distributed more uniformly), 3. a phenomenon of transient sequences in one satellite orbit which is close to geomagnetic meridian. In the present paper phenomenological features of transients are explained in assumption that the observed transients have to be divided in two classes: 1. transients related to local, lower in the atmosphere, lightning at distance not more than hundreds km from satellite detector field of view in the atmosphere and 2. transients generated by far away lightning. Local transients are luminous and presumably are events called "transient luminous events" (TLE). In distribution on luminosity those events have some threshold Q~1023 and their differential luminosity distribution is approximated by power law exponent "-2". Remote transients have to be considered separately. Their origin may be related to electromagnetic pulses (EMP) or waves (whistler, EMW) generated by lightning. The EMP-EMW is transmitted in the ionosphere- ground channel to large distances R with low absorption. The part of EMP-EMW "visible" in the detector aperture diminishes with distance as R-1 due to observation geometry. The EMP-EMW triggers the electric discharge in the upper atmosphere (lower ionosphere, ~70 km). Estimates of resulting transients luminosity and their correlation with geomagnetic field are in progress.

Vibrational structure of the S 2 (1B u) excited state of diphenyloctatetraene observed by femtosecond stimulated Raman spectroscopy

NASA Astrophysics Data System (ADS)

Kukura, Philipp; McCamant, David W.; Davis, Paul H.; Mathies, Richard A.

2003-11-01

Femtosecond time-resolved stimulated Raman spectroscopy (FSRS) is used to study the vibrational structure and dynamics of the S 2 state of diphenyloctatetraene. Strong vibrational features at 1184, 1259 and 1578 cm -1 whose linewidths are determined by the S 2 electronic lifetime are observed at early times after photoexcitation at 397 nm. Kinetic analysis of the integrated Raman intensities as well as the transient absorption reveals an exponential decay of the S 2 state on the order of 100 fs. These results demonstrate the ability of FSRS to study the vibrational structure of excited state and chemical reaction dynamics on the femtosecond timescale.

Nonlinear Optical Spectroscopy of Two-Dimensional Materials

NASA Astrophysics Data System (ADS)

Cui, Qiannan

Nonlinear optical properties of two-dimensional (2D) materials, such as transition metal dichalcogenides (TMDs), graphene, black phosphorus, and so on, play a key role of understanding nanoscale light-matter interactions, as well as developing nanophotonics applications from solar cells to quantum computation. With ultrafast lasers, we experimentally study nonlinear optical properties of 2D materials. Employing transient absorption microscopy, we study several members of 2D materials, such as WSe2, TiS3 and ReS2. The dynamical saturable absorption process of 2D excitons is spatiotemporally resolved. Intrinsic parameters of these 2D materials, such as exciton lifetime, exciton diffusion coefficient, and exciton mobility, are effectively measured. Especially, in-plane anisotropy of transient absorption and diffusive transport is observed for 2D excitons in monolayer ReS2, demonstrating the in-plane degree of freedom. Furthermore, with quantum interference and control nanoscopy, we all-optically inject, detect and manipulate nanoscale ballistic charge currents in a ReS2 thin film. By tuning the phase difference between one photon absorption and two photon absorption transition paths, sub-picosecond timescale of ballistic currents is coherently controlled for the first time in TMDs. In addition, the spatial resolution is two-order of magnitude smaller than optical diffraction limit. The second-order optical nonlinearity of 2D monolayers is resolved by second harmonic generation (SHG) microscopy. We measure the second-order susceptibility of monolayer MoS 2. The angular dependence of SHG in monolayer MoS2 shows strong symmetry dependence on its crystal lattice structure. Hence, second harmonic generation microscopy can serve as a powerful tool to noninvasively determine the crystalline directions of 2D monolayers. The real and imaginary parts of third-order optical nonlinearity of 2D monolayers are resolved by third harmonic generation (THG) microscopy and two-photon transient absorption microscopy, respectively. With third harmonic generation microscopy, we observe strong and anisotropic THG in monolayer and multilayer ReS2. Comparing with 2D materials with hexagonal lattice, such as MoS2, the third-order susceptibility is higher by one order of magnitude in ReS2 with a distorted 1T structure. The in-plane anisotropy of THG is attributed to the lattice distortion in ReS2 after comparing with a symmetry analysis. With two-photon transient absorption microscopy, we observe a giant two-photon absorption coefficient of monolayer WS2.

Charge carrier trapping and acoustic phonon modes in single CdTe nanowires.

PubMed

Lo, Shun Shang; Major, Todd A; Petchsang, Nattasamon; Huang, Libai; Kuno, Masaru K; Hartland, Gregory V

2012-06-26

Semiconductor nanostructures produced by wet chemical synthesis are extremely heterogeneous, which makes single particle techniques a useful way to interrogate their properties. In this paper the ultrafast dynamics of single CdTe nanowires are studied by transient absorption microscopy. The wires have lengths of several micrometers and lateral dimensions on the order of 30 nm. The transient absorption traces show very fast decays, which are assigned to charge carrier trapping into surface defects. The time constants vary for different wires due to differences in the energetics and/or density of surface trap sites. Measurements performed at the band edge compared to the near-IR give slightly different time constants, implying that the dynamics for electron and hole trapping are different. The rate of charge carrier trapping was observed to slow down at high carrier densities, which was attributed to trap-state filling. Modulations due to the fundamental and first overtone of the acoustic breathing mode were also observed in the transient absorption traces. The quality factors for these modes were similar to those measured for metal nanostructures, and indicate a complex interaction with the environment.

Fusion of Ultraviolet-Visible and Infrared Transient Absorption Spectroscopy Data to Model Ultrafast Photoisomerization.

PubMed

Debus, Bruno; Orio, Maylis; Rehault, Julien; Burdzinski, Gotard; Ruckebusch, Cyril; Sliwa, Michel

2017-08-03

Ultrafast photoisomerization reactions generally start at a higher excited state with excess of internal vibrational energy and occur via conical intersections. This leads to ultrafast dynamics which are difficult to investigate with a single transient absorption spectroscopy technique, be it in the ultraviolet-visible (UV-vis) or infrared (IR) domain. On one hand, the information available in the UV-vis domain is limited as only slight spectral changes are observed for different isomers. On the other hand, the interpretation of vibrational spectra is strongly hindered by intramolecular relaxation and vibrational cooling. These limitations can be circumvented by fusing UV-vis and IR transient absorption spectroscopy data in a multiset multivariate curve resolution analysis. We apply this approach to describe the spectrodynamics of the ultrafast cis-trans photoisomerization around the C-N double bond observed for aromatic Schiff bases. Twisted intermediate states could be elucidated, and isomerization was shown to occur through a continuous complete rotation. More broadly, data fusion can be used to rationalize a vast range of ultrafast photoisomerization processes of interest in photochemistry.

Ultrafast chemical reactions in shocked nitromethane probed with dynamic ellipsometry and transient absorption spectroscopy.

PubMed

Brown, Kathryn E; McGrane, Shawn D; Bolme, Cynthia A; Moore, David S

2014-04-10

Initiation of the shock driven chemical reactions and detonation of nitromethane (NM) can be sensitized by the addition of a weak base; however, the chemical mechanism by which sensitization occurs remains unclear. We investigated the shock driven chemical reaction in NM and in NM sensitized with diethylenetriamine (DETA), using a sustained 300 ps shock driven by a chirped Ti:sapphire laser. We measured the solutions' visible transient absorption spectra and measured interface particle and shock velocities of the nitromethane solutions using ultrafast dynamic ellipsometry. We found there to be a volume-increasing reaction that takes place around interface particle velocity up = 2.4 km/s and up = 2.2 km/s for neat NM and NM with 5% DETA, respectively. The rate at which transient absorption increases is similar in all mixtures, but with decreasing induction times for solutions with increasing DETA concentrations. This result supports the hypothesis that the chemical reaction mechanisms for shocked NM and NM with DETA are the same. Data from shocked NM are compared to literature experimental and theoretical data.

Two-Flux Method for Transient Radiative Transfer in a Semitransparent Layer

NASA Technical Reports Server (NTRS)

Siegel, Robert

1996-01-01

The two-flux method was used to obtain transient solutions for a plane layer including internal reflections and scattering. The layer was initially at uniform temperature, and was heated or cooled by external radiation and convection. The two-flux equations were examined as a means for evaluating the radiative flux gradient in the transient energy equation. Comparisons of transient temperature distributions using the two-flux method were made with results where the radiative flux gradient was evaluated from the exact radiative transfer equations. Good agreement was obtained for optical thicknesses from 0.5 to 5 and for refractive indices of 1 and 2. Illustrative results obtained with the two-flux method demonstrate the effect of isotropic scattering coupled with changing the refractive index. For small absorption with large scattering the maximum layer temperature is increased when the refractive index is increased. For larger absorption the effect is opposite, and the maximum temperature decreases with increased refractive index .

A Mote in Andromeda's Disk: A Misidentified Periodic AGN behind M31

NASA Astrophysics Data System (ADS)

Dorn-Wallenstein, Trevor; Levesque, Emily M.; Ruan, John J.

2017-11-01

We identify an object previously thought to be a star in the disk of M31, J0045+41, as a background z≈ 0.215 active galactic nucleus (AGN) seen through a low-absorption region of M31. We present moderate resolution spectroscopy of J0045+41 obtained using GMOS at Gemini-North. The spectrum contains features attributable to the host galaxy. We model the spectrum to estimate the AGN contribution, from which we estimate the luminosity and virial mass of the central engine. Residuals to our fit reveal a blueshifted component to the broad Hα and Hβ at a relative velocity of ˜4800 km s-1. We also detect Na I absorption in the Milky Way rest-frame. We search for evidence of periodicity using g-band photometry from the Palomar Transient Factory and find evidence for multiple periodicities ranging from ˜80-350 days. Two of the detected periods are in a 1:4 ratio, which is identical to the predictions of hydrodynamical simulations of binary supermassive black hole systems. If these signals arise due to such a system, J0045+41 is well within the gravitational wave regime. We calculate the time until inspiral due to gravitational radiation, assuming reasonable values of the mass ratio of the two black holes. We discuss the implications of our findings and forthcoming work to identify other such interlopers in the light of upcoming photometric surveys such as the Zwicky Transient Facility or the Large Synoptic Survey Telescope projects.

Characterizing caged molecules through flash photolysis and transient absorption spectroscopy.

PubMed

Kao, Joseph P Y; Muralidharan, Sukumaran

2013-01-01

Caged molecules are photosensitive molecules with latent biological activity. Upon exposure to light, they are rapidly transformed into bioactive molecules such as neurotransmitters or second messengers. They are thus valuable tools for using light to manipulate biology with exceptional spatial and temporal resolution. Since the temporal performance of the caged molecule depends critically on the rate at which bioactive molecules are generated by light, it is important to characterize the kinetics of the photorelease process. This is accomplished by initiating the photoreaction with a very brief but intense pulse of light (i.e., flash photolysis) and monitoring the course of the ensuing reactions through various means, the most common of which is absorption spectroscopy. Practical guidelines for performing flash photolysis and transient absorption spectroscopy are described in this chapter.

Charge Transfer from Carbon Nanotubes to Silicon in Flexible Carbon Nanotube/Silicon Solar Cells.

PubMed

Li, Xiaokai; Mariano, Marina; McMillon-Brown, Lyndsey; Huang, Jing-Shun; Sfeir, Matthew Y; Reed, Mark A; Jung, Yeonwoong; Taylor, André D

2017-12-01

Mechanical fragility and insufficient light absorption are two major challenges for thin flexible crystalline Si-based solar cells. Flexible hybrid single-walled carbon nanotube (SWNT)/Si solar cells are demonstrated by applying scalable room-temperature processes for the fabrication of solar-cell components (e.g., preparation of SWNT thin films and SWNT/Si p-n junctions). The flexible SWNT/Si solar cells present an intrinsic efficiency ≈7.5% without any additional light-trapping structures. By using these solar cells as model systems, the charge transport mechanisms at the SWNT/Si interface are investigated using femtosecond transient absorption. Although primary photon absorption occurs in Si, transient absorption measurements show that SWNTs also generate and inject excited charge carriers to Si. Such effects can be tuned by controlling the thickness of the SWNTs. Findings from this study could open a new pathway for designing and improving the efficiency of photocarrier generation and absorption for high-performance ultrathin hybrid SWNT/Si solar cells. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly sensitive transient absorption imaging of graphene and graphene oxide in living cells and circulating blood.

PubMed

Li, Junjie; Zhang, Weixia; Chung, Ting-Fung; Slipchenko, Mikhail N; Chen, Yong P; Cheng, Ji-Xin; Yang, Chen

2015-07-23

We report a transient absorption (TA) imaging method for fast visualization and quantitative layer analysis of graphene and GO. Forward and backward imaging of graphene on various substrates under ambient condition was imaged with a speed of 2 μs per pixel. The TA intensity linearly increased with the layer number of graphene. Real-time TA imaging of GO in vitro with capability of quantitative analysis of intracellular concentration and ex vivo in circulating blood were demonstrated. These results suggest that TA microscopy is a valid tool for the study of graphene based materials.

Transient Infrared Measurement of Laser Absorption Properties of Porous Materials

NASA Astrophysics Data System (ADS)

Marynowicz, Andrzej

2016-06-01

The infrared thermography measurements of porous building materials have become more frequent in recent years. Many accompanying techniques for the thermal field generation have been developed, including one based on laser radiation. This work presents a simple optimization technique for estimation of the laser beam absorption for selected porous building materials, namely clinker brick and cement mortar. The transient temperature measurements were performed with the use of infrared camera during laser-induced heating-up of the samples' surfaces. As the results, the absorbed fractions of the incident laser beam together with its shape parameter are reported.

Characterization of photo-induced valence tautomerism in a cobalt-dioxolene complex by ultrafast spectroscopy

NASA Astrophysics Data System (ADS)

Beni, A.; Bogani, L.; Bussotti, L.; Dei, A.; Gentili, P. L.; Righini, R.

2005-01-01

The valence tautomerism of low-spin CoIII(Cat-N-BQ)(Cat-N-SQ) was investigated by means of UV-vis pump-probe transient absorption spectroscopy in chloroform. By exciting the CT transition of the complex at 480 nm, an intramolecular electron transfer process is selectively triggered. The photo-induced charge transfer is pursued by a cascade of two main molecular events characterized by the ultrafast transient absorption spectroscopy: the first gives rise to the metastable high-spin CoII(Cat-N-BQ)2 that, secondly, reaches the chemical equilibrium with the reactant species.

Ultrafast relaxation dynamics of nitric oxide synthase studied by visible broadband transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hung, Chih-Chang; Yabushita, Atsushi; Kobayashi, Takayoshi; Chen, Pei-Feng; Liang, Keng S.

2017-09-01

Ultrafast dynamics of endothelial nitric oxide synthase (eNOS) oxygenase domain was studied by transient absorption spectroscopy pumping at Soret band. The broadband visible probe spectrum has visualized the relaxation dynamics from the Soret band to Q-band and charge transfer (CT) band. Supported by two-dimensional correlation spectroscopy, global fitting analysis has successfully concluded the relaxation dynamics from the Soret band to be (1) electronic transition to Q-band (0.16 ps), (2) ligand dissociation and CT (0.94 ps), (3) relaxation of the CT state (4.0 ps), and (4) ligand rebinding (59 ps).

Spectral Features and Charge Dynamics of Lead Halide Perovskites: Origins and Interpretations.

PubMed

Sum, Tze Chien; Mathews, Nripan; Xing, Guichuan; Lim, Swee Sien; Chong, Wee Kiang; Giovanni, David; Dewi, Herlina Arianita

2016-02-16

Lead halide perovskite solar cells are presently the forerunner among the third generation solution-processed photovoltaic technologies. With efficiencies exceeding 20% and low production costs, they are prime candidates for commercialization. Critical insights into their light harvesting, charge transport, and loss mechanisms have been gained through time-resolved optical probes such as femtosecond transient absorption spectroscopy (fs-TAS), transient photoluminescence spectroscopy, and time-resolved terahertz spectroscopy. Specifically, the discoveries of long balanced electron-hole diffusion lengths and gain properties in halide perovskites underpin their significant roles in uncovering structure-function relations and providing essential feedback for materials development and device optimization. In particular, fs-TAS is becoming increasingly popular in perovskite characterization studies, with commercial one-box pump-probe systems readily available as part of a researcher's toolkit. Although TAS is a powerful probe in the study of charge dynamics and recombination mechanisms, its instrumentation and data interpretation can be daunting even for experienced researchers. This issue is exacerbated by the sensitive nature of halide perovskites where the kinetics are especially susceptible to pump fluence, sample preparation and handling and even degradation effects that could lead to disparate conclusions. Nonetheless, with end-users having a clear understanding of TAS's capabilities, subtleties, and limitations, cutting-edge work with deep insights can still be performed using commercial setups as has been the trend for ubiquitous spectroscopy instruments like absorption, fluorescence, and transient photoluminescence spectrometers. Herein, we will first briefly examine the photophysical processes in lead halide perovskites, highlighting their novel properties. Next, we proceed to give a succinct overview of the fundamentals of pump-probe spectroscopy in relation to the spectral features of halide perovskites and their origins. In the process, we emphasize some key findings of seminal photophysical studies and draw attention to the interpretations that remain divergent and the open questions. This is followed by a general description into how we prepare and conduct the TAS characterization of CH3NH3PbI3 thin films in our laboratory with specific discussions into the potential pitfalls and the influence of thin film processing on the kinetics. Lastly, we conclude with our views on the challenges and opportunities from the photophysical perspective for the field and our expectations for systems beyond lead halide perovskites.

Ultraviolet Spectroscopy of Tidal Disruption Flares

NASA Astrophysics Data System (ADS)

Cenko, Stephen B.

2017-08-01

When a star passes within the sphere of disruption of a massive black hole, tidal forces will overcome self-gravity and unbind the star. While approximately half of the stellar debris is ejected at high velocities, the remaining material stays bound to the black hole and accretes, resulting in a luminous, long-lived transient known as a tidal disruption flare (TDF). In addition to serving as unique laboratories for accretion physics,TDFs offer the hope of measuring black hole masses in galaxies much too distant for resolved kinematic studies.In order to realize this potential, we must better understand the detailed processes by which the bound debris circularizes and forms an accretion disk. Spectroscopy is critical to this effort, as emission and absorption line diagnostics provide insight into the location and physical state (velocity, density, composition) of the emitting gas (in analogy with quasars). UV spectra are particularly critical, as most strong atomic features fall in this bandpass, and high-redshift TDF discoveries from LSST will sample rest-frame UV wavelengths.Here I present recent attempts to obtain UV spectra of tidal disruption flares. I describe the UV spectrum of ASASSN-14li, in which we detect three classes of features: narrow absorption from the Milky Way (probably a high-velocity cloud), and narrow absorption and broad (2000-8000 km s-1) emission lines at or near the systemic host velocity. The absorption lines are blueshifted with respect to the emission lines by 250-400 km s-1. Due both to this velocity offset and the lack of common low-ionization features (Mg II, Fe II), we argue these arise from the same absorbing material responsible for the low-velocity outflow discovered at X-ray wavelengths. The broad nuclear emission lines display a remarkable abundance pattern: N III], N IV], and He II are quite prominent, while the common quasar emission lines of C III] and Mg II are weak or entirely absent. Detailed modeling of this spectrum will help elucidate fundamental questions regarding the nature of the emission processes at work in TDFs, while future UV spectroscopy of ASASSN-14li would help to confirm (or refute) the previously proposed connection between TDFs and “N-rich” quasars.

Generation and decay dynamics of triplet excitons in Alq3 thin films under high-density excitation conditions.

PubMed

Watanabe, Sadayuki; Furube, Akihiro; Katoh, Ryuzi

2006-08-31

We studied the generation and decay dynamics of triplet excitons in tris-(8-hydroxyquinoline) aluminum (Alq3) thin films by using transient absorption spectroscopy. Absorption spectra of both singlet and triplet excitons in the film were identified by comparison with transient absorption spectra of the ligand molecule (8-hydroxyquinoline) itself and the excited triplet state in solution previously reported. By measuring the excitation light intensity dependence of the absorption, we found that exciton annihilation dominated under high-density excitation conditions. Annihilation rate constants were estimated to be gammaSS = (6 +/- 3) x 10(-11) cm3 s(-1) for single excitons and gammaTT = (4 +/- 2) x 10(-13) cm3 s(-1) for triplet excitons. From detailed analysis of the light intensity dependence of the quantum yield of triplet excitons under high-density conditions, triplet excitons were mainly generated through fission from highly excited singlet states populated by singlet-singlet exciton annihilation. We estimated that 30% of the highly excited states underwent fission.

Measurement of transient gas flow parameters by diode laser absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolshov, M A; Kuritsyn, Yu A; Liger, V V

2015-04-30

An absorption spectrometer based on diode lasers is developed for measuring two-dimension maps of temperature and water vapour concentration distributions in the combustion zones of two mixing supersonic flows of fuel and oxidiser in the single run regime. The method of measuring parameters of hot combustion zones is based on detection of transient spectra of water vapour absorption. The design of the spectrometer considerably reduces the influence of water vapour absorption along the path of a sensing laser beam outside the burning chamber. The optical scheme is developed, capable of matching measurement results in different runs of mixture burning. Amore » new algorithm is suggested for obtaining information about the mixture temperature by constructing the correlation functions of the experimental spectrum with those simulated from databases. A two-dimensional map of temperature distribution in a test chamber is obtained for the first time under the conditions of plasma-induced combusion of the ethylene – air mixture. (laser applications and other topics in quantum electronics)« less

Detection of non-absorbing charge dynamics via refractive index change in dye-sensitized solar cells.

PubMed

Kuwahara, Shota; Hata, Hiroaki; Taya, Soichiro; Maeda, Naotaka; Shen, Qing; Toyoda, Taro; Katayama, Kenji

2013-04-28

The carrier dynamics in dye-sensitized solar cells was investigated by using the transient grating, in addition to the transient absorption method and transient photocurrent method on the order of microseconds to seconds. The signals for the same sample were obtained under a short-circuit condition to compare the carrier dynamics via refractive index change with the transient photocurrent measurement. Optically silent carrier dynamics by transient absorption have been successfully observed via a refractive index change. The corresponding signal components were originated from the charge dynamics at the solid/liquid interface, especially on the liquid side; rearrangement or diffusion motion of charged redox species occurred when the injected electrons were trapped at the TiO2 surface and when the electron-electrolyte recombination occurred at the interface. The assignments were confirmed from the dependence on the viscosity of the solvent and the presence of 4-tert-butyl pyridine. As the viscosity of the solvent increased, the rearrangement and the motion of the charged redox species were delayed. Since the rearrangement dynamics was changed by the presence of 4-tert-butyl pyridine, it affected not only the TiO2 surface but also the redox species close to the interface.

Possible stretched exponential parametrization for humidity absorption in polymers.

PubMed

Hacinliyan, A; Skarlatos, Y; Sahin, G; Atak, K; Aybar, O O

2009-04-01

Polymer thin films have irregular transient current characteristics under constant voltage. In hydrophilic and hydrophobic polymers, the irregularity is also known to depend on the humidity absorbed by the polymer sample. Different stretched exponential models are studied and it is shown that the absorption of humidity as a function of time can be adequately modelled by a class of these stretched exponential absorption models.

Diiodobodipy-styrylbodipy Dyads: Preparation and Study of the Intersystem Crossing and Fluorescence Resonance Energy Transfer.

PubMed

Wang, Zhijia; Xie, Yun; Xu, Kejing; Zhao, Jianzhang; Glusac, Ksenija D

2015-07-02

2,6-Diiodobodipy-styrylbodipy dyads were prepared to study the competing intersystem crossing (ISC) and the fluorescence-resonance-energy-transfer (FRET), and its effect on the photophysical property of the dyads. In the dyads, 2,6-diiodobodipy moiety was used as singlet energy donor and the spin converter for triplet state formation, whereas the styrylbodipy was used as singlet and triplet energy acceptors, thus the competition between the ISC and FRET processes is established. The photophysical properties were studied with steady-state UV-vis absorption and fluorescence spectroscopy, electrochemical characterization, and femto/nanosecond time-resolved transient absorption spectroscopies. FRET was confirmed with steady state fluorescence quenching and fluorescence excitation spectra and ultrafast transient absorption spectroscopy (kFRET = 5.0 × 10(10) s(-1)). The singlet oxygen quantum yield (ΦΔ = 0.19) of the dyad was reduced as compared with that of the reference spin converter (2,6-diiodobodipy, ΦΔ = 0.85), thus the ISC was substantially inhibited by FRET. Photoinduced intramolecular electron transfer (ET) was studied by electrochemical data and fluorescence quenching. Intermolecular triplet energy transfer was studied with nanosecond transient absorption spectroscopy as an efficient (ΦTTET = 92%) and fast process (kTTET = 5.2 × 10(4) s(-1)). These results are useful for designing organic triplet photosensitizers and for the study of the photophysical properties.

Direct Observation of Excimer-Mediated Intramolecular Electron Transfer in a Cofacially-Stacked Perylene Bisimide Pair.

PubMed

Sung, Jooyoung; Nowak-Król, Agnieszka; Schlosser, Felix; Fimmel, Benjamin; Kim, Woojae; Kim, Dongho; Würthner, Frank

2016-07-27

We have elucidated excimer-mediated intramolecular electron transfer in cofacially stacked PBIs tethered by two phenylene-butadiynylene loops. The electron transfer between energetically equivalent PBIs is revealed by the simultaneous observation of the PBI radical anion and cation bands in the transient absorption spectra. The fluorescence decay time of the excimer states is in good agreement with the rise time of PBI radical bands in transient absorption spectra suggesting that the electron transfer dynamics proceed via the excimer state. We can conclude that the excimer state effectuates the efficient charge transfer in the cofacially stacked PBI dimer.

Highly sensitive transient absorption imaging of graphene and graphene oxide in living cells and circulating blood

PubMed Central

Li, Junjie; Zhang, Weixia; Chung, Ting-Fung; Slipchenko, Mikhail N.; Chen, Yong P.; Cheng, Ji-Xin; Yang, Chen

2015-01-01

We report a transient absorption (TA) imaging method for fast visualization and quantitative layer analysis of graphene and GO. Forward and backward imaging of graphene on various substrates under ambient condition was imaged with a speed of 2 μs per pixel. The TA intensity linearly increased with the layer number of graphene. Real-time TA imaging of GO in vitro with capability of quantitative analysis of intracellular concentration and ex vivo in circulating blood were demonstrated. These results suggest that TA microscopy is a valid tool for the study of graphene based materials. PMID:26202216

Single-shot transient absorption spectroscopy with a 45  ps pump-probe time delay range.

PubMed

Wilson, Kelly S; Wong, Cathy Y

2018-02-01

We report a single-shot transient absorption apparatus that successfully uses a tilted pump pulse to spatially encode a 45 ps pump-probe time delay. The time delay range is significantly improved over other reported instruments by using a spatial light modulator to flatten the intensity of the excitation field at the sample position. The full time delay range of the instrument is demonstrated by measuring a long-lived dye. A signal-to-noise ratio of >35 is attained in 8 s. This advance will enable the measurement of excited state dynamics of systems that are not at structural equilibrium.

Acoustic vibrations of single suspended gold nanostructures

NASA Astrophysics Data System (ADS)

Major, Todd A.

The acoustic vibrations for single gold nanowires and gold plates were studied using time-resolved ultrafast transient absorption. The objective of this work was to remove the contribution of the supporting substrate from the damping of the acoustic vibrations of the metal nano-objects. This was achieved by suspending the nano-objects across trenches created by photolithography and reactive ion etching. Transient absorption measurements for single suspended gold nanowires were initially completed in air and water environments. The acoustic vibrations for gold nanowires over the trench in air last typically for several nanoseconds, whereas gold nanowires in water are damped more quickly. Continuum mechanics models suggest that the acoustic impedance mismatch between air and water dominates the damping rate. Later transient absorption studies on single suspended gold nanowires were completed in glycerol and ethylene glycol environments. However, our continuum mechanical model suggests nearly complete damping in glycerol due to its high viscosity, but similar damping rates are seen between the two liquids. The continuum mechanics model thus incorrectly addresses high viscosity effects on the lifetimes of the acoustic vibrations, and more complicated viscoelastic interactions occur for the higher viscosity liquids. (Abstract shortened by UMI.).

Transient Absorption of Attosecond Pulses by He Atoms in Presence of Near-Infrared Laser Fields: A TDDFT Analysis of Sub-Cycle Temporal Structures

NASA Astrophysics Data System (ADS)

Heslar, John; Telnov, Dmitry; Chu, Shih-I.

2013-05-01

We study transient absorption of extreme ultraviolet (XUV) attosecond pulses in presence of near-infrared (NIR) laser fields by analyzing the population and photon emission of excited atomic energy levels. We consider He atoms and apply a self-interaction-free fully ab initio time-dependent density functional theory (TDDFT). Our method is based on the Krieger-Li-Iafrate (KLI) treatment of the optimized effective potential and incorporates explicitly the self-interaction correction. We focus on the sub-cycle (with respect to NIR field) temporal behavior of the population of the excited energy levels and related dynamics of photon emission. We observe and identify sub-cycle shifts in the photon emission spectrum as a function of the time delay between the XUV and NIR pulses. In the region where the two pulses overlap, the photon emission peaks have an oscillatory structure with a period of 1.3 fs, which is half of the NIR laser optical cycle. Such a structure was also observed in recent experiments on transient absorption. This work was partially supported by DOE and by MOE-NSC-NTU-Taiwan.

Use of interfacial layers to prolong hole lifetimes in hematite probed by ultrafast transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Paradzah, Alexander T.; Diale, Mmantsae; Maabong, Kelebogile; Krüger, Tjaart P. J.

2018-04-01

Hematite is a widely investigated material for applications in solar water oxidation due primarily to its small bandgap. However, full realization of the material continues to be hampered by fast electron-hole recombination rates among other weaknesses such as low hole mobility, short hole diffusion length and low conductivity. To address the problem of fast electron-hole recombination, researchers have resorted to growth of nano-structured hematite, doping and use of under-layers. Under-layer materials enhance the photo-current by minimising electron-hole recombination through suppressing of back electron flow from the substrate, such as fluorine-doped tin oxide (FTO), to hematite. We have carried out ultrafast transient absorption spectroscopy on hematite in which Nb2O5 and SnO2 materials were used as interfacial layers to enhance hole lifetimes. The transient absorption data was fit with four different lifetimes ranging from a few hundred femtoseconds to a few nanoseconds. We show that the electron-hole recombination is slower in samples where interfacial layers are used than in pristine hematite. We also develop a model through target analysis to illustrate the effect of under-layers on electron-hole recombination rates in hematite thin films.

Evaluating the Nature of So-Called S*-State Feature in Transient Absorption of Carotenoids in Light-Harvesting Complex 2 (LH2) from Purple Photosynthetic Bacteria

PubMed Central

2016-01-01

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S* state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation–bacteriochlorophyll anion pair. These findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes. PMID:27726397

Evaluating the nature of so-called S*-State feature in transient absorption of carotenoids in light-harvesting complex 2 (LH2) from purple photosynthetic bacteria

DOE PAGES

Niedzwiedzki, Dariusz M.; Hunter, C. Neil; Blankenship, Robert E.

2016-10-11

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S*more » state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation- bacteriochlorophyll anion pair. Lastly, these findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.« less

Evaluating the nature of so-called S*-State feature in transient absorption of carotenoids in light-harvesting complex 2 (LH2) from purple photosynthetic bacteria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Niedzwiedzki, Dariusz M.; Hunter, C. Neil; Blankenship, Robert E.

Carotenoids are a class of natural pigments present in all phototrophic organisms, mainly in their light-harvesting proteins in which they play roles of accessory light absorbers and photoprotectors. Extensive time-resolved spectroscopic studies of these pigments have revealed unexpectedly complex photophysical properties, particularly for carotenoids in light-harvesting LH2 complexes from purple bacteria. An ambiguous, optically forbidden electronic excited state designated as S* has been postulated to be involved in carotenoid excitation relaxation and in an alternative carotenoid-to-bacteriochlorophyll energy transfer pathway, as well as being a precursor of the carotenoid triplet state. However, no definitive and satisfactory origin of the carotenoid S*more » state in these complexes has been established, despite a wide-ranging series of studies. Here, we resolve the ambiguous origin of the carotenoid S* state in LH2 complex from Rba. sphaeroides by showing that the S* feature can be seen as a combination of ground state absorption bleaching of the carotenoid pool converted to cations and the Stark spectrum of neighbor neutral carotenoids, induced by temporal electric field brought by the carotenoid cation- bacteriochlorophyll anion pair. Lastly, these findings remove the need to assign an S* state, and thereby significantly simplify the photochemistry of carotenoids in these photosynthetic antenna complexes.« less

Design and analysis of frequency-selective surface enabled microbolometers

NASA Astrophysics Data System (ADS)

Liu, Tao; Qu, Chuang; Almasri, Mahmoud; Kinzel, Edward

2016-05-01

Frequency Selective Surfaces (FSS) are periodic array of sub-wavelength antenna elements. They allow the absorptance and reflectance of a surface to be engineered with respect to wavelength, polarization and angle-of-incidence. This paper applies this technique to microbolometers for uncooled infrared sensing applications. Both narrowband and broadband near perfect absorbing surfaces are synthesized and applied engineer the response of microbolometers. The paper focuses on simple FSS geometries (hexagonal close packed disk arrays) that can be fabricated using conventional lithographic tools for use at thermal infrared wavelengths (feature sizes > 1 μm). The affects of geometry and material selection for this geometry is described in detail. In the microbolometer application, the FSS controls the absorption rather than a conventional Fabry-Perot cavity and this permits an improved thermal design. A coupled full wave electromagnetic/transient thermal model of the entire microbolometer is presented and analyzed using the finite element method. The absence of the cavity also permits more flexibility in the design of the support arms/contacts. This combined modeling permits prediction of the overall device sensitivity, time-constant and the specific detectivity.

Systematic investigations on fused π-system compounds of seven benzene rings prepared by photocyclization of diphenanthrylethenes.

PubMed

Fujino, Shota; Yamaji, Minoru; Okamoto, Hideki; Mutai, Toshiki; Yoshikawa, Isao; Houjou, Hirohiko; Tani, Fumito

2017-06-14

We studied the photoproducts of 1-(n-phenanthryl)-2-(m-phenanthryl)ethenes (nEm; n, m = 1, 3 and 9) for understanding photocyclization patterns based on NMR spectroscopy. The crystal structures of the photoproducts were analyzed by X-ray crystallography, and the photophysical features of the photocyclized molecules were investigated based on emission and transient absorption measurements. Phenanthrene derivatives substituted at the 1- and 3-positions were prepared for synthesizing nEm by photocyclization of stilbene derivatives. We obtained four types of primary photoproducts (n@m) from the corresponding nEm. Two of them were found to have racemic molecular structures in the single crystal determined by X-ray crystallography. Besides the primary photoproducts, two types of secondary photoproducts (n@mPP) were isolated. Fluorescence quantum yields and lifetimes of the obtained photoproducts were determined in solution whereas the definite fluorescence quantum yields were obtained in the powder. Observation of the triplet-triplet absorption spectra in solution by laser photolysis techniques showed that intersystem crossing to the triplet state competes with the fluorescence process.

Annihilation limit of a visible-to-UV photon upconversion composition ascertained from transient absorption kinetics.

PubMed

Deng, Fan; Blumhoff, Jörg; Castellano, Felix N

2013-05-30

Noncoherent sensitized green-to-near-visible upconversion has been achieved utilizing palladium(II) octaethylporphyrin (PdOEP) as the triplet sensitizer and anthracene as the energy acceptor/annihilator in vacuum degassed toluene. Selective 547 nm excitation of PdOEP with incident irradiance as low as 600 μW/cm(2) results in the observation of anthryl fluorescence at higher energy. Stern-Volmer analysis of the dynamic phosphorescence quenching of PdOEP by anthracene possesses an extremely large K(SV) of 810,000 M(-1), yielding a triplet-triplet energy transfer quenching constant of 3.3 × 10(9) M(-1) s(-1). Clear evidence for the subsequent triplet-triplet annihilation (TTA) of anthracene was afforded by numerous experiments, one of the most compelling was an excitation scan illustrating that the Q-band absorption features of PdOEP are solely responsible for sensitizing the anti-Stokes fluorescence. The upconverted emission intensity with respect to the excitation power was shown to vary between quadratic and linear using either coherent or noncoherent light sources, illustrating the expected kinetic limits for the light producing photochemistry under continuous wave illumination. Time-resolved experiments directly comparing the total integrated anthracene intensity/time fluorescence data produced through upconversion (λ(ex) = 547 nm, delayed signal) and with direct excitation (λ(ex) = 355 nm, prompt signal) under conditions where the laser pulse is completely absorbed by the sample reveal annihilation efficiencies of approximately 40%. Similarly, the delayed fluorescence kinetic analysis reported by Schmidt and co-workers (J. Phys. Chem. Lett. 2010, 1, 1795-1799) was used to reveal the maximum possible efficiency from a model red-to-yellow upconverting composition and this treatment was applied to the anthryl triplet absorption decay transients of anthracene measured for the PdOEP/anthracene composition at 430 nm. From this analysis approximately 50% of the anthryl triplets that decay by TTA produce singlet fluorescence, consistent with the notion that annihilation spin statistics does not impose efficiency limits on upconversion photochemistry.

Transient absorption phenomena and related structural transformations in femtosecond laser-excited Si

NASA Astrophysics Data System (ADS)

Kudryashov, Sergey I.

2004-09-01

Analysis of processes affecting transient optical absorption and photogeneration of electron-hole plasma in silicon pumped by an intense NIR or visible femtosecond laser pulse has been performed taking into account the most important electron-photon, electron-electron and electron-phonon interactions and, as a result, two main regimes of such laser-matter interaction have been revealed. The first regime is concerned with indirect interband optical absorption in Si, enhanced by a coherent shrinkage of its smallest indirect bandgap due to dynamic Franz-Keldysh effect (DFKE). The second regime takes place due to the critical renormalization of the Si direct bandgap along Λ-axis of its first Brillouin zone because of DFKE and the deformation potential electron-phonon interaction and occurs as intense direct single-photon excitation of electrons into one of the quadruplet of equivalent Λ-valleys in the lowest conduction band, which is split down due to the electron-phonon interaction.

Negligible shift of 3Ag- potential in longer-chain carotenoids as revealed by a single persistent peak of 3Ag-→1Ag- stimulated emission followed by 3Ag-←1Ag- transient-absorption

NASA Astrophysics Data System (ADS)

Li, Chunyong; Miki, Takeshi; Kakitani, Yoshinori; Koyama, Yasushi; Nagae, Hiroyoshi

2007-12-01

Upon excitation of lycopene, anhydrorhodovibrin or spirilloxanthin to the 1Bu+(0) state, stimulated emission followed by transient-absorption was observed as a single peak with the 3Ag-(0) energy that had been determined by measurement of resonance-Raman excitation profiles. This observation was explained in terms of negligible shift of the 3Ag- potential, in reference to the 1Ag- potential, where only the 3Ag-(υ)→1Ag-(υ) emission and the 3Ag-(υ)←1Ag-(υ) absorption become allowed during the vibrational relaxation of υ = 2 → 1 → 0, starting from the 3Ag-(2) level generated by diabatic internal conversion from the 1Bu+(0) level, in anhydrorhodovibrin, for example.

Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy

PubMed Central

Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.; Cushing, Scott K.; Borja, Lauren J.; Gandman, Andrey; Kaplan, Christopher J.; Oh, Myoung Hwan; Prell, James S.; Prendergast, David; Pemmaraju, Chaitanya D.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si0.25Ge0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M4,5-edge (∼30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons across the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct (ΔEgap,Ge,direct=0.8 eV) and Si0.25Ge0.75 indirect gaps (ΔEgap,Si0.25Ge0.75,indirect=0.95 eV) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si0.25Ge0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution. PMID:28653020

Final Cassini RADAR Observation of Titan's Magic Island Region and Ligeia Mare

NASA Astrophysics Data System (ADS)

Hofgartner, J. D.; Hayes, A.; Lunine, J. I.; Stiles, B. W.; Malaska, M. J.; Wall, S. D.

2017-12-01

Cassini arrived in the Saturn system shortly after the Oct. 2002 northern winter solstice and the mission will end shortly after the May 2017 northern summer solstice. A main objective of the Cassini Solstice mission is to study seasonal and temporal changes and at Titan this includes changes of the hydrocarbon lakes/seas. Titan's Magic Islands are transient bright features in the north polar sea, Ligeia Mare that were observed to be temporal changes in Cassini RADAR images. The Magic Islands were discovered in a July 2013 image as anomalously bright features that were not present in four previous observations from Feb. 2007 - May 2013. The region of the Magic Islands was again anomalously bright in an Aug. 2014 image and the total areal extent of the anomalously bright region had increased by more than a factor of three. The transient features were not, however, observed in a Jan. 2015 image. Thus in seven observations spanning much of the Cassini mission the bright features were observed to appear, increase in extent, and then disappear. They are referred to as Titan's Magic Islands because of their appearing/disappearing behavior and resemblance in appearance to islands. These transient bright features are not actually islands. The transients were concluded to be most consistent with waves, floating solids, suspended solids, and bubbles. Tides, sea level changes, and seafloor changes are unlikely to be the primary cause of these temporal changes. Whether these temporal changes are also seasonal changes was unclear. The final Cassini RADAR imaging observation of Titan in Apr. 2017 included the region of the Magic Islands. The transient bright features were not present during this observation. The geometry of the observation was such that, had the transients been present, their brightness may have ruled out some of the remaining hypotheses. Their absence however, is less constraining but consistent with their transient nature. Waves, floating solids, suspended solids, and bubbles remain the most likely hypotheses. Other regions of Ligeia Mare were also imaged in the Apr. 2017 observation and no transient features were observed elsewhere in the sea. The specific process responsible for these transient features and the role of seasonal changes in their appearance and disappearance remains an open research question.

Using high spectral resolution spectrophotometry to study broad mineral absorption features on Mars

NASA Technical Reports Server (NTRS)

Blaney, D. L.; Crisp, D.

1993-01-01

Traditionally telescopic measurements of mineralogic absorption features have been made using relatively low to moderate (R=30-300) spectral resolution. Mineralogic absorption features tend to be broad so high resolution spectroscopy (R greater than 10,000) does not provide significant additional compositional information. Low to moderate resolution spectroscopy allows an observer to obtain data over a wide wavelength range (hundreds to thousands of wavenumbers) compared to the several wavenumber intervals that are collected using high resolution spectrometers. However, spectrophotometry at high resolution has major advantages over lower resolution spectroscopy in situations that are applicable to studies of the Martian surface, i.e., at wavelengths where relatively weak surface absorption features and atmospheric gas absorption features both occur.

Picosecond sulfur K-edge X-ray absorption spectroscopy with applications to excited state proton transfer

DOE PAGES

Van Kuiken, Benjamin E.; Ross, Matthew R.; Strader, Matthew L.; ...

2017-05-08

Picosecond X-ray absorption (XA) spectroscopy at the S K-edge (~2.4 keV) is demonstrated and used to monitor excited state dynamics in a small organosulfur molecule (2-Thiopyridone, 2TP) following optical excitation. Multiple studies have reported that the thione (2TP) is converted into the thiol (2-Mercaptopyridine, 2MP) following photoexcitation. However, the timescale and photochemical pathway of this reaction remain uncertain. In this work, time-resolved XA spectroscopy at the S K-edge is used to monitor the formation and decay of two transient species following 400nm excitation of 2TP dissolved in acetonitrile. The first transient species forms within the instrument response time (70 ps)more » and decays within 6 ns. The second transient species forms on a timescale of ~400 ps and decays on a 15 ns timescale. Time-dependent density functional theory is used to identify the first and second transient species as the lowestlying triplet states of 2TP and 2MP, respectively. This study demonstrates transient S K-edge XA spectroscopy as a sensitive and viable probe of time-evolving charge dynamics near sulfur sites in small molecules with future applications towards studying complex biological and material systems.« less

Femtosecond transient absorption spectroscopy of silanized silicon quantum dots

NASA Astrophysics Data System (ADS)

Kuntermann, Volker; Cimpean, Carla; Brehm, Georg; Sauer, Guido; Kryschi, Carola; Wiggers, Hartmut

2008-03-01

Excitonic properties of colloidal silicon quantum dots (Si qdots) with mean sizes of 4nm were examined using stationary and time-resolved optical spectroscopy. Chemically stable silicon oxide shells were prepared by controlled surface oxidation and silanization of HF-etched Si qdots. The ultrafast relaxation dynamics of photogenerated excitons in Si qdot colloids were studied on the picosecond time scale from 0.3psto2.3ns using femtosecond-resolved transient absorption spectroscopy. The time evolution of the transient absorption spectra of the Si qdots excited with a 150fs pump pulse at 390nm was observed to consist of decays of various absorption transitions of photoexcited electrons in the conduction band which overlap with both the photoluminescence and the photobleaching of the valence band population density. Gaussian deconvolution of the spectroscopic data allowed for disentangling various carrier relaxation processes involving electron-phonon and phonon-phonon scatterings or arising from surface-state trapping. The initial energy and momentum relaxation of hot carriers was observed to take place via scattering by optical phonons within 0.6ps . Exciton capturing by surface states forming shallow traps in the amorphous SiOx shell was found to occur with a time constant of 4ps , whereas deeper traps presumably localized in the Si-SiOx interface gave rise to exciton trapping processes with time constants of 110 and 180ps . Electron transfer from initially populated, higher-lying surface states to the conduction band of Si qdots (>2nm) was observed to take place within 400 or 700fs .

Photoreverse Reaction Dynamics of Octopus Rhodopsin

PubMed Central

Inoue, Keiichi; Tsuda, Motoyuki; Terazima, Masahide

2007-01-01

Photoreverse reactions of octopus rhodopsin (Rh) from acid-metarhodopsin (Acid-Meta), which is the final product of the photoreaction of Rh, to Rh were studied by the time-resolved transient absorption and transient grating methods. The time course of the absorption signal showed a rapid change within 500 ns followed by one phase with a time constant of ∼470 μs, whereas the transient grating signal indicates three phases with time constants of <500 ns, ∼490 μs, and 2.6 ms. The faster two phases indicate the conformational change in the vicinity of the chromophore, and the slowest one represents conformational change far from the chromophore. The absorption spectrum of the first intermediate created just after the laser excitation (<500 ns) is already very similar to the final product, Rh. This behavior is quite different from that of the forward reaction from Rh to Acid-Meta, in which several intermediates with different absorption spectra are involved within 50 ns–500 μs. This result indicates that the conformation around the chromophore is easily adjusted from all-trans to 11-cis forms compared with that from 11-cis to all-trans forms. Furthermore, it was found that the protein energy is quickly relaxed after the excitation. One of the significantly different properties between Rh and Acid-Meta is the diffusion coefficient (D). D is reduced by about half the transformation from Rh to Acid-Meta. This large reduction was interpreted in terms of the helix opening of the Rh structure. PMID:17325000

Segmental transport of Ca²⁺ and Mg²⁺ along the gastrointestinal tract.

PubMed

Lameris, Anke L; Nevalainen, Pasi I; Reijnen, Daphne; Simons, Ellen; Eygensteyn, Jelle; Monnens, Leo; Bindels, René J M; Hoenderop, Joost G J

2015-02-01

Calcium (Ca(2+)) and magnesium (Mg(2+)) ions are involved in many vital physiological functions. Since dietary intake is the only source of minerals for the body, intestinal absorption is essential for normal homeostatic levels. The aim of this study was to characterize the absorption of Ca(2+) as well as Mg(2+) along the gastrointestinal tract at a molecular and functional level. In both humans and mice the Ca(2+) channel transient receptor potential vanilloid subtype 6 (TRPV6) is expressed in the proximal intestinal segments, whereas Mg(2+) channel transient receptor potential melastatin subtype 6 (TRPM6) is expressed in the distal parts of the intestine. A method was established to measure the rate of Mg(2+) absorption from the intestine in a time-dependent manner by use of (25)Mg(2+). In addition, local absorption of Ca(2+) and Mg(2+) in different segments of the intestine of mice was determined by using surgically implanted intestinal cannulas. By these methods, it was demonstrated that intestinal absorption of Mg(2+) is regulated by dietary needs in a vitamin D-independent manner. Also, it was shown that at low luminal concentrations, favoring transcellular absorption, Ca(2+) transport mainly takes place in the proximal segments of the intestine, whereas Mg(2+) absorption predominantly occurs in the distal part of the gastrointestinal tract. Vitamin D treatment of mice increased serum Mg(2+) levels and 24-h urinary Mg(2+) excretion, but not intestinal absorption of (25)Mg(2+). Segmental cannulation of the intestine and time-dependent absorption studies using (25)Mg(2+) provide new ways to study intestinal Mg(2+) absorption. Copyright © 2015 the American Physiological Society.

Transient thermal effect, nonlinear refraction and nonlinear absorption properties of graphene oxide sheets in dispersion.

PubMed

Zhang, Xiao-Liang; Liu, Zhi-Bo; Li, Xiao-Chun; Ma, Qiang; Chen, Xu-Dong; Tian, Jian-Guo; Xu, Yan-Fei; Chen, Yong-Sheng

2013-03-25

The nonlinear refraction (NLR) properties of graphene oxide (GO) in N, N-Dimethylformamide (DMF) was studied in nanosecond, picosecond and femtosecond time regimes by Z-scan technique. Results show that the dispersion of GO in DMF exhibits negative NLR properties in nanosecond time regime, which is mainly attributed to transient thermal effect in the dispersion. The dispersion also exhibits negative NLR in picosecond and femtosecond time regimes, which are arising from sp(2)- hybridized carbon domains and sp(3)- hybridized matrix in GO sheets. To illustrate the relations between NLR and nonlinear absorption (NLA), NLA properties of the dispersion were also studied in nanosecond, picosecond and femtosecond time regimes.

Femtosecond Chirp-Free Transient Absorption Method And Apparatus

DOEpatents

McBranch, Duncan W.; Klimov, Victor I.

2001-02-20

A method and apparatus for femtosecond transient absorption comprising phase-sensitive detection, spectral scanning and simultaneous controlling of a translation stage to obtain TA spectra information having at least a sensitivity two orders of magnitude higher than that for single-shot methods, with direct, simultaneous compensation for chirp as the data is acquired. The present invention includes a amplified delay translation stage which generates a splittable frequency-doubled laser signal at a predetermined frequency f, a controllable means for synchronously modulating one of the laser signals at a repetition rate of f/2, applying the laser signals to a material to be sample, and acquiring data from the excited sample while simultaneously controlling the controllable means for synchronously modulating.

X-ray absorption of a warm dense aluminum plasma created by an ultra-short laser pulse

NASA Astrophysics Data System (ADS)

Lecherbourg, L.; Renaudin, P.; Bastiani-Ceccotti, S.; Geindre, J.-P.; Blancard, C.; Cossé, P.; Faussurier, G.; Shepherd, R.; Audebert, P.

2007-05-01

Point-projection K-shell absorption spectroscopy has been used to measure absorption spectra of transient aluminum plasma created by an ultra-short laser pulse. The 1s-2p and 1s-3p absorption lines of weakly ionized aluminum were measured for an extended range of densities in a low-temperature regime. Independent plasma characterization was obtained using frequency domain interferometry diagnostic (FDI) that allows the interpretation of the absorption spectra in terms of spectral opacities. A detailed opacity code using the density and temperature inferred from the FDI reproduce the measured absorption spectra except in the last stage of the recombination phase.

Ensemble Classifier Strategy Based on Transient Feature Fusion in Electronic Nose

NASA Astrophysics Data System (ADS)

Bagheri, Mohammad Ali; Montazer, Gholam Ali

2011-09-01

In this paper, we test the performance of several ensembles of classifiers and each base learner has been trained on different types of extracted features. Experimental results show the potential benefits introduced by the usage of simple ensemble classification systems for the integration of different types of transient features.

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis.

PubMed

Kärkäs, Markus D; Porco, John A; Stephenson, Corey R J

2016-09-14

The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis.

Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Laboni; Kumar, Rahul; Maity, Dilip K.

A pulse radiolysis study on pyrrolidinium cation based ionic liquids is presented here in this paper. Time-resolved absorption spectra for 1-methyl-1-propylpyrrolidinium dicyanamide (DCA) at 500 ns after the electron pulse show broad absorption bands at wavelengths below 440 nm and at 640 nm. In pyrrolidinium bis(trifluoromethylsulfonyl)imide (NTf 2) and tris(perfluoroethyl)trifluorophosphate (FAP) ILs, the transient absorption below 440 nm is much weaker. The absorption at 500 ns, which increases with wavelength from 500 nm to beyond 800 nm, was assigned to the tail of the solvated electron NIR absorption spectrum, since it disappears in the presence of N 2O. In themore » DCA IL, the presence of a reducing species was confirmed by the formation of pyrene radical anion. The difference in the transient species in the case of the DCA IL compared to other two ILs should be due to the anion, with cations being similar. In pseudohalide ILs such as DCA, radicals are formed by direct hole trapping by the anion (X – + h + → X•), followed by addition to the parent anion. Prediction of the UV/vis absorption spectra of the dimer radical anion by computational calculation supports the experimental results. The oxidizing efficiency of (DCA) 2•– and its reduction potential (E(DCA)2•–/(2DCA–)) have been determined.« less

Pulse Radiolysis and Computational Studies on a Pyrrolidinium Dicyanamide Ionic Liquid: Detection of the Dimer Radical Anion

DOE PAGES

Das, Laboni; Kumar, Rahul; Maity, Dilip K.; ...

2018-03-06

A pulse radiolysis study on pyrrolidinium cation based ionic liquids is presented here in this paper. Time-resolved absorption spectra for 1-methyl-1-propylpyrrolidinium dicyanamide (DCA) at 500 ns after the electron pulse show broad absorption bands at wavelengths below 440 nm and at 640 nm. In pyrrolidinium bis(trifluoromethylsulfonyl)imide (NTf 2) and tris(perfluoroethyl)trifluorophosphate (FAP) ILs, the transient absorption below 440 nm is much weaker. The absorption at 500 ns, which increases with wavelength from 500 nm to beyond 800 nm, was assigned to the tail of the solvated electron NIR absorption spectrum, since it disappears in the presence of N 2O. In themore » DCA IL, the presence of a reducing species was confirmed by the formation of pyrene radical anion. The difference in the transient species in the case of the DCA IL compared to other two ILs should be due to the anion, with cations being similar. In pseudohalide ILs such as DCA, radicals are formed by direct hole trapping by the anion (X – + h + → X•), followed by addition to the parent anion. Prediction of the UV/vis absorption spectra of the dimer radical anion by computational calculation supports the experimental results. The oxidizing efficiency of (DCA) 2•– and its reduction potential (E(DCA)2•–/(2DCA–)) have been determined.« less

Suppression of thermal transients in advanced LIGO interferometers using CO2 laser preheating

NASA Astrophysics Data System (ADS)

Jaberian Hamedan, V.; Zhao, C.; Ju, L.; Blair, C.; Blair, D. G.

2018-06-01

In high optical power interferometric gravitational wave detectors, such as Advanced LIGO, the thermal effects due to optical absorption in the mirror coatings and the slow thermal response of fused silica substrate cause time dependent changes in the mirror profile. After locking, high optical power builds up in the arm cavities. Absorption induced heating causes optical cavity transverse mode frequencies to drift over a period of hours, relative to the fundamental mode. At high optical power this can cause time dependent transient parametric instability, which can lead to interferometer disfunction. In this paper, we model the use of CO2 laser heating designed to enable the interferometer to be maintained in a thermal condition such that transient changes in the mirrors are greatly reduced. This can minimize transient parametric instability and compensate dark port power fluctuations. Modeling results are presented for both single compensation where a CO2 laser acting on one test mass per cavity, and double compensation using one CO2 laser for each test mass. Using parameters of the LIGO Hanford Observatory X-arm as an example, single compensation allows the maximum mode frequency shift to be limited to 6% of its uncompensated value. However, single compensation causes transient degradation of the contrast defect. Double compensation minimise contrast defect degradation and reduces transients to less than 1% if the CO2 laser spot is positioned within 2 mm of the cavity beam position.

High Harmonic Generation XUV Spectroscopy for Studying Ultrafast Photophysics of Coordination Complexes

NASA Astrophysics Data System (ADS)

Ryland, Elizabeth S.; Lin, Ming-Fu; Benke, Kristin; Verkamp, Max A.; Zhang, Kaili; Vura-Weis, Josh

2017-06-01

Extreme ultraviolet (XUV) spectroscopy is an inner shell technique that probes the M_{2,3}-edge excitation of atoms. Absorption of the XUV photon causes a 3p→3d transition, the energy and shape of which is directly related to the element and ligand environment. This technique is thus element-, oxidation state-, spin state-, and ligand field specific. A process called high-harmonic generation (HHG) enables the production of ultrashort (˜20fs) pulses of collimated XUV photons in a tabletop instrument. This allows transient XUV spectroscopy to be conducted as an in-lab experiment, where it was previously only possible at accelerator-based light sources. Additionally, ultrashort pulses provide the capability for unprecedented time resolution (˜50fs IRF). This technique has the capacity to serve a pivotal role in the study of electron and energy transfer processes in materials and chemical biology. I will present the XUV transient absorption instrument we have built, along with ultrafast transient M_{2,3}-edge absorption data of a series of small inorganic molecules in order to demonstrate the high specificity and time resolution of this tabletop technique as well as how our group is applying it to the study of ultrafast electronic dynamics of coordination complexes.

The Transient Dermal Exposure II: Post-Exposure Absorption and Evaporation of Volatile Compounds

PubMed Central

FRASCH, H. FREDERICK; BUNGE, ANNETTE L.

2016-01-01

The transient dermal exposure is one where the skin is exposed to chemical for a finite duration, after which the chemical is removed and no residue remains on the skin’s surface. Chemical within the skin at the end of the exposure period can still enter the systemic circulation. If it has some volatility, a portion of it will evaporate from the surface before it has a chance to be absorbed by the body. The fate of this post-exposure “skin depot” is the focus of this theoretical study. Laplace domain solutions for concentration distribution, flux, and cumulative mass absorption and evaporation are presented, and time domain results are obtained through numerical inversion. The Final Value Theorem is applied to obtain the analytical solutions for the total fractional absorption by the body and evaporation from skin at infinite time following a transient exposure. The solutions depend on two dimensionless variables: χ, the ratio of evaporation rate to steady-state dermal permeation rate; and the ratio of exposure time to membrane lag time. Simple closed form algebraic equations are presented that closely approximate the complete analytical solutions. Applications of the theory to the dermal risk assessment of pharmaceutical, occupational, and environmental exposures are presented for four example chemicals. PMID:25611182

RXTE Observations of the 1A 1118-61 in an Outburst, and the Discovery of a Cyclotron Line

NASA Technical Reports Server (NTRS)

Doroshenko, V.; Suchy, S.; Santangelo, A; Staubert, R.; Kreykenbohm, I.; Rothschild, R.; Pottschmidt, K.; Wilms, J.

2010-01-01

We present the analysis of RXTE monitoring data obtained during the January 2009 outburst of the hard X-ray transient IA 1118-61. Using these observations the broadband (3.5-120 keV) spectrum of the source was measured for the first time ever. We have found that the broadband continuum spectrum of the source is similar to other accreting pulsars and is well described by several conventionally used phenomenological models. We have discovered that regardless of the applied continuum model, a prominent broad absorption feature at approx. 55 keV is observed. We interpret this feature as a Cyclotron Resonance Scattering Feature (CRSF). The observed CRSF energy is one of the highest known and corresponds to a magnetic field of B approx. 4.8 x 10(exp 12) G in the scattering region. Furthermore, our data suggests an iron emission line presence, which was not reported previously for lA 1118-61 as well. Timing properties of the source, including a strong spin-up, were found to be similar to those observed by CGRO/BATSE during the previous outburst, however the broadband capabilities of RXTE reveal a more complicated energy dependency of the pulse-profile.

Pastes: what do they contain? How do they work?

PubMed

Juch, R D; Rufli, T; Surber, C

1994-01-01

Pastes are semisolid stiff preparations containing a high proportion of finely powdered material. Powders such as zinc oxide, titanium dioxide, starch, kaolin or talc are incorporated in high concentrations into a preferably lipophilic, greasy vehicle. A clinically distinctive feature which is generally attributed to pastes is the quality to absorb exudates by nature of the powder or other absorptive components. Reviewing the various pharmacopoeias serious doubts arise from the various formulas of pastes and their absorptive features. The zinc oxide pastes of the USP XXII, the DAB 10 and BP 88 (US, German and British pharmacopoeias). are composed of petrolatum, zinc oxide and starch. Petrolatum, a highly lipophilic, water-immiscible vehicle surrounds the powder particles preventing any absorption of water or exudates. The goal of our investigation was to test a simple experimental setting to characterize the clinically important absorptive feature of powders and pastes. The absorptive features of the powders were determined by the method of Enslin. The absorptive features of the paste preparations were calculated from the weight difference between the paste preparation before and after incubation with water using a simple standardized procedure. The absorptive features of titanium dioxide, zinc oxide, kaolin, corn starch and methylcellulose powder in pharmacopoeia quality were determined. Zinc oxide and kaolin powder showed the highest absorption of 1,000 mg water/g powder (100%). The water absorption of corn starch and titanium dioxide was 700 and 450 mg/g powder, respectively. The absorptive features of a series of paste preparations were studied in a simple experimental setting. The data show that two-phase pastes consisting of two immiscible components, one (the dispersed or inner phase; powder) being suspended in the other (the continuous or outer phase; lipophilic vehicle), have no absorptive features. In contrast, three-phase pastes consisting of a hydrophilic two-phase emulsion with high concentrations of incorporated powder (cream pastes) show considerable water uptake. We conclude that the classical two-phase pastes such as the zinc oxide pastes have no absorptive features. On the contrary, these formulations are highly occlusive. Therefore lipophilic pastes are only indicated when protection of intact skin against aggressive body exudates and humidity is required. The hydrophilic three-phase pastes or cream pastes show considerable water uptake and fulfil common expectations of pastes to dry the skin.

Separating higher-order nonlinearities in transient absorption microscopy

NASA Astrophysics Data System (ADS)

Wilson, Jesse W.; Anderson, Miguel; Park, Jong Kang; Fischer, Martin C.; Warren, Warren S.

2015-08-01

The transient absorption response of melanin is a promising optically-accessible biomarker for distinguishing malignant melanoma from benign pigmented lesions, as demonstrated by earlier experiments on thin sections from biopsied tissue. The technique has also been demonstrated in vivo, but the higher optical intensity required for detecting these signals from backscattered light introduces higher-order nonlinearities in the transient response of melanin. These components that are higher than linear with respect to the pump or the probe introduce intensity-dependent changes to the overall response that complicate data analysis. However, our data also suggest these nonlinearities might be advantageous to in vivo imaging, in that different types of melanins have different nonlinear responses. Therefore, methods to separate linear from nonlinear components in transient absorption measurements might provide additional information to aid in the diagnosis of melanoma. We will discuss numerical methods for analyzing the various nonlinear contributions to pump-probe signals, with the ultimate objective of real time analysis using digital signal processing techniques. To that end, we have replaced the lock-in amplifier in our pump-probe microscope with a high-speed data acquisition board, and reprogrammed the coprocessor field-programmable gate array (FPGA) to perform lock-in detection. The FPGA lock-in offers better performance than the commercial instrument, in terms of both signal to noise ratio and speed. In addition, the flexibility of the digital signal processing approach enables demodulation of more complicated waveforms, such as spread-spectrum sequences, which has the potential to accelerate microscopy methods that rely on slow relaxation phenomena, such as photo-thermal and phosphorescence lifetime imaging.

Optical properties and electronic energy relaxation of metallic Au144(SR)60 nanoclusters.

PubMed

Yi, Chongyue; Tofanelli, Marcus A; Ackerson, Christopher J; Knappenberger, Kenneth L

2013-12-04

Electronic energy relaxation of Au144(SR)60(q) ligand-protected nanoclusters, where SR = SC6H13 and q = -1, 0, +1, and +2, was examined using femtosecond time-resolved transient absorption spectroscopy. The observed differential transient spectra contained three distinct components: (1) transient bleaches at 525 and 600 nm, (2) broad visible excited-state absorption (ESA), and (3) stimulated emission (SE) at 670 nm. The bleach recovery kinetics depended upon the excitation pulse energy and were thus attributed to electron-phonon coupling typical of metallic nanostructures. The prominent bleach at 525 nm was assigned to a core-localized plasmon resonance (CLPR). ESA decay kinetics were oxidation-state dependent and could be described using a metal-sphere charging model. The dynamics, emission energy, and intensity of the SE peak exhibited dielectric-dependent responses indicative of Superatom charge transfer states. On the basis of these data, the Au144(SR)60 system is the smallest-known nanocluster to exhibit quantifiable electron dynamics and optical properties characteristic of metals.

Transient phenomena in the pulse radiolysis of retinyl polyenes. 5. Association of radical cations with parent molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bobrowski, K.; Das, P.K.

1986-02-27

At relatively high concentrations (1-10 mM) in O/sub 2/-saturated acetone, pulse radiolysis of all-trans-retinal, -retinoic acid, and -methyl retinoate gives rise to fast transient absorption processes that are best explained in terms of association of radical cations with parent polyenes to form dimers. From the concentration dependence of initial decay/formation kinetics, equilibrium constants (K) for monomer/dimer interconversion are measured to be 220-440 M/sup -1/ (in acetone). On going from acetone to 1,2-dichloroethane, K values for retinal and retinoic acid increase almost by an order of magnitude. For all trans-retinol and retinyl acetate, radical cation dimer formation appears to be negligiblemore » in the concentration range 1-10 mM of the polyene substrates (based on the lack of transient absorption changes seen with retinal and retinoic acid/ester). 24 references, 6 figures, 1 table.« less

Spatial localization of excitons and charge carriers in hybrid perovskite thin films

DOE PAGES

Simpson, Mary Jane; Doughty, Benjamin; Yang, Bin; ...

2015-07-21

The fundamental photophysics underlying the remarkably high power conversion efficiency of organic-inorganic hybrid perovskite-based solar cells has been increasingly studied using complementary spectroscopic techniques. The spatially heterogeneous polycrystalline morphology of the photoactive layers owing to the presence of distinct crystalline grains has been generally neglected in optical measurements and therefore the reported results are typically averaged over hundreds or even thousands of such grains. Here, we apply femtosecond transient absorption microscopy to spatially and temporally probe ultrafast electronic excited-state dynamics in pristine methylammonium lead tri-iodide (CH 3NH 3PbI 3) thin films and composite structures. We found that the electronic excited-statemore » relaxation kinetics are extremely sensitive to the sample location probed, which was manifested by position-dependent decay timescales and transient signals. As a result, analysis of transient absorption kinetics acquired at distinct spatial positions enabled us to identify contributions of excitons and free charge carriers.« less

Transient Spectra in TDDFT: Corrections and Correlations

NASA Astrophysics Data System (ADS)

Parkhill, John; Nguyen, Triet

We introduce an atomistic, all-electron, black-box electronic structure code to simulate transient absorption (TA) spectra and apply it to simulate pyrazole and a GFP chromophore derivative. The method is an application of OSCF2, our dissipative extension of time-dependent density functional theory. We compare our simulated spectra directly with recent ultra-fast spectroscopic experiments, showing that they are usefully predicted. We also relate bleaches in the TA signal to Fermi-blocking which would be missed in a simplified model. An important ingredient in the method is the stationary-TDDFT correction scheme recently put forwards by Fischer, Govind, and Cramer which allows us to overcome a limitation of adiabatic TDDFT. We demonstrate that OSCF2 is able to predict both the energies of bleaches and induced absorptions, as well as the decay of the transient spectrum, with only the molecular structure as input. With remaining time we will discuss corrections which resolve the non-resonant behavior of driven TDDFT, and correlated corrections to mean-field dynamics.

Measurement of the dipole moments of excited states and photochemical transients by microwave dielectric absorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fessenden, R.W.; Carton, P.M.; Shimamori, H.

1982-09-16

Time-resolved changes in microwave dielectric absorption have been used to study transients formed by laser flash photolysis. Details of the method and apparatus are given. Applications both to the measurements of the dipole moments of transients and to decay kinetics are given. The dipole moments of the lowest triplet states of a number of aromatic compounds (mostly ketones) have been measured in benzene solution at room temperature. States of n..pi..* character generally possess smaller dipole moments than the corresponding ground states while states of ..pi pi..* character (for example, fluorenone) have larger values than the ground state. The triplets ofmore » 4-(dimethylamino)benzaldehyde and 4,4'-bis(dimethylamino)benzophenone have rather high values of dipole moment (10.5 and 8.4 D, respectively) showing their charge-transfer character. The triplet state of benzil was found to have zero or near-zero dipole moment, thus confirming that the triplet state is of a transstructure. 7 figures, 1 table.« less

SUBARU/HDS STUDY OF HE 1015-2050: SPECTRAL EVIDENCE OF R CORONAE BOREALIS LIGHT DECLINE

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goswami, Aruna; Aoki, Wako, E-mail: aruna@iiap.res.in

2013-02-01

Hydrogen deficiency and a sudden optical light decline of about 6-8 mag are two principal characteristics of R Coronae Borealis (RCB) stars. The high latitude carbon star HE 1015-2050 was identified as a hydrogen-deficient carbon star from low-resolution spectroscopy. Photometric data of the Catalina Real-Time Transient Survey gathered between 2006 February and 2012 May indicate that the object exhibits no variability. However, a high-resolution (R {approx} 50, 000) optical spectrum of this object obtained with the 8.2 m Subaru telescope using High Dispersion Spectrograph on the 2012 January 13 offers sufficient spectral evidence that the object is a cool HdCmore » star of RCB type undergoing light decline. In contrast to the Na I D broad absorption features seen in the low-resolution spectra on several occasions, the high-resolution spectrum exhibits Na I D{sub 2} and D{sub 1} features in emission. A few emission lines due to Mg I, Sc II, Ti I, Ti II, Fe II, and Ba I are also observed in the spectrum of this object for the first time. Such emission features combined with neutral and singly ionized lines of Ca, Ti, Fe, etc., in absorption are reportedly seen in RCBs spectra in the early stage of decline or during the recovery to maximum. Further, the light decline of RCBs is ascribed to the formation of a cloud of soot that obscures the visible photosphere. The presence of such circumstellar material is evident from the polarimetric observations with an estimated V-band percentage polarization of {approx}1.7% for this object.« less

Spectroscopic and photochemical properties of open-chain carotenoids.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frank, H. A.; Josue, J. S.; Bautista, J. A.

2002-02-28

The spectroscopic properties of open-chain, all-trans-C{sub 30} carotenoids having seven, eight and nine {pi}-electron conjugated carbon-carbon double bonds were studied using steady-state absorption, fluorescence, fluorescence excitation and time-resolved absorption spectroscopy. These diapocarotenes were purified by high performance liquid chromatography (HPLC) prior to the spectroscopic experiments. The fluorescence data show a systematic crossover from dominant S{sub 1} {yields} S{sub 0} (2{sup 1}Ag{yields} 1{sup 1}Ag) emission to dominant S{sub 2} {yields} S{sub 0} (1{sup 1}Bu {yields} 1{sup 1}Ag) with increasing extent of conjugation. The low temperatures facilitated the determination of the spectral origins of the S{sub 1} {yields} S{sub 0} (2{sup 1}Agmore » {yields} 1{sup 1}Ag) emissions, which were assigned by Gaussian deconvolution of the experimental line shapes. The lifetimes of the S{sub 1} states of the molecules were measured by transient absorption spectroscopy and were found to decrease as the conjugated chain length increases. The energy gap law for radiationless transitions is used to correlate the S{sub 1} energies with the dynamics. These molecules provide a systematic series for understanding the structural features that control the photochemical properties of open-chain, diapocarotenoids. The implications of these results on the roles of carotenoids in photosynthetic organisms are discussed.« less

Absorption of a laser light pulse in a dense plasma.

NASA Technical Reports Server (NTRS)

Mehlman-Balloffet, G.

1973-01-01

An experimental study of the absorption of a laser light pulse in a transient, high-density, high-temperature plasma is presented. The plasma is generated around a metallic anode tip by a fast capacitive discharge occurring in vacuum. The amount of transmitted light is measured for plasmas made of different metallic ions in the regions of the discharge of high electronic density. Variation of the transmission during the laser pulse is also recorded. Plasma electrons are considered responsible for the very high absorption observed.

Transient Resonance Raman Spectroscopy of a Light-Driven Sodium-Ion-Pump Rhodopsin from Indibacter alkaliphilus.

PubMed

Kajimoto, Kousuke; Kikukawa, Takashi; Nakashima, Hiroki; Yamaryo, Haruki; Saito, Yuta; Fujisawa, Tomotsumi; Demura, Makoto; Unno, Masashi

2017-05-04

Sodium-ion-pump rhodopsin (NaR) is a microbial rhodopsin that transports Na + during its photocycle. Here we explore the photocycle mechanism of NaR from Indibacter alkaliphilus with transient absorption and transient resonance Raman spectroscopy. The transient absorption data indicate that the photocycle of NaR is K (545 nm) → L (490 nm)/M (420 nm) → O 1 (590 nm) → O 2 (560 nm) → NaR, where the L and M are formed as equilibrium states. The presence of K, L, M, and O intermediates was confirmed by the resonance Raman spectra with 442 and 532 nm excitation. The main component of the transient resonance Raman spectra was due to L which contains a 13-cis retinal protonated Schiff base. The presence of an enhanced hydrogen out-of-plane band as well as its sensitivity to the H/D exchange indicate that the retinal chromophore is distorted near the Schiff base region in L. Moreover, the retinal Schiff base of the L state forms a hydrogen bond that is stronger than that of the dark state. These observations are consistent with a Na + pumping mechanism that involves a proton transfer from the retinal Schiff base to a key aspartate residue (Asp116 in Krokinobacter eikastus rhodopsin 2) in the L/M states.

Synthesis, characterization and photophysical properties of ferrocenyl and mixed sandwich cobaltocenyl ester linked meso-triaryl corrole dyads

NASA Astrophysics Data System (ADS)

Achary, B. Shivaprasad; Ramya, A. R.; Trivedi, Rajiv; Bangal, P. R.; Giribabu, L.

We report here the design and synthesis of corrole-metallocene dyads consisting of a metallocene (either ferrocene (Dyad 1) or mixed sandwich η5-[C5H4(COOH)]Co(η4-C4Ph4) (Dyad 2)) connected via an ester linkage at meso phenyl position. Both the dyads were characterized by 1H NMR, MALDI-TOF, UV-visible, fluorescence spectroscopies (steady-state, picosecond time-resolved), femtosecond transient absorption spectroscopy (fs-TA) and electrochemical methods. The absorption spectra of these dyads showed slight broadening and splitting of the Soret band that indicates a weak ground state interaction between the corrole macrocycle and metallocene part of the present donor-acceptor (D-A) system. However, in both the dyad systems, fluorescence emission of the corrole was quenched in polar solvents as compared to its parent compound 10-(4-hydroxyphenyl)-5,15-bis-(pentafluorophenyl ) corrole (Ph-Corr). The quenching was more pronounced in ferrocene derivatives than in cobaltocenyl derivatives. Transient absorption studies confirm the absence of photoinduced electron transfer from metallocene to correl for these dyad systems and the quenching of singlet state of corrole is found to enhance intersystem crossing due to heavy atom effect. Corrole-ferrocene and corrole-mixed sandwich η5-[C5H4(COOH)]Co(η4-C4Ph4) dyads have been designed, synthesized and characterized by various spectroscopic techniques. Emission intensitiy of both dyads were quenched in polar solvents whereas transient absorption studies indicates that the quenching coule be due to the heavy atom effect.

Transient absorption microscopy studies of energy relaxation in graphene oxide thin film.

PubMed

Murphy, Sean; Huang, Libai

2013-04-10

Spatial mapping of energy relaxation in graphene oxide (GO) thin films has been imaged using transient absorption microscopy (TAM). Correlated AFM images allow us to accurately determine the thickness of the GO films. In contrast to previous studies, correlated TAM-AFM allows determination of the effect of interactions of GO with the substrate and between stacked GO layers on the relaxation dynamics. Our results show that energy relaxation in GO flakes has little dependence on the substrate, number of stacked layers, and excitation intensity. This is in direct contrast to pristine graphene, where these factors have great consequences in energy relaxation. This suggests intrinsic factors rather than extrinsic ones dominate the excited state dynamics of GO films.

Photoinduced Charge Shifts and Electron Transfer in Viologen-Tetraphenylborate Complexes: Push-Pull Character of the Exciplex.

PubMed

Santos, Willy G; Budkina, Darya S; Deflon, Victor M; Tarnovsky, Alexander N; Cardoso, Daniel R; Forbes, Malcolm D E

2017-06-14

Viologen-tetraarylborate ion-pair complexes were prepared and investigated by steady-state and time-resolved spectroscopic techniques such as fluorescence and femtosecond transient absorption. The results highlight a charge transfer transition that leads to changes in the viologen structure in the excited singlet state. Femtosecond transient absorption reveals the formation of excited-state absorption and stimulated emission bands assigned to the planar (k obs < 10 12 s -1 ) and twisted (k obs ∼ 10 10 s -1 ) structures between two pyridinium groups in the viologen ion. An efficient photoinduced electron transfer from the tetraphenylborate anionic moiety to the viologen dication was observed less than 1 μs after excitation. This is a consequence of the push-pull character of the electron donor twisted viologen structure, which helps formation of the borate triplet state. The borate triplet state is deactivated further via a second electron transfer process, generating viologen cation radical (V •+ ).

Multiphoton-gated cycloreversion reaction of a fluorescent diarylethene derivative as revealed by transient absorption spectroscopy.

PubMed

Nagasaka, Tatsuhiro; Kunishi, Tomohiro; Sotome, Hikaru; Koga, Masafumi; Morimoto, Masakazu; Irie, Masahiro; Miyasaka, Hiroshi

2018-06-07

The one- and two-photon cycloreversion reactions of a fluorescent diarylethene derivative with oxidized benzothiophene moieties were investigated by means of ultrafast laser spectroscopy. Femtosecond transient absorption spectroscopy under the one-photon excitation condition revealed that the excited closed-ring isomer is simply deactivated into the initial ground state with a time constant of 2.6 ns without remarkable cycloreversion, the results of which are consistent with the very low cycloreversion reaction yield (<10-5) under steady-state light irradiation. On the other hand, an efficient cycloreversion reaction was observed under irradiation with a picosecond laser pulse at 532 nm. The excitation intensity dependence of the cycloreversion reaction indicates that a highly excited state attained by the stepwise two-photon absorption is responsible for the marked increase of the cycloreversion reaction, and the quantum yield at the highly excited state was estimated to be 0.018 from quantitative analysis, indicating that the reaction is enhanced by a factor of >1800.

Au279(SR)84: The Smallest Gold Thiolate Nanocrystal That Is Metallic and the Birth of Plasmon.

PubMed

Sakthivel, Naga Arjun; Stener, Mauro; Sementa, Luca; Fortunelli, Alessandro; Ramakrishna, Guda; Dass, Amala

2018-03-15

We report a detailed study on the optical properties of Au 279 (SR) 84 using steady-state and transient absorption measurements to probe its metallic nature, time-dependent density functional theory (TDDFT) studies to correlate the optical spectra, and density of states (DOS) to reveal the factors governing the origin of the collective surface plasmon resonance (SPR) oscillation. Au 279 is the smallest identified gold nanocrystal to exhibit SPR. Its optical absorption exhibits SPR at 510 nm. Power-dependent bleach recovery kinetics of Au 279 suggests that electron dynamics dominates its relaxation and it can support plasmon oscillations. Interestingly, TDDFT and DOS studies with different tail group residues (-CH 3 and -Ph) revealed the important role played by the tail groups of ligands in collective oscillation. Also, steady-state and time-resolved absorption for Au 36 , Au 44 , and Au 133 were studied to reveal the molecule-to-metal evolution of aromatic AuNMs. The optical gap and transient decay lifetimes decrease as the size increases.

The Mysterious 6565 Å Absorption Feature of the Galactic Halo

NASA Astrophysics Data System (ADS)

Sethi, Shiv K.; Shchekinov, Yuri; Nath, Biman B.

2017-12-01

We consider various possible scenarios to explain the recent observation of what has been called a broad Hα absorption in our Galactic halo, with peak optical depth τ ≃ 0.01 and equivalent width W≃ 0.17 \\mathringA . We show that the absorbed feature cannot arise from the circumgalactic and ISM Hα absorption. As the observed absorption feature is quite broad ({{Δ }}λ ≃ 30 \\mathringA ), we also consider CNO lines that lie close to Hα as possible alternatives to explain the feature. We show that such lines could also not account for the observed feature. Instead, we suggest that it could arise from diffuse interstellar bands (DIBs) carriers or polyaromatic hydrocarbons (PAHs) absorption. While we identify several such lines close to the Hα transition, we are unable to determine the molecule responsible for the observed feature, partly because of selection effects that prevent us from identifying DIBs/PAHs features close to Hα using local observations. Deep integration of a few extragalactic sources with high spectral resolution might allow us to distinguish between different possible explanations.

Inherited Fe and Ti electron transition spectroscopic features in altered ultramafic-carbonatite intrusives

NASA Astrophysics Data System (ADS)

Shavers, E. J.; Ghulam, A.; Encarnacion, J. P.

2016-12-01

Spectroscopic reflectance in the visible to short-wave infrared region is an important tool for remote geologic mapping and is applied at scales from satellite to field measurements. Remote geologic mapping is challenging in regions subject to significant surficial weathering. Here we identify absorption features found in altered volcanic pipes and dikes in the Avon Volcanic District, Missouri, that are inherited from the original ultramafic and carbonatite lithology. Alteration ranges from small degree hydrothermal alteration to extensive laterization. The absorption features are three broad minima centered near 690, 890, and 1100 nm. Features in this region are recognized to be caused by ferric and ferrous Fe minerals including olivine, carbonates, chlorite, and goethite all of which are found among the Avon pipes and dikes that are in various stages of alteration. Iron-related intervalence charge transfer and crystal field perturbations of ions are the principal causes of the spectroscopic features in the visible to near-infrared region yet spectra are also distorted by factors like texture and the presence of opaque minerals known to reduce overall reflectance. In the Avon samples, Fe oxide content can reach >15 wt% leading to prominent absorption features even in the less altered ultramafics with reflectance curve maxima as low as 5%. The exaggerated minima allow the altered intrusive rocks to stand out among other weathered lithologies that will often have clay features in the region yet have lower iron concentration. The absorption feature centered near 690 nm is particularly noteworthy. Broad mineral-related absorption features centered at this wavelength are rare but have been linked to Ti3+ in octahedral coordination. The reduced form of Ti is not common in surface lithologies. Titanium-rich andradite has Ti3+ in the octahedral position, is resistant to weathering, is found among the Avon lithologies including ultramafic, carbonatite, and carbonated breccia, and is identified here as the cause of the 690 nm absorption feature. The Ti3+ absorption feature centered near 690 nm and strong Fe absorption features at 890 and 1100 nm may be useful indicators of rare intrusive lithologies in remote geologic mapping.

Attosecond transient absorption of a bound wave packet coupled to a smooth continuum

DOE PAGES

Dahlström, Jan Marcus; Pabst, Stefan; Lindroth, Eva

2017-10-16

Here, we investigate the possibility of using transient absorption of a coherent bound electron wave packet in hydrogen as an attosecond pulse characterization technique. In a recent work, we have shown that photoionization of such a coherent bound electron wave packet opens up for pulse characterization with unprecedented temporal accuracy—independent of the atomic structure—with maximal photoemission at all kinetic energies given a wave packet with zero relative phase. Here, we perform numerical propagation of the time-dependent Schrödinger equation and analytical calculations based on perturbation theory to show that the energy-resolved maximal absorption of photons from the attosecond pulse does not uniquely occur at a zero relative phase of the initial wave packet. Instead, maximal absorption occurs at different relative wave packet phases, distributed as a non-monotonous function with a smoothmore » $$-\\pi /2$$ shift across the central photon energy (given a Fourier-limited Gaussian pulse). Similar results are also found in helium. Our finding is surprising, because it implies that the energy-resolved photoelectrons are not mapped one-to-one with the energy-resolved absorbed photons of the attosecond pulse.« less

Two-photon absorption and transient photothermal imaging of pigments in tissues

NASA Astrophysics Data System (ADS)

Ye, Tong; Fu, Dan; Matthews, Thomas E.; Hong, Lian; Simon, John D.; Warren, Warren S.

2008-02-01

As a main pigment in skin tissues, melanin plays an important role in photo-protecting skin from UV radiation. However, melanogenesis may be altered due to disease or environmental factors; for example, sun exposure may cause damage and mutation of melanocytes and induce melanoma. Imaging pigmentation changes may provide invaluable information to catch the malignant transformation in its early stage and in turn improve the prognosis of patients. We have demonstrated previously that transmission mode, two-photon, one- or two-color absorption microscopy could provide remarkable contrast in imaging melanin in skin. In this report we demonstrate significantly improved sensitivity, so that we are now able to image in epi-mode (or back reflection) in two-photon absorption. This improvement makes possible for us to characterize the different types of pigmentation on the skin in vivo at virtually any location. Another finding is that we can also image transient photothermal dynamics due to the light absorption of melanin. By carefully choosing excitation and probe wavelengths, we might be able to image melanin in different structures under different micro-environments in skin, which could provide useful photochemical and photophysical insights in understanding how pigments are involved in photoprotection and photodamage of cells.

Attosecond transient absorption of a bound wave packet coupled to a smooth continuum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dahlström, Jan Marcus; Pabst, Stefan; Lindroth, Eva

Here, we investigate the possibility of using transient absorption of a coherent bound electron wave packet in hydrogen as an attosecond pulse characterization technique. In a recent work, we have shown that photoionization of such a coherent bound electron wave packet opens up for pulse characterization with unprecedented temporal accuracy—independent of the atomic structure—with maximal photoemission at all kinetic energies given a wave packet with zero relative phase. Here, we perform numerical propagation of the time-dependent Schrödinger equation and analytical calculations based on perturbation theory to show that the energy-resolved maximal absorption of photons from the attosecond pulse does not uniquely occur at a zero relative phase of the initial wave packet. Instead, maximal absorption occurs at different relative wave packet phases, distributed as a non-monotonous function with a smoothmore » $$-\\pi /2$$ shift across the central photon energy (given a Fourier-limited Gaussian pulse). Similar results are also found in helium. Our finding is surprising, because it implies that the energy-resolved photoelectrons are not mapped one-to-one with the energy-resolved absorbed photons of the attosecond pulse.« less

Broadband ultrafast transient absorption of multiple exciton dynamics in lead sulfide nanocrystals

NASA Astrophysics Data System (ADS)

Gesuele, Felice; Wong, Chee Wei; Sfeir, Matthew; Misewich, James; Koh, Weonkyu; Murray, Christopher

2011-03-01

Multiple exciton generation (MEG) is under intense investigation as potential third-generation solar photovoltaics with efficiencies beyond the Shockley-Queisser limit. We examine PbS nanocrystals, dispersed and vigorously stirred in TCE solution, by means of supercontinuum femtosecond transient absorption (TA). TA spectra show the presence of first and second order bleaches for the 1Sh-Se and 1Ph-Pe excitonic transition while photoinduced absorption for the 1Sh,e-Ph,e transitions. We found evidence of carrier multiplication (MEG for single absorbed photon) from the analysis of the first and second order bleaches, in the limit of low number of absorbed photons (Nabs ~ 0.01), for energy three times and four times the Energy gap. The MEG efficiency, derived from the ratio between early-time to long-time TA signal, presents a strongly dispersive behavior with maximum red shifted respect the first absorption peak. Analysis of population dynamics shows that in presence of biexciton, the 1Sh-Se bleach peak is red-shifted indicating a positive binding energy. MEG efficiency estimation will be discussed with regards to spectral integration, correlated higher-order and first excitonic transitions, as well as the nanocrystal morphologies.

Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy

DOE PAGES

Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.; ...

2017-06-06

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si 0.25Ge 0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M 4,5-edge (~30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons acrossmore » the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct (ΔE gap,Ge,direct = 0.8 eV) and Si 0.25Ge 0.75 indirect gaps (ΔE gap,Si0.25Ge0.75,indirect = 0.95 eV) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si 0.25Ge 0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution.« less

Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters.

PubMed

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y; Nobusada, Katsuyuki; Jin, Rongchao

2016-04-07

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.

Ultrafast carrier thermalization and trapping in silicon-germanium alloy probed by extreme ultraviolet transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zürch, Michael; Chang, Hung-Tzu; Kraus, Peter M.

Semiconductor alloys containing silicon and germanium are of growing importance for compact and highly efficient photonic devices due to their favorable properties for direct integration into silicon platforms and wide tunability of optical parameters. Here, we report the simultaneous direct and energy-resolved probing of ultrafast electron and hole dynamics in a silicon-germanium alloy with the stoichiometry Si 0.25Ge 0.75 by extreme ultraviolet transient absorption spectroscopy. Probing the photoinduced dynamics of charge carriers at the germanium M 4,5-edge (~30 eV) allows the germanium atoms to be used as reporter atoms for carrier dynamics in the alloy. The photoexcitation of electrons acrossmore » the direct and indirect band gap into conduction band (CB) valleys and their subsequent hot carrier relaxation are observed and compared to pure germanium, where the Ge direct (ΔE gap,Ge,direct = 0.8 eV) and Si 0.25Ge 0.75 indirect gaps (ΔE gap,Si0.25Ge0.75,indirect = 0.95 eV) are comparable in energy. In the alloy, comparable carrier lifetimes are observed for the X, L, and Γ valleys in the conduction band. A midgap feature associated with electrons accumulating in trap states near the CB edge following intraband thermalization is observed in the Si 0.25Ge 0.75 alloy. The successful implementation of the reporter atom concept for capturing the dynamics of the electronic bands by site-specific probing in solids opens a route to study carrier dynamics in more complex materials with femtosecond and sub-femtosecond temporal resolution.« less

Effects of single atom doping on the ultrafast electron dynamics of M 1Au 24(SR) 18 (M = Pd, Pt) nanoclusters

DOE PAGES

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; ...

2016-02-29

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M 1@Au 24(SR) 18 (M = Pd, Pt; R = CH 2CH 2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M 1Au 12 core states; (2) core to shell relaxation in a few picoseconds; and (3)more » relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au 25(SR) 18 cluster. As a result, the detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.« less

Apparatus and method for transient thermal infrared emission spectrometry

DOEpatents

McClelland, John F.; Jones, Roger W.

1991-12-24

A method and apparatus for enabling analysis of a solid material (16, 42) by applying energy from an energy source (20, 70) top a surface region of the solid material sufficient to cause transient heating in a thin surface layer portion of the solid material (16, 42) so as to enable transient thermal emission of infrared radiation from the thin surface layer portion, and by detecting with a spectrometer/detector (28, 58) substantially only the transient thermal emission of infrared radiation from the thin surface layer portion of the solid material. The detected transient thermal emission of infrared radiation is sufficiently free of self-absorption by the solid material of emitted infrared radiation, so as to be indicative of characteristics relating to molecular composition of the solid material.

VizieR Online Data Catalog: Absorption velocities for 21 super-luminous SNe Ic (Liu+, 2017)

NASA Astrophysics Data System (ADS)

Liu, Y.-Q.; Modjaz, M.; Bianco, F. B.

2018-04-01

We have collected the spectra of all available super-luminous supernovae (SLSNe) Ic that have a date of maximum light published before April of 2016. These SLSNe Ic were mainly discovered and observed by the All-Sky Automated Survey for Supernovae (ASAS-SN), the Catalina Real-Time Transient Survey, the Dark Energy Survey (DES), the Hubble Space Telescope Cluster Supernova Survey, the Pan-STARRS1 Medium Deep Survey (PS1), the Public ESO Spectroscopic Survey of Transient Objects (PESSTO), the Intermediate Palomar Transient Factory (iPTF) as well as the Palomar Transient Factory (PTF), and the Supernova Legacy Survey (SNLS). See table 1. (2 data files).

Design and development of a probe-based multiplexed multi-species absorption spectroscopy sensor for characterizing transient gas-parameter distributions in the intake systems of I.C. engines

DOE PAGES

Jatana, Gurneesh; Geckler, Sam; Koeberlein, David; ...

2016-09-01

We designed and developed a 4-probe multiplexed multi-species absorption spectroscopy sensor system for gas property measurements on the intake side of commercial multi-cylinder internal-combustion (I.C.) engines; the resulting cycle- and cylinder-resolved concentration, temperature and pressure measurements are applicable for assessing spatial and temporal variations in the recirculated exhaust gas (EGR) distribution at various locations along the intake gas path, which in turn is relevant to assessing cylinder charge uniformity, control strategies, and CFD models. Furthermore, the diagnostic is based on absorption spectroscopy and includes an H 2O absorption system (utilizing a 1.39 m distributed feedback (DFB) diode laser) for measuringmore » gas temperature, pressure, and H 2O concentration, and a CO 2 absorption system (utilizing a 2.7 m DFB laser) for measuring CO 2 concentration. The various lasers, optical components and detectors were housed in an instrument box, and the 1.39- m and 2.7- m lasers were guided to and from the engine-mounted probes via optical fibers and hollow waveguides, respectively. The 5kHz measurement bandwidth allows for near-crank angle resolved measurements, with a resolution of 1.2 crank angle degrees at 1000 RPM. Our use of compact stainless steel measurement probes enables simultaneous multi-point measurements at various locations on the engine with minimal changes to the base engine hardware; in addition to resolving large-scale spatial variations via simultaneous multi-probe measurements, local spatial gradients can be resolved by translating individual probes. Along with details of various sensor design features and performance, we also demonstrate validation of the spectral parameters of the associated CO 2 absorption transitions using both a multi-pass heated cell and the sensor probes.« less

Absorption and emission of single attosecond light pulses in an autoionizing gaseous medium dressed by a time-delayed control field

NASA Astrophysics Data System (ADS)

Chu, Wei-Chun; Lin, C. D.

2013-01-01

An extreme ultraviolet (EUV) single attosecond pulse passing through a laser-dressed dense gas is studied theoretically. The weak EUV pulse pumps the helium gas from the ground state to the 2s2p(1P) autoionizing state, which is coupled to the 2s2(1S) autoionizing state by a femtosecond infrared laser with the intensity in the order of 1012 W/cm2. The simulation shows how the transient absorption and emission of the EUV are modified by the coupling laser. A simple analytical expression for the atomic response derived for δ-function pulses reveals the strong modification of the Fano lineshape in the spectra, where these features are quite universal and remain valid for realistic pulse conditions. We further account for the propagation of pulses in the medium and show that the EUV signal at the atomic resonance can be enhanced in the gaseous medium by more than 50% for specifically adjusted laser parameters, and that this enhancement persists as the EUV propagates in the gaseous medium. Our result demonstrates the high-level control of nonlinear optical effects that are achievable with attosecond pulses.

Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

DOE PAGES

Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto; ...

2017-01-30

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B 12

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Nicholas A.; Deb, Aniruddha; Alonso-Mori, Roberto

Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B 12, cyanocobalamin (CNCbl), in solution. Cobalamins are important biological cofactors involved in methyl transfer, radical rearrangement, and light-activated gene regulation, while also holding promise as light-activated agents for spatiotemporal controlled delivery of therapeutics. We introduce polarized femtosecond XANES, combined with UV–visible spectroscopy, to reveal sequential structural evolution of CNCbl in the excited electronic state. Femtosecond polarized XANES provides the crucial structural dynamics link between computed potential energy surfaces and optical transient absorption spectroscopy. Polarization selectivity can be used to uniquely identify electronic contributionsmore » and structural changes, even in isotropic samples when well-defined electronic transitions are excited. Our XANES measurements reveal that the structural changes upon photoexcitation occur mainly in the axial direction, where elongation of the axial Co–CN bond and Co–N Im bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. In conclusion, these observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.« less

New styryl phenanthroline derivatives as model D-π-A-π-D materials for non-linear optics.

PubMed

Bonaccorso, Carmela; Cesaretti, Alessio; Elisei, Fausto; Mencaroni, Letizia; Spalletti, Anna; Fortuna, Cosimo Gianluca

2018-04-27

Four novel push-pull systems combining a central phenanthroline acceptor moiety and two substituted benzene rings, as a part of the conjugated π-system between the donor and the acceptor moieties, have been synthetized through a straightforward and efficient one-step synthetic procedure. The chromophores display high fluorescence and a peculiar fluorosolvatochromic behavior. Ultrafast investigation by means of state-of-the-art femtosecond-resolved transient absorption and fluorescence up-conversion spectroscopies allowed the role of intramolecular charge transfer (ICT) states to be evidenced, also revealing the crucial role played by both the polarity and proticity of the medium on the excited state dynamics of the chromophores. The ICT processes, responsible for the solvatochromism, also lead to interesting non-linear optical (NLO) properties: namely great two photon absorption cross-sections (hundreds of GM), investigated by the Two Photon Excited Fluorescence (TPEF) technique, and large second order hyperpolarizability coefficients, estimated through a convenient solvatochromic method. These features thus make the investigated styryl phenanthroline molecules model D-π-A-π-D compounds for non-linear optical applications. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modeling Photochemical Dynamics in Optically Active Energetic Materials

NASA Astrophysics Data System (ADS)

Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R. Jason; Tretiak, Sergei

Most high explosives (HEs) absorb in the UV range, making it difficult to develop HEs that can be excited with standard lasers. The conventional optical initiation mechanisms require high laser intensity and occur via indirect thermal or shock processes. A photochemical initiation mechanism could allow control over the chemistry contributing to decomposition leading to initiation. We combine UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) with Nonadiabatic Excited State Molecular Dynamics (NA-ESMD) to model the photochemical pathways in nitromethane (NM), a low sensitivity HE known to undergo UV photolysis. We investigate the ultrafast photodecomposition of NM from the nπ* state excited at 266 nm. The FSRS photoproduct spectrum points to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of 20 fs were predicted from simulations. Predicted time scales reveal that NO2 dissociation occurs in 81 +/-4 fs and methyl nitrite formation is much slower at 452 +/-9 fs corresponding to the absorption feature in the TA spectrum. The relative time scales are consistent with isomerization by NO2 dissociation and ONO rebinding.

Zethrene biradicals: How pro-aromaticity is expressed in the ground electronic state and in the lowest energy singlet, triplet, and ionic states

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zafra, José Luis; González Cano, Rafael C.; Ruiz Delgado, M. Carmen

A analysis of the electronic and molecular structures of new molecular materials based on zethrene is presented with particular attention to those systems having a central benzo-quinoidal core able to generate Kekulé biradicals whose stability is provided by the aromaticity recovery in this central unit. These Kekulé biradicals display singlet ground electronic states thanks to double spin polarization and have low-energy lying triplet excited states also featured by the aromaticity gain. Pro-aromatization is also the driving force for the stabilization of the ionized species. Moreover, the low energy lying singlet excited states also display a profound biradical fingerprint allowing tomore » singlet exciton fission. These properties are discussed in the context of the size of the zethrene core and of its substitution. The work encompasses all known long zethrenes and makes use of a variety of experimental techniques, such as Raman, UV-Vis-NIR absorption, transient absorption, in situ spectroelectrochemistry and quantum chemical calculations. This study reveals how the insertion of suitable molecular modules (i.e., quinoidal) opens the door to new intriguing molecular properties exploitable in organic electronics.« less

Singlet exciton fission in polycrystalline pentacene: from photophysics toward devices.

PubMed

Wilson, Mark W B; Rao, Akshay; Ehrler, Bruno; Friend, Richard H

2013-06-18

Singlet exciton fission is the process in conjugated organic molecules bywhich a photogenerated singlet exciton couples to a nearby chromophore in the ground state, creating a pair of triplet excitons. Researchers first reported this phenomenon in the 1960s, an event that sparked further studies in the following decade. These investigations used fluorescence spectroscopy to establish that exciton fission occurred in single crystals of several acenes. However, research interest has been recently rekindled by the possibility that singlet fission could be used as a carrier multiplication technique to enhance the efficiency of photovoltaic cells. The most successful architecture to-date involves sensitizing a red-absorbing photoactive layer with a blue-absorbing material that undergoes fission, thereby generating additional photocurrent from higher-energy photons. The quest for improved solar cells has spurred a drive to better understand the fission process, which has received timely aid from modern techniques for time-resolved spectroscopy, quantum chemistry, and small-molecule device fabrication. However, the consensus interpretation of the initial studies using ultrafast transient absorption spectroscopy was that exciton fission was suppressed in polycrystalline thin films of pentacene, a material that would be otherwise expected to be an ideal model system, as well as a viable candidate for fission-sensitized photovoltaic devices. In this Account, we review the results of our recent transient absorption and device-based studies of polycrystalline pentacene. We address the controversy surrounding the assignment of spectroscopic features in transient absorption data, and illustrate how a consistent interpretation is possible. This work underpins our conclusion that singlet fission in pentacene is extraordinarily rapid (∼80 fs) and is thus the dominant decay channel for the photoexcited singlet exciton. Further, we discuss our demonstration that triplet excitons generated via singlet fission in pentacene can be dissociated at an interface with a suitable electron acceptor, such as fullerenes and infrared-absorbing inorganic semiconducting quantum dots. We highlight our recent reports of a pentacene/PbSe hybrid solar cell with a power conversion efficiency of 4.7% and of a pentacene/PbSe/amorphous silicon photovoltaic device. Although substantive challenges remain, both to better our understanding of the mechanism of singlet exciton fission and to optimize device performance, this realization of a solar cell where photocurrent is simultaneously contributed from a blue-absorbing fission-capable material and an infrared-absorbing conventional cell is an important step towards a dual-bandgap, single-junction, fission-enhanced photovoltaic device, which could one day surpass the Shockley-Queisser limit.

The Rise of SN 2014J in the Nearby Galaxy M 82

NASA Technical Reports Server (NTRS)

A.Goobar; Johansson, J.; Amanullah, R.; Cao, Y.; Perley, D.A.; Kasliwal, M. M.; Ferreti, R.; Nugent, P. E.; Harris, C.; Cenko, S. B.

2014-01-01

We report on the discovery of SN 2014J in the nearby galaxy M 82. Given its proximity, it offers the best opportunity to date to study a thermonuclear supernova over a wide range of the electromagnetic spectrum. Optical, near-IR and mid-IR observations on the rising lightcurve, orchestrated by the intermediate Palomar Transient Factory (iPTF), show that SN 2014J is a spectroscopically normal Type Ia supernova, albeit exhibiting high-velocity features in its spectrum and heavily reddened by dust in the host galaxy. Our earliest detections start just hours after the fitted time of explosion. We use high-resolution optical spectroscopy to analyze the dense intervening material and do not detect any evolution in the resolved absorption features during the lightcurve rise. Similarly to other highly reddened Type Ia supernovae, a low value of total-to-selective extinction, R (sub V) less than or approximately equal to 2, provides the best match to our observations. We also study pre-explosion optical and near-IR images from HST with special emphasis on the sources nearest to the SN location.

Use of ultrafast dispersed pump-dump-probe and pump-repump-probe spectroscopies to explore the light-induced dynamics of peridinin in solution.

PubMed

Papagiannakis, Emmanouil; Vengris, Mikas; Larsen, Delmar S; van Stokkum, Ivo H M; Hiller, Roger G; van Grondelle, Rienk

2006-01-12

Optical pump-induced dynamics of the highly asymmetric carotenoid peridinin in methanol was studied by dispersed pump-probe, pump-dump-probe, and pump-repump-probe transient absorption spectroscopy in the visible region. Dispersed pump-probe measurements show that the decay of the initially excited S2 state populates two excited states, the S1 and the intramolecular charge-transfer (ICT) state, at a ratio determined by the excitation wavelength. The ensuing spectral evolution occurs on the time scale of a few picoseconds and suggests the equilibration of these states. Dumping the stimulated emission of the ICT state with an additional 800-nm pulse after 400- and 530-nm excitation preferentially removes the ICT state contribution from the broad excited-state absorption, allowing for its spectral characterization. At the same time, an unrelaxed ground-state species, which has a subpicosecond lifetime, is populated. The application of the 800-nm pulse at early times, when the S2 state is still populated, led to direct generation of the peridinin cation, observed for the first time in a transient absorption experiment. The excited and ground electronic states manifold of peridinin has been reconstructed using target analysis; this approach combined with the measured multipulse spectroscopic data allows us to estimate the spectra and time scales of the corresponding transient states.

Excited-State Deactivation of Branched Phthalocyanine Compounds.

PubMed

Zhu, Huaning; Li, Yang; Chen, Jun; Zhou, Meng; Niu, Yingli; Zhang, Xinxing; Guo, Qianjin; Wang, Shuangqing; Yang, Guoqiang; Xia, Andong

2015-12-21

The excited-state relaxation dynamics and chromophore interactions in two phthalocyanine compounds (bis- and trisphthalocyanines) are studied by using steady-state and femtosecond transient absorption spectral measurements, where the excited-state energy-transfer mechanism is explored. By exciting phthalocyanine compounds to their second electronically excited states and probing the subsequent relaxation dynamics, a multitude of deactivation pathways are identified. The transient absorption spectra show the relaxation pathway from the exciton state to excimer state and then back to the ground state in bisphthalocyanine (bis-Pc). In trisphthalocyanine (tris-Pc), the monomeric and dimeric subunits are excited and the excitation energy transfers from the monomeric vibrationally hot S1 state to the exciton state of a pre-associated dimer, with subsequent relaxation to the ground state through the excimer state. The theoretical calculations and steady-state spectra also show a face-to-face conformation in bis-Pc, whereas in tris-Pc, two of the three phthalocyanine branches form a pre-associated face-to-face dimeric conformation with the third one acting as a monomeric unit; this is consistent with the results of the transient absorption experiments from the perspective of molecular structure. The detailed structure-property relationships in phthalocyanine compounds is useful for exploring the function of molecular aggregates in energy migration of natural photosynthesis systems. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mechanical behaviour of TWIP steel under shear loading

NASA Astrophysics Data System (ADS)

Vincze, G.; Butuc, M. C.; Barlat, F.

2016-08-01

Twinning induced plasticity steels (TWIP) are very good candidate for automotive industry applications because they potentially offer large energy absorption before failure due to their exceptional strain hardening capability and high strength. However, their behaviour is drastically influenced by the loading conditions. In this work, the mechanical behaviour of a TWIP steel sheet sample was investigated at room temperature under monotonic and reverse simple shear loading. It was shown that all the expected features of load reversal such as Bauschinger effect, transient strain hardening with high rate and permanent softening, depend on the prestrain level. This is in agreement with the fact that these effects, which occur during reloading, are related to the rearrangement of the dislocation structure induced during the predeformation. The homogeneous anisotropic hardening (HAH) approach proposed by Barlat et al. (2011) [1] was successfully employed to predict the experimental results.

Fabrication of Planar Heterojunction Perovskite Solar Cells by Controlled Low-Pressure Vapor Annealing.

PubMed

Li, Yanbo; Cooper, Jason K; Buonsanti, Raffaella; Giannini, Cinzia; Liu, Yi; Toma, Francesca M; Sharp, Ian D

2015-02-05

A new method for achieving high efficiency planar CH3NH3I3-xClx perovskite photovoltaics, based on a low pressure, reduced temperature vapor annealing is demonstrated. Heterojunction devices based on this hybrid halide perovskite exhibit a top PCE of 16.8%, reduced J-V hysteresis, and highly repeatable performance without need for a mesoporous or nanocrystalline metal oxide layer. Our findings demonstrate that large hysteresis is not an inherent feature of planar heterojunctions, and that efficient charge extraction can be achieved with uniform halide perovskite materials with desired composition. X-ray diffraction, valence band spectroscopy, and transient absorption measurements of these thin films reveal that structural modifications induced by chlorine clearly dominate over chemical and electronic doping effects, without affecting the Fermi level or photocarrier lifetime in the material.

Feasibility study on a short-pulsed IR wavelength for effective calculus fragmentation

NASA Astrophysics Data System (ADS)

Kang, Hyun Wook

2015-05-01

Laser-induced lithotripsy has been used for a minimally-invasive surgery to treat kidney-stone disease associated with urinary obstruction. A short-pulsed Tm:YAG laser (λ = 2.01 µm) was developed to improve fragmentation efficiency and was evaluated with a Ho:YAG laser (λ = 2.12 μm) as to its ablation feature and mass removal rate. Application of a train of sub-microsecond pulses with a lower energy at a frequency of 500 Hz created multiple events of cavitation that accompanied strong acoustic transients. During Tm:YAG irradiation, both high light absorption and secondary photomechanical impacts readily fragmented the calculus into small pieces (< 3 mm) and removed them 130 times faster than photothermal Ho:YAG lithotripsy. The proposed short-pulsed Tm:YAG approach may be an effective lithotripter for treating calculus disease.

Photochemical Approaches to Complex Chemotypes: Applications in Natural Product Synthesis

PubMed Central

2016-01-01

The use of photochemical transformations is a powerful strategy that allows for the formation of a high degree of molecular complexity from relatively simple building blocks in a single step. A central feature of all light-promoted transformations is the involvement of electronically excited states, generated upon absorption of photons. This produces transient reactive intermediates and significantly alters the reactivity of a chemical compound. The input of energy provided by light thus offers a means to produce strained and unique target compounds that cannot be assembled using thermal protocols. This review aims at highlighting photochemical transformations as a tool for rapidly accessing structurally and stereochemically diverse scaffolds. Synthetic designs based on photochemical transformations have the potential to afford complex polycyclic carbon skeletons with impressive efficiency, which are of high value in total synthesis. PMID:27120289

Transient and stationary spectroscopy of cytochrome c: ultrafast internal conversion controls photoreduction.

PubMed

Löwenich, Dennis; Kleinermanns, Karl; Karunakaran, Venugopal; Kovalenko, Sergey Alexander

2008-01-01

Photoreduction of cytochrome c (Cyt c) has been reinvestigated using femtosecond-to-nanosecond transient absorption and stationary spectroscopy. Femtosecond spectra of oxidized Cyt c, recorded in the probe range 270-1000 nm, demonstrate similar evolution upon 266 or 403 nm excitation: an ultrafast 0.3 ps internal conversion followed by a 4 ps vibrational cooling. Late transient spectra after 20 ps, from the cold ground-state chromophore, reveal a small but measurable signal from reduced Cyt c. The yield phi for Fe3+-->Fe2+ photoreduction is measured to be phi(403) = 0.016 and phi(266) = 0.08 for 403 and 266 nm excitation. These yields lead to a guess of the barrier E(f)(A) = 55 kJ mol(-1) for thermal ground-state electron transfer (ET). Nanosecond spectra initially show the typical absorption from reduced Cyt c and then exhibit temperature-dependent sub-microsecond decays (0.5 micros at 297 K), corresponding to a barrier E(A)(b) = 33 kJ mol(-1) for the back ET reaction and a reaction energy DeltaE = 22 kJ mol(-1). The nanosecond transients do not decay to zero on a second time scale, demonstrating the stability of some of the reduced Cyt c. The yields calculated from this stable reduced form agree with quasistationary reduction yields. Modest heating of Cyt c leads to its efficient thermal reduction as demonstrated by differential stationary absorption spectroscopy. In summary, our results point to ultrafast internal conversion of oxidized Cyt c upon UV or visible excitation, followed by Fe-porphyrin reduction due to thermal ground-state ET as the prevailing mechanism.

Temperature dependence of the hydrated electron's excited-state relaxation. II. Elucidating the relaxation mechanism through ultrafast transient absorption and stimulated emission spectroscopy

NASA Astrophysics Data System (ADS)

Farr, Erik P.; Zho, Chen-Chen; Challa, Jagannadha R.; Schwartz, Benjamin J.

2017-08-01

The structure of the hydrated electron, particularly whether it exists primarily within a cavity or encompasses interior water molecules, has been the subject of much recent debate. In Paper I [C.-C. Zho et al., J. Chem. Phys. 147, 074503 (2017)], we found that mixed quantum/classical simulations with cavity and non-cavity pseudopotentials gave different predictions for the temperature dependence of the rate of the photoexcited hydrated electron's relaxation back to the ground state. In this paper, we measure the ultrafast transient absorption spectroscopy of the photoexcited hydrated electron as a function of temperature to confront the predictions of our simulations. The ultrafast spectroscopy clearly shows faster relaxation dynamics at higher temperatures. In particular, the transient absorption data show a clear excess bleach beyond that of the equilibrium hydrated electron's ground-state absorption that can only be explained by stimulated emission. This stimulated emission component, which is consistent with the experimentally known fluorescence spectrum of the hydrated electron, decreases in both amplitude and lifetime as the temperature is increased. We use a kinetic model to globally fit the temperature-dependent transient absorption data at multiple temperatures ranging from 0 to 45 °C. We find the room-temperature lifetime of the excited-state hydrated electron to be 137 ±40 fs, in close agreement with recent time-resolved photoelectron spectroscopy (TRPES) experiments and in strong support of the "non-adiabatic" picture of the hydrated electron's excited-state relaxation. Moreover, we find that the excited-state lifetime is strongly temperature dependent, changing by slightly more than a factor of two over the 45 °C temperature range explored. This temperature dependence of the lifetime, along with a faster rate of ground-state cooling with increasing bulk temperature, should be directly observable by future TRPES experiments. Our data also suggest that the red side of the hydrated electron's fluorescence spectrum should significantly decrease with increasing temperature. Overall, our results are not consistent with the nearly complete lack of temperature dependence predicted by traditional cavity models of the hydrated electron but instead agree qualitatively and nearly quantitatively with the temperature-dependent structural changes predicted by the non-cavity hydrated electron model.

Characterizing the absorption and aging behavior of DUV optical material by high-resolution excimer laser calorimetry

NASA Astrophysics Data System (ADS)

Mann, Klaus R.; Eva, Eric

1998-06-01

Absorption loss in DUV optics during 193 nm irradiation is investigated by employing a high-resolution calorimetric technique which allows determining both single and two photon absorption coefficients at energy densities of several 10 mJ/cm2, avoiding a significant thermal load on the samples. UV calorimetry is also employed to investigate laser induced aging phenomena, e.g. color center formation in fused silica or CaF2. A separation of transient and cumulative effects as a function of intensity can be achieved, giving insight into various loss mechanisms. Moreover, the influence of dielectric coatings on the absorption characteristics is discussed.

Use of ruthenium dyes for subnanosecond detector fidelity testing in real time transient absorption

NASA Astrophysics Data System (ADS)

Byrdin, Martin; Thiagarajan, Viruthachalam; Villette, Sandrine; Espagne, Agathe; Brettel, Klaus

2009-04-01

Transient absorption spectroscopy is a powerful tool for the study of photoreactions on time scales from femtoseconds to seconds. Typically, reactions slower than ˜1 ns are recorded by the "classical" technique; the reaction is triggered by an excitation flash, and absorption changes accompanying the reaction are recorded in real time using a continuous monitoring light beam and a detection system with sufficiently fast response. The pico- and femtosecond region can be accessed by the more recent "pump-probe" technique, which circumvents the difficulties of real time detection on a subnanosecond time scale. This is paid for by accumulation of an excessively large number of shots to sample the reaction kinetics. Hence, it is of interest to extend the classical real time technique as far as possible to the subnanosecond range. In order to identify and minimize detection artifacts common on a subnanosecond scale, like overshoot, ringing, and signal reflections, rigorous testing is required of how the detection system responds to fast changes of the monitoring light intensity. Here, we introduce a novel method to create standard signals for detector fidelity testing on a time scale from a few picoseconds to tens of nanoseconds. The signals result from polarized measurements of absorption changes upon excitation of ruthenium complexes {[Ru(bpy)3]2+ and a less symmetric derivative} by a short laser flash. Two types of signals can be created depending on the polarization of the monitoring light with respect to that of the excitation flash: a fast steplike bleaching at magic angle and a monoexponentially decaying bleaching for parallel polarizations. The lifetime of the decay can be easily varied via temperature and viscosity of the solvent. The method is applied to test the performance of a newly developed real time transient absorption setup with 300 ps time resolution and high sensitivity.

Spectral and kinetic properties of radicals derived from oxidation of quinoxalin-2-one and its methyl derivative.

PubMed

Skotnicki, Konrad; De la Fuente, Julio R; Cañete, Alvaro; Bobrowski, Krzysztof

2014-11-19

The kinetics and spectral characteristics of the transients formed in the reactions of •OH and •N3 with quinoxalin-2(1H)-one (Q), its methyl derivative, 3-methylquinoxalin-2(1H)-one (3-MeQ) and pyrazin-2-one (Pyr) were studied by pulse radiolysis in aqueous solutions at pH 7. The transient absorption spectra recorded in the reactions of •OH with Q and 3-MeQ consisted of an absorption band with λmax = 470 nm assigned to the OH-adducts on the benzene ring, and a second band with λmax = 390 nm (for Q) and 370 nm (for 3-MeQ) assigned, inter alia, to the N-centered radicals on a pyrazin-2-one ring. The rate constants of the reactions of •OH with Q and 3-MeQ were found to be in the interval (5.9-9.7) × 109 M-1·s-1 and were assigned to their addition to benzene and pyrazin-2-one rings and H-abstraction from the pyrazin-2-one nitrogen. In turn, the transient absorption spectrum observed in the reaction of •N3 exhibits an absorption band with λmax = 350 nm. This absorption was assigned to the N-centered radical on the Pyr ring formed after deprotonation of the respective radical cation resulting from one-electron oxidation of 3-MeQ. The rate constant of the reaction of •N3 with 3 MeQ was found to be (6.0 ± 0.5) × 109 M-1·s-1. Oxidation of 3-MeQ by •N3 and Pyr by •OH and •N3 confirms earlier spectral assignments. With the rate constant of the •OH radical with Pyr (k = 9.2 ± 0.2) × 109 M-1·s‒1, a primary distribution of the •OH attack was estimated nearly equal between benzene and pyrazin-2-one rings.

[Spectral analysis of transient species of quinoline degradation].

PubMed

Wang, Shi-Long; Zhu, Da-Zhang; Sun, Xiao-Yu; Shi, Jun; Ni, Ya-Ming; Wang, Wen-Feng; Yao, Si-De

2006-08-01

Quinoline's degradation was studied by pulse radiolysis. It was found that hydrated electron, hydrogen radical, hydroxyl radical and SO4*- can react with quinoline. The absorption spectra of the transient species of quinoline were obtained, and related constants were determined, but it was found that the species of Br2*- and N3*- can't react with quinoline. The results give us some advices for studing the degradation of quinoline.

Capturing local structure modulations of photoexcited BiVO4 by ultrafast transient XAFS.

PubMed

Uemura, Yohei; Kido, Daiki; Koide, Akihiro; Wakisaka, Yuki; Niwa, Yasuhiro; Nozawa, Shunsuke; Ichiyanagi, Kohei; Fukaya, Ryo; Adachi, Shin-Ichi; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yabashi, Makina; Hatada, Keisuke; Iwase, Akihide; Kudo, Akihiko; Takakusagi, Satoru; Yokoyama, Toshihiko; Asakura, Kiyotaka

2017-06-29

Ultrafast excitation of photocatalytically active BiVO 4 was characterized by femto- and picosecond transient X-ray absorption fine structure spectroscopy. An initial photoexcited state (≪500 fs) changed to a metastable state accompanied by a structural change with a time constant of ∼14 ps. The structural change might stabilize holes on oxygen atoms since the interaction between Bi and O increases.

FE K EMISSION AND ABSORPTION FEATURES IN THE XMM-EPIC SPECTRUM OF THE SEYFERT GALAXY IC 4329A

NASA Technical Reports Server (NTRS)

Markowitz, A.; Reeves, J. N.; Braito, V.

2001-01-01

We present a re-analysis of the XMM-Newton long-look of the X-ray bright Seyfert galaxy IC 4329a. The Fe K bandpass is dominated by two peaks, consistent with emission from neutral or near-neutral Fe Ka and KP. A relativistic diskline model whereby both peaks are the result of one doubly-peaked diskline profile is found to be a poor description of the data. Models using two relativistic disklines are found to describe the emission profile well. A low-inclination, moderately-relativistic dual-diskline model is possible if the contribution from narrow components, due to distant material, is small or absent. A high-inclination, moderately relativistic profile for each peak is possible if there are roughly equal contributions from both the broad and narrow components. Upper limits on Fe XXV and Fe XXVI emission and absorption at the systemic velocity of IC 4329a are obtained. We also present the results of RXTE monitoring of this source obtained so far; the combined XMM-Newton and RXTE data sets allow us to explore the time-resolved spectral behavior of this source on time scales ranging from hours to 2 years. We find no strong evidence for variability of the Fe Ka emission line on any time scale probed, likely due to the minimal level of continuum variability. We detect a narrow absorption line, at a energy of 7.68 keV in the rest frame of the source; its significance has been confirmed using Monte Carlo simulations. This feature is most likely due to absorption from Fe XXVI blueshifted to approximately 0.1c relative to the systemic velocity, making IC 4329a the lowest-redshift AGN known with a high-velocity, highly-ionized outflow component. As is often the case with similar outflows seen in high-luminosity quasars, the estimated mass outflow rate is larger than the inflow accretion rate, signaling that the outflow represents a substantial portion of the total energy budget of the AGN. The outflow could arise from a radiatively-driven disk wind, or it may be in the form of a discrete, transient blob of ejected material.

Weak Fault Feature Extraction of Rolling Bearings Based on an Improved Kurtogram.

PubMed

Chen, Xianglong; Feng, Fuzhou; Zhang, Bingzhi

2016-09-13

Kurtograms have been verified to be an efficient tool in bearing fault detection and diagnosis because of their superiority in extracting transient features. However, the short-time Fourier Transform is insufficient in time-frequency analysis and kurtosis is deficient in detecting cyclic transients. Those factors weaken the performance of the original kurtogram in extracting weak fault features. Correlated Kurtosis (CK) is then designed, as a more effective solution, in detecting cyclic transients. Redundant Second Generation Wavelet Packet Transform (RSGWPT) is deemed to be effective in capturing more detailed local time-frequency description of the signal, and restricting the frequency aliasing components of the analysis results. The authors in this manuscript, combining the CK with the RSGWPT, propose an improved kurtogram to extract weak fault features from bearing vibration signals. The analysis of simulation signals and real application cases demonstrate that the proposed method is relatively more accurate and effective in extracting weak fault features.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laycock, Silas; Cappallo, Rigel; Oram, Kathleen

We report the discovery of a large amplitude (factor of ∼100) X-ray transient (IC 10 X-2, CXOU J002020.99+591758.6) in the nearby dwarf starburst galaxy IC 10 during our Chandra monitoring project. Based on the X-ray timing and spectral properties, and an optical counterpart observed with Gemini, the system is a high-mass X-ray binary consisting of a luminous blue supergiant and a neutron star. The highest measured luminosity of the source was 1.8 × 10{sup 37} erg s{sup –1}during an outburst in 2003. Observations before, during, and after a second outburst in 2010 constrain the outburst duration to be less thanmore » 3 months (with no lower limit). The X-ray spectrum is a hard power law (Γ = 0.3) with fitted column density (N{sub H} = 6.3 × 10{sup 21} atom cm{sup –2}), consistent with the established absorption to sources in IC 10. The optical spectrum shows hydrogen Balmer lines strongly in emission at the correct blueshift (-340 km s{sup –1}) for IC 10. The N III triplet emission feature is seen, accompanied by He II [4686] weakly in emission. Together these features classify the star as a luminous blue supergiant of the OBN subclass, characterized by enhanced nitrogen abundance. Emission lines of He I are seen, at similar strength to Hβ. A complex of Fe II permitted and forbidden emission lines are seen, as in B[e] stars. The system closely resembles galactic supergiant fast X-ray transients, in terms of its hard spectrum, variability amplitude, and blue supergiant primary.« less

Ultrafast laser control of autoionizing resonances observed in attosecond transient absorption

NASA Astrophysics Data System (ADS)

Liao, Chen-Ting; Harkema, Nathan; Sandhu, Arvinder

2017-04-01

Attosecond and femtosecond extreme ultraviolet (XUV) pulses can be used to probe electron dynamics in high-lying excited states that autoionize on a femtosecond timescale, thus providing information on the process of Auger decay and its interference with the continua. Here we utilize XUV pulses in connection with infrared (IR) pulses to perform attosecond transient absorption spectroscopy of the impulsive response of argon autoionizing Rydberg states in the vicinity of the 3s-1 4 p resonance. We show that by tuning the time delay and field polarization of IR pulse, it is possible to control the dipolar coupling between neighboring states and hence the spectral line shape of the resonance, such as the transition between Breit-Wigner to Beutler-Fano profiles. NSF Grant No. PHY-1505556.

On some control problems of dynamic of reactor

NASA Astrophysics Data System (ADS)

Baskakov, A. V.; Volkov, N. P.

2017-12-01

The paper analyzes controllability of the transient processes in some problems of nuclear reactor dynamics. In this case, the mathematical model of nuclear reactor dynamics is described by a system of integro-differential equations consisting of the non-stationary anisotropic multi-velocity kinetic equation of neutron transport and the balance equation of delayed neutrons. The paper defines the formulation of the linear problem on control of transient processes in nuclear reactors with application of spatially distributed actions on internal neutron sources, and the formulation of the nonlinear problems on control of transient processes with application of spatially distributed actions on the neutron absorption coefficient and the neutron scattering indicatrix. The required control actions depend on the spatial and velocity coordinates. The theorems on existence and uniqueness of these control actions are proved in the paper. To do this, the control problems mentioned above are reduced to equivalent systems of integral equations. Existence and uniqueness of the solution for this system of integral equations is proved by the method of successive approximations, which makes it possible to construct an iterative scheme for numerical analyses of transient processes in a given nuclear reactor with application of the developed mathematical model. Sufficient conditions for controllability of transient processes are also obtained. In conclusion, a connection is made between the control problems and the observation problems, which, by to the given information, allow us to reconstruct either the function of internal neutron sources, or the neutron absorption coefficient, or the neutron scattering indicatrix....

Impulsive Collision Dynamics of CO Super Rotors from an Optical Centrifuge.

PubMed

Murray, Matthew J; Ogden, Hannah M; Toro, Carlos; Liu, Qingnan; Mullin, Amy S

2016-11-18

We report state-resolved collision dynamics for CO molecules prepared in an optical centrifuge and measured with high-resolution transient IR absorption spectroscopy. Time-resolved polarization-sensitive measurements of excited CO molecules in the J=29 rotational state reveal that the oriented angular momentum of CO rotors is relaxed by impulsive collisions. The translational energy gains for molecules in the initial plane of rotation are threefold larger than for randomized angular momentum orientations, indicating the presence of anisotropic kinetic energy. The transient data show enhanced population for CO molecules in the initial plane of rotation immediately following the optical centrifuge pulse. A comparison with previous CO 2 super rotor studies illustrates the behavior of molecular gyroscopes; spatial reorientation of CO 2 J=76 rotors takes substantially longer than that for CO J=29 rotors, despite similarities in classical rotational period and rotational energy gap. High-resolution transient IR absorption measurements of the CO J=29-39 rotational states show that the collisional depopulation rates increase with J quantum number. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tracking Co(I) Intermediate in operando in Photocatalytic Hydrogen Evolution by X-ray transient Absorption Spectroscopy and DFT Calculation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhi-Jun; Zhan, Fei; Xiao, Hongyan

X-ray transient absorption spectroscopy (XTA) and optical transient spectroscopy (OTA) were used to probe the Co(I) intermediate generated in situ from an aqueous photocatalytic hydrogen evolution system, with [RuII(bpy)3]Cl2·6H2O as the photosensitizer, ascorbic acid/ascorbate as the electron donor, and the Co-polypyridyl complex ([CoII(DPABpy) Cl]Cl) as the pre-catalyst. Upon exposure to light, the XTA measured at Co K-edge visualizes the grow and decay of the Co(I) intermediate, and reveals its Co-N bond contraction of 0.09 ± 0.03 Å. Density functional theory (DFT) calculations support the bond contraction and illustrate that the metal-to-ligand π back-bonding greatly stabilizes the penta-coordinated Co(I) intermediate, whichmore » provides easy photon access. To the best of our knowledge, this is the first example of capturing the penta-coordinated Co(I) intermediate in operando with bond contraction by XTA, thereby providing new insights for fundamental understanding of structure– function relationship of cobalt-based molecular catalysts.« less

Pump and probe spectroscopy with continuous wave quantum cascade lasers.

PubMed

Kirkbride, James M R; Causier, Sarah K; Dalton, Andrew R; Weidmann, Damien; Ritchie, Grant A D

2014-02-07

This paper details infra-red pump and probe studies on nitric oxide conducted with two continuous wave quantum cascade lasers both operating around 5 μm. The pump laser prepares a velocity selected population in a chosen rotational quantum state of the v = 1 level which is subsequently probed using a second laser tuned to a rotational transition within the v = 2 ← v = 1 hot band. The rapid frequency scan of the probe (with respect to the molecular collision rate) in combination with the velocity selective pumping allows observation of marked rapid passage signatures in the transient absorption profiles from the polarized vibrationally excited sample. These coherent transient signals are influenced by the underlying hyperfine structure of the pump and probe transitions, the sample pressure, and the coherent properties of the lasers. Pulsed pump and probe studies show that the transient absorption signals decay within 1 μs at 50 mTorr total pressure, reflecting both the polarization and population dephasing times of the vibrationally excited sample. The experimental observations are supported by simulation based upon solving the optical Bloch equations for a two level system.

Analytical solution of the transient temperature profile in gain medium of passively Q-switched microchip laser.

PubMed

Han, Xiahui; Li, Jianlang

2014-11-01

The transient temperature evolution in the gain medium of a continuous wave (CW) end-pumped passively Q-switched microchip (PQSM) laser is analyzed. By approximating the time-dependent population inversion density as a sawtooth function of time and treating the time-dependent pump absorption of a CW end-pumped PQSM laser as the superposition of an infinite series of short pumping pulses, the analytical expressions of transient temperature evolution and distribution in the gain medium for four- and three-level laser systems, respectively, are given. These analytical solutions are applied to evaluate the transient temperature evolution and distribution in the gain medium of CW end-pumped PQSM Nd:YAG and Yb:YAG lasers.

Picosecond absorption spectroscopy of self-trapped excitons and transient Ce states in LaBr3 and LaBr3:Ce

NASA Astrophysics Data System (ADS)

Li, Peiyun; Gridin, Sergii; Ucer, K. Burak; Williams, Richard T.; Menge, Peter R.

2018-04-01

Picosecond time-resolved optical absorption spectra induced by two-photon interband excitation of LaBr3 are reported. The spectra are similar in general characteristics to self-trapped exciton (STE) absorption previously measured in alkali halides and alkaline-earth halides. A broad ultraviolet absorption band results from excitation of the self-trapped hole within the STE. A series of infrared and red-visible bands results from excitation of the bound outer electron within the STE similar to bands found in alkali halides corresponding to different degrees of "off-center" relaxation. Induced absorption in cerium-doped LaBr3 after band-gap excitation of the host exhibits similar STE spectra, except it decays faster on the tens-of-picoseconds scale in proportion to the Ce concentration. This is attributed to dipole-dipole energy transfer from STE to Ce3 + dopant ions. The absorption spectra were also measured after direct excitation of the Ce3 + ions with sufficient intensity to drive two- and three-photon resonantly enhanced excitation. In this case, the spectrum attributed to STEs created adjacent to Ce3 + ions decays in 1 ps suggesting dipole-dipole transfer from the nearest-neighbor separation. A transient absorption band at 2.1 eV growing with Ce concentration is found and attributed to a charge-transfer excitation of the Ce3 +* excited state responsible for scintillation in LaBr3:Ce crystals. This study concludes that the energy transport from host to activator responsible for the scintillation of LaBr3:Ce proceeds by STE creation and dipole-dipole transfer more than by sequential trapping of holes and electrons on Ce3 + ions.

Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra.

PubMed

Vilas, F; Gaffey, M J

1989-11-10

Absorption features having depths up to 5% are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

Phyllosilicate absorption features in main-belt and outer-belt asteroid reflectance spectra

NASA Technical Reports Server (NTRS)

Vilas, Faith; Gaffey, Michael J.

1989-01-01

Absorption features having depths up to 5 percent are identified in high-quality, high-resolution reflectance spectra of 16 dark asteroids in the main belt and in the Cybele and Hilda groups. Analogs among the CM2 carbonaceous chondrite meteorites exist for some of these asteroids, suggesting that these absorptions are due to iron oxides in phyllosilicates formed on the asteroidal surfaces by aqueous alteration processes. Spectra of ten additional asteroids, located beyond the outer edge of the main belt, show no discernible absorption features, suggesting that aqueous alteration did not always operate at these heliocentric distances.

Fluence-dependent singlet exciton dynamics in length-sorted chirality-enriched single-walled carbon nanotubes.

PubMed

Park, Jaehong; Deria, Pravas; Olivier, Jean-Hubert; Therien, Michael J

2014-02-12

We utilize individualized, length-sorted (6,5)-chirality enriched single-walled carbon nanotubes (SWNTs) having dimensions of 200 and 800 nm, femtosecond transient absorption spectroscopy, and variable excitation fluences that modulate the exciton density per nanotube unit length, to interrogate nanotube exciton/biexciton dynamics. For pump fluences below 30 μJ/cm(2), transient absorption (TA) spectra of (6,5) SWNTs reveal the instantaneous emergence of the exciton to biexciton transition (E11 → E11,BX) at 1100 nm; in contrast, under excitation fluences exceeding 100 μJ/cm(2), this TA signal manifests a rise time (τ rise ∼ 250 fs), indicating that E11 state repopulation is required to produce this signal. Femtosecond transient absorption spectroscopic data acquired over the 900-1400 nm spectral region of the near-infrared (NIR) region for (6,5) SWNTs, as a function of nanotube length and exciton density, reveal that over time delays that exceed 200 fs exciton-exciton interactions do not occur over spatial domains larger than 200 nm. Furthermore, the excitation fluence dependence of the E11 → E11,BX transient absorption signal demonstrates that relaxation of the E11 biexciton state (E11,BX) gives rise to a substantial E11 state population, as increasing delay times result in a concomitant increase of E11 → E11,BX transition oscillator strength. Numerical simulations based on a three-state model are consistent with a mechanism whereby biexcitons are generated at high excitation fluences via sequential SWNT ground- and E11-state excitation that occurs within the 980 nm excitation pulse duration. These studies that investigate fluence-dependent TA spectral evolution show that SWNT ground → E11 and E11 → E11,BX excitations are coresonant and provide evidence that E11,BX → E11 relaxation constitutes a significant decay channel for the SWNT biexciton state over delay times that exceed 200 fs, a finding that runs counter to assumptions made in previous analyses of SWNT biexciton dynamical data where exciton-exciton annihilation has been assumed to play a dominant role.

The co-existence of hot and cold gas in debris discs

NASA Astrophysics Data System (ADS)

Rebollido, I.; Eiroa, C.; Montesinos, B.; Maldonado, J.; Villaver, E.; Absil, O.; Bayo, A.; Canovas, H.; Carmona, A.; Chen, Ch.; Ertel, S.; Garufi, A.; Henning, Th.; Iglesias, D. P.; Launhardt, R.; Liseau, R.; Meeus, G.; Moór, A.; Mora, A.; Olofsson, J.; Rauw, G.; Riviere-Marichalar, P.

2018-06-01

Context. Debris discs have often been described as gas-poor discs as the gas-to-dust ratio is expected to be considerably lower than in primordial, protoplanetary discs. However, recent observations have confirmed the presence of a non-negligible amount of cold gas in the circumstellar (CS) debris discs around young main-sequence stars. This cold gas has been suggested to be related to the outgassing of planetesimals and cometary-like objects. Aims: The goal of this paper is to investigate the presence of hot gas in the immediate surroundings of the cold-gas-bearing debris-disc central stars. Methods: High-resolution optical spectra of all currently known cold-gas-bearing debris-disc systems, with the exception of β Pic and Fomalhaut, have been obtained from La Palma (Spain), La Silla (Chile), and La Luz (Mexico) observatories. To verify the presence of hot gas around the sample of stars, we have analysed the Ca II H&K and the Na I D lines searching for non-photospheric absorptions of CS origin, usually attributed to cometary-like activity. Results: Narrow, stable Ca II and/or Na I absorption features have been detected superimposed to the photospheric lines in 10 out of the 15 observed cold-gas-bearing debris-disc stars. Features are found at the radial velocity of the stars, or slightly blue- or red-shifted, and/or at the velocity of the local interstellar medium (ISM). Some stars also present transient variable events or absorptions extended towards red wavelengths (red wings). These are the first detections of such Ca II features in 7 out of the 15 observed stars. Although an ISM origin cannot categorically be excluded, the results suggest that the stable and variable absorptions arise from relatively hot gas located in the CS close-in environment of the stars. This hot gas is detected in at least 80%, of edge-on cold-gas-bearing debris discs, while in only 10% of the discs seen close to face-on. We interpret this result as a geometrical effect, and suggest that the non-detection of hot gas absorptions in some face-on systems is due to the disc inclination and likely not to the absence of the hot-gas component. This gas is likely released in physical processes related in some way to the evaporation of exocomets, evaporation of dust grains, or grain-grain collisions close to the central star. The reduced spectra are only available at the CDS (ascii files) and at the FEROS archive (FITS files) via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A3

Laser photolysis studies of ω-bond dissociation in aromatic carbonyls with a C-C triple bond stimulated by triplet sensitization.

PubMed

Yamaji, Minoru; Horimoto, Ami; Marciniak, Bronislaw

2017-07-14

We have prepared three types of carbonyl compounds, benzoylethynylmethyl phenyl sulfide (2@SPh), (p-benzoyl)phenylethynylmethyl phenyl sulfide (3@SPh) and p-(benzoylethynyl)benzyl phenyl sulfide (4@SPh) with benzoyl and phenylthiylmethyl groups, which are interconnected with a C-C triple bond and a phenyl ring. Laser flash photolysis of 3@SPh and 4@SPh in acetonitrile provided the transient absorption spectra of the corresponding triplet states where no chemical reactions were recognized. Upon laser flash photolysis of 2@SPh, the absorption band due to the phenylthiyl radical (PTR) was obtained, indicating that the C-S bond cleaved in the excited state. Triplet sensitization of these carbonyl compounds using acetone and xanthone was conducted using laser photolysis techniques. The formation of triplet 3@SPh was seen in the transient absorption, whereas the PTR formation was observed for 2@SPh and 4@SPh, indicating that the triplet states were reactive for the C-S bond dissociation. The C-S bond dissociation mechanism for 4@SPh upon triplet sensitization is discussed in comparison with those for 2@SPh and 3@SPh.

Storage of feature conjunctions in transient auditory memory.

PubMed

Gomes, H; Bernstein, R; Ritter, W; Vaughan, H G; Miller, J

1997-11-01

The purpose of this study was to determine whether feature conjunctions are stored in transient auditory memory. The mismatch negativity (MMN), an event-related potential that is elicited by stimuli that differ from a series of preceding stimuli, was used in this endeavour. A tone that differed from the preceding series of stimuli in the conjunction of two of its features, both present in preceding stimuli but in different combinations, was found to elicit the MMN. The data are interpreted to indicate that information about the conjunction of features is stored in the memory.

Interstellar silicate dust in the z = 0.685 absorber toward TXS 0218+357

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aller, Monique C.; Kulkarni, Varsha P.; Liger, Nicholas

2014-04-10

We report the detection of interstellar silicate dust in the z {sub abs} = 0.685 absorber along the sightline toward the gravitationally lensed blazar TXS 0218+357. Using Spitzer Space Telescope Infrared Spectrograph data, we detect the 10 μm silicate absorption feature with a detection significance of 10.7σ. We fit laboratory-derived silicate dust profile templates obtained from the literature to the observed 10 μm absorption feature and find that the best single-mineral fit is obtained using an amorphous olivine template with a measured peak optical depth of τ{sub 10} = 0.49 ± 0.02, which rises to τ{sub 10} ∼ 0.67 ±more » 0.04 if the covering factor is taken into account. We also detected the 18 μm silicate absorption feature in our data with a >3σ significance. Due to the proximity of the 18 μm absorption feature to the edge of our covered spectral range, and associated uncertainty about the shape of the quasar continuum normalization near 18 μm, we do not independently fit this feature. We find, however, that the shape and depth of the 18 μm silicate absorption are well matched to the amorphous olivine template prediction, given the optical depth inferred for the 10 μm feature. The measured 10 μm peak optical depth in this absorber is significantly higher than those found in previously studied quasar absorption systems. However, the reddening, 21 cm absorption, and velocity spread of Mg II are not outliers relative to other studied absorption systems. This high optical depth may be evidence for variations in dust grain properties in the interstellar medium between this and the previously studied high redshift galaxies.« less

THE 3–4  μ m SPECTRA OF JUPITER TROJAN ASTEROIDS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, M. E., E-mail: mbrown@caltech.edu

To date, reflectance spectra of Jupiter Trojan asteroids have revealed no distinctive absorption features. For this reason, the surface composition of these objects remains a subject of speculation. Spectra have revealed, however, that the Jupiter Trojan asteroids consist of two distinct sub-populations that differ in the optical to near-infrared colors. The origins and compositional differences between the two sub-populations remain unclear. Here, we report the results from a 2.2–3.8 μ m spectral survey of a collection of 16 Jupiter Trojan asteroids, divided equally between the two sub-populations. We find clear spectral absorption features centered around 3.1 μ m in themore » less-red population. Additional absorption consistent with that expected from organic materials might also be present. No such features are see in the red population. A strong correlation exists between the strength of the 3.1 μ m absorption feature and the optical to near-infrared color of the objects. While, traditionally, absorptions such as these in dark asteroids are modeled as being due to fine-grain water frost, we find it physically implausible that the special circumstances required to create such fine-grained frost would exist on a substantial fraction of the Jupiter Trojan asteroids. We suggest, instead, that the 3.1 μ m absorption on Trojans and other dark asteroids could be due to N–H stretch features. Additionally, we point out that reflectivities derived from WISE observations show a strong absorption beyond 4 μ m for both populations. The continuum of 3.1 μ m features and the common absorption beyond 4 μ m might suggest that both sub-populations of Jupiter Trojan asteroids formed in the same general region of the early solar system.« less

Spatially Resolved HCN Absorption Features in the Circumnuclear Region of NGC 1052

NASA Astrophysics Data System (ADS)

Sawada-Satoh, Satoko; Roh, Duk-Gyoo; Oh, Se-Jin; Lee, Sang-Sung; Byun, Do-Young; Kameno, Seiji; Yeom, Jae-Hwan; Jung, Dong-Kyu; Kim, Hyo-Ryoung; Hwang, Ju-Yeon

2016-10-01

We present the first VLBI detection of HCN molecular absorption in the nearby active galactic nucleus NGC 1052. Utilizing the 1 mas resolution achieved by the Korean VLBI Network, we have spatially resolved the HCN absorption against a double-sided nuclear jet structure. Two velocity features of HCN absorption are detected significantly at the radial velocity of 1656 and 1719 km s-1, redshifted by 149 and 212 km s-1 with respect to the systemic velocity of the galaxy. The column density of the HCN molecule is estimated to be 1015-1016 cm-2, assuming an excitation temperature of 100-230 K. The absorption features show high optical depth localized on the receding jet side, where the free-free absorption occurred due to the circumnuclear torus. The size of the foreground absorbing molecular gas is estimated to be on approximately one-parsec scales, which agrees well with the approximate size of the circumnuclear torus. HCN absorbing gas is likely to be several clumps smaller than 0.1 pc inside the circumnuclear torus. The redshifted velocities of the HCN absorption features imply that HCN absorbing gas traces ongoing infall motion inside the circumnuclear torus onto the central engine.

The origin of blueshifted absorption features in the X-ray spectrum of PG 1211+143: outflow or disc

NASA Astrophysics Data System (ADS)

Gallo, L. C.; Fabian, A. C.

2013-07-01

In some radio-quiet active galactic nuclei (AGN), high-energy absorption features in the X-ray spectra have been interpreted as ultrafast outflows (UFOs) - highly ionized material (e.g. Fe XXV and Fe XXVI) ejected at mildly relativistic velocities. In some cases, these outflows can carry energy in excess of the binding energy of the host galaxy. Needless to say, these features demand our attention as they are strong signatures of AGN feedback and will influence galaxy evolution. For the same reason, alternative models need to be discussed and refuted or confirmed. Gallo and Fabian proposed that some of these features could arise from resonance absorption of the reflected spectrum in a layer of ionized material located above and corotating with the accretion disc. Therefore, the absorbing medium would be subjected to similar blurring effects as seen in the disc. A priori, the existence of such plasma above the disc is as plausible as a fast wind. In this work, we highlight the ambiguity by demonstrating that the absorption model can describe the ˜7.6 keV absorption feature (and possibly other features) in the quasar PG 1211+143, an AGN that is often described as a classic example of a UFO. In this model, the 2-10 keV spectrum would be largely reflection dominated (as opposed to power law dominated in the wind models) and the resonance absorption would be originating in a layer between about 6 and 60 gravitational radii. The studies of such features constitute a cornerstone for future X-ray observatories like Astro-H and Athena+. Should our model prove correct, or at least important in some cases, then absorption will provide another diagnostic tool with which to probe the inner accretion flow with future missions.

Photoinduced electron-transfer in perylenediimide triphenylamine-based dendrimers: single photon timing and femtosecond transient absorption spectroscopy.

PubMed

Fron, Eduard; Pilot, Roberto; Schweitzer, Gerd; Qu, Jianqiang; Herrmann, Andreas; Müllen, Klaus; Hofkens, Johan; Van der Auweraer, Mark; De Schryver, Frans C

2008-05-01

The excited state dynamics of two generations perylenediimide chromophores substituted in the bay area with dendritic branches bearing triphenylamine units as well as those of the respective reference compounds are investigated. Using single photon timing and multi-pulse femtosecond transient absorption experiments a direct proof of a reversible charge transfer occurring from the peripheral triphenylamine to the electron acceptor perylenediimide core is revealed. Femtosecond pump-dump-probe experiments provide evidence for the ground state dynamics by populating excited vibronic levels. It is found by the means of both techniques that the rotational isomerization of the dendritic branches occurs on a time scale that ranges up to 1 ns. This time scale of the isomerization depends on the size of the dendritic arms and is similar both in the ground and excited state.

Findings on rings and inner satellites of Saturn of Pioneer 11

NASA Astrophysics Data System (ADS)

van Allen, J. A.

1982-09-01

The introductory part of this paper gives a short account of the theory of absorption by planetary rings and satellites of energetic charged particles that are trapped in a planet's magnetic field and describes the observable consequences of such absorption processes. The previously published University of Iowa observations of absorption features during Pioneer 11's passage through Saturn's inner radiation belt on 1 September 1979 are critically reanalyzed and related to other evidence on rings and satellites inside 2.9 Saturn radii, especially that from the imaging system on Voyagers 1 and 2. It is found (a) that satellites 1979 S1, 1979 S2, and 1980 S3 are almost certainly identical; (b) that the evidence for 1979 S4 is weak to nonexistent; (c) that 1979 S5 and two other nearby absorption features and 1979 S6 and one other nearby absorption feature are probably caused by longitudinal and radial structure of Ring F and not by satellites; and (d) that absorption feature 1979 S3 at 169,200 + or - 600 km is identified with the optically observed Ring G.

Investigating a physical basis for spectroscopic estimates of leaf nitrogen concentration

USGS Publications Warehouse

Kokaly, R.F.

2001-01-01

The reflectance spectra of dried and ground plant foliage are examined for changes directly due to increasing nitrogen concentration. A broadening of the 2.1-??m absorption feature is observed as nitrogen concentration increases. The broadening is shown to arise from two absorptions at 2.054 ??m and 2.172 ??m. The wavelength positions of these absorptions coincide with the absorption characteristics of the nitrogen-containing amide bonds in proteins. The observed presence of these absorption features in the reflectance spectra of dried foliage is suggested to form a physical basis for high correlations established by stepwise multiple linear regression techniques between the reflectance of dry plant samples and their nitrogen concentration. The consistent change in the 2.1-??m absorption feature as nitrogen increases and the offset position of protein absorptions compared to those of other plant components together indicate that a generally applicable algorithm may be developed for spectroscopic estimates of nitrogen concentration from the reflectance spectra of dried plant foliage samples. ?? 2001 Published by Elsevier Science Ireland Ltd.

Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C 70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortiz, Michael; Cho, Sung; Niklas, Jens

Ultrafast photoinduced electron transfer (PIET) dynamics of a C 70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C 70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, R EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (T ET ≤ 0.4 ps) and very slow charge recombination (T CR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cmmore » -1) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C 70@COP-5 complex.« less

Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C 70 -Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium

DOE PAGES

Ortiz, Michael; Cho, Sung; Niklas, Jens; ...

2017-03-13

Ultrafast photoinduced electron transfer (PIET) dynamics of a C 70-encapsulated bisporphyrin covalent organic polyhedron hybrid (C 70@COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, R EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (T ET ≤ 0.4 ps) and very slow charge recombination (T CR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cmmore » -1) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C 70@COP-5 complex.« less

Through-Space Ultrafast Photoinduced Electron Transfer Dynamics of a C70-Encapsulated Bisporphyrin Covalent Organic Polyhedron in a Low-Dielectric Medium.

PubMed

Ortiz, Michael; Cho, Sung; Niklas, Jens; Kim, Seonah; Poluektov, Oleg G; Zhang, Wei; Rumbles, Garry; Park, Jaehong

2017-03-29

Ultrafast photoinduced electron transfer (PIET) dynamics of a C 70 -encapsulated bisporphyrin covalent organic polyhedron hybrid (C 70 @COP-5) is studied in a nonpolar toluene medium with fluorescence and transient absorption spectroscopies. This structurally rigid donor (D)-acceptor (A) molecular hybrid offers a new platform featuring conformationally predetermined cofacial D-A orientation with a fixed edge-to-edge separation, R EE (2.8 Å), without the aid of covalent bonds. Sub-picosecond PIET (τ ET ≤ 0.4 ps) and very slow charge recombination (τ CR ≈ 600 ps) dynamics are observed. The origin of these dynamics is discussed in terms of enhanced D-A coupling (V = 675 cm -1 ) and extremely small reorganization energy (λ ≈ 0.18 eV), induced by the intrinsic structural rigidity of the C 70 @COP-5 complex.

Electrically controlled crossing of energy levels in quantum dots in two-dimensional topological insulators

NASA Astrophysics Data System (ADS)

Sukhanov, Aleksei A.

2017-05-01

We study the energy spectra of bound states in quantum dots (QDs) formed by an electrostatic potential in two-dimensional topological insulator (TI) and their transformation with changes in QD depth and radius. It is found that, unlike a trivial insulator, the energy difference between the levels of the ground state and first excited state can decrease with decreasing the radius and increasing the depth of the QD so that these levels intersect under some critical condition. The crossing of the levels results in unusual features of optical properties caused by intraceneter electron transitions. In particular, it leads to significant changes of light absorption due to electron transitions between such levels and to the transient electroluminescence induced by electrical tuning of QD and TI parameters. In the case of magnetic TIs, the polarization direction of the absorbed or emitted circularly polarized light is changed due to the level crossing.

Panchromatic polymer-polymer ternary solar cells enhanced by Forster resonance energy transfer and solvent vapor annealing

DOE PAGES

Goh, Tenghooi; Sfeir, Matthew Y.; Huang, Jing -Shun; ...

2015-08-04

Thanks to the bulk-heterojunction (BHJ) feature of polymer solar cells (PSC), additional light active components can be added with ease to form ternary solar cells. This strategy has achieved great success largely due to expanded spectral response range and improved power conversion efficiency (PCE) without incurring excessive processing costs. Here, we report ternary blend polymer–polymer solar cells comprised of PTB7, P3HT, and PC71BM with PCE as high as 8.2%. Analyses of femtosecond time resolved photoluminescence and transient absorption spectroscopy data confirm that P3HT is effective in transferring energy non-radiatively by inducing excitons and prolonging their overall lifetime in PTB7. Asmore » a result, solvent vapor annealing (SVA) treatment was employed to rectify the overly-coarse morphology, thus enhancing the fill factor, reducing interfacial recombination, and boosting the PCE to 8.7%.« less

Picosecond time-resolved absorption and fluorescence dynamics in the artificial bacteriorhodopsin pigment BR6.11.

PubMed

Brack, T L; Delaney, J K; Atkinson, G H; Albeck, A; Sheves, M; Ottolenghi, M

1993-08-01

The picosecond molecular dynamics in an artificial bacteriorhodopsin (BR) pigment containing a structurally modified all-trans retinal chromphore with a six-membered ring bridging the C11=C12-C13 positions (BR6.11) are measured by picosecond transient absorption and picosecond time-resolved fluorescence spectroscopy. Time-dependent intensity and spectral changes in absorption in the 570-650-nm region are monitored for delays as long as 5 ns after the 7-ps, 573-nm excitation of BR6.11. Two intermediates, J6.11 and K6.11/1, both with enhanced absorption to the red (> 600 nm) of the BR6.11 spectrum are observed within approximately 50 ps. The J6.11 intermediate decays with a time constant of 12 +/- 3 ps to form K6.11/1. The K6.11/1 intermediate decays with an approximately 100-ps time constant to form a third intermediate, K6.11/2, which is observed through diminished 650-nm absorption (relative to that of K6.11/1). No other transient absorption changes are found during the remainder of the initial 5-ns period of the BR6.11 photoreaction. Fluorescence in the 650-900-nm region is observed from BR6.11, K6.11/1, and K6.11/2, but no emission assignable to J6.11 is found. The BR6.11 fluroescence spectrum has a approximately 725-nm maximum which is blue-shifted by approximately 15 nm relative to that of native BR-570 and is 4.2 +/- 1.5 times larger in intensity (same sample optical density). No differences in the profile of the fluorescence spectra of BR6.11 and the intermediates K6.11/1 and K6.11/2 are observed. Following ground-state depletion of the BR6.11 population, the time-resolved fluroescence intensity monitored at 725 nm increases with two time constants, 12 +/- 3 and approximately 100 ps, both of which correlate well with changes in the picosecond transient absorption data. The resonance Raman spectrum of ground-state BR6.11, measured with low-energy, 560-nm excitation, is significantly different from the spectrum of native BR-570, thus confirming that the picosecond transient absorption and picosecond time resolved fluorescence data are assignable to BR6.11 and its photoreaction alone and not to BR-570 reformed during there constitution process (<5% of the BR6.11 sample could be attributed to native BR-570).The J6.11 and K6.11 absorption and fluorescence data presented here are generally analogous to those measured for native J-625 and K-590, respectively, and therefore, the primary events in the BR6.11 photoreaction can be correlated with those in the native BR photocycle. The BR6.11 photoreaction, however, exhibits important differences including slower formation rates for J and K intermediates as well as the presence of a second K intermediate. These results demonstrate that the restricted motion in the C11=C12-C13 region of retinal found in BR6.11 does not greatly change the overall photoreaction mechanism,but does alter the rates at which processes occur.

Weak Fault Feature Extraction of Rolling Bearings Based on an Improved Kurtogram

PubMed Central

Chen, Xianglong; Feng, Fuzhou; Zhang, Bingzhi

2016-01-01

Kurtograms have been verified to be an efficient tool in bearing fault detection and diagnosis because of their superiority in extracting transient features. However, the short-time Fourier Transform is insufficient in time-frequency analysis and kurtosis is deficient in detecting cyclic transients. Those factors weaken the performance of the original kurtogram in extracting weak fault features. Correlated Kurtosis (CK) is then designed, as a more effective solution, in detecting cyclic transients. Redundant Second Generation Wavelet Packet Transform (RSGWPT) is deemed to be effective in capturing more detailed local time-frequency description of the signal, and restricting the frequency aliasing components of the analysis results. The authors in this manuscript, combining the CK with the RSGWPT, propose an improved kurtogram to extract weak fault features from bearing vibration signals. The analysis of simulation signals and real application cases demonstrate that the proposed method is relatively more accurate and effective in extracting weak fault features. PMID:27649171

Vectorial atomic magnetometer based on coherent transients of laser absorption in Rb vapor

NASA Astrophysics Data System (ADS)

Lenci, L.; Auyuanet, A.; Barreiro, S.; Valente, P.; Lezama, A.; Failache, H.

2014-04-01

We have designed and tested an atomic vectorial magnetometer based on the analysis of the coherent oscillatory transients in the transmission of resonant laser light through a Rb vapor cell. We show that the oscillation amplitudes at the Larmor frequency and its first harmonic are related through a simple formula to the angles determining the orientation of the magnetic field vector. The magnetometer was successfully applied to the measurement of the ambient magnetic field.

Observing and understanding the ultrafast photochemistry in small molecules: applications to sunscreens.

PubMed

Baker, Lewis A; Stavros, Vasilios G

2016-09-01

In this review, we discuss the importance of biological and artificial photoprotection against overexposure to harmful ultraviolet radiation. Transient electronic and transient vibrational absorption spectroscopies are highlighted as important tools in understanding the energy transfer in small molecules, with a focus on the application to commercial sunscreens with representative examples given. Oxybenzone, a common ingredient in commercial sunscreens and sinapoyl malate, a biological sunscreen in plant leaves are presented as case studies.

Detailed transient heme structures of Mb-CO in solution after CO dissociation: an X-ray transient absorption spectroscopic study.

PubMed

Stickrath, Andrew B; Mara, Michael W; Lockard, Jenny V; Harpham, Michael R; Huang, Jier; Zhang, Xiaoyi; Attenkofer, Klaus; Chen, Lin X

2013-04-25

Although understanding the structural dynamics associated with ligand photodissociation is necessary in order to correlate structure and function in biological systems, few techniques are capable of measuring the ultrafast dynamics of these systems in solution-phase at room temperature. We present here a detailed X-ray transient absorption (XTA) study of the photodissociation of CO-bound myoglobin (Fe(II)CO-Mb) in room-temperature aqueous buffer solution with a time resolution of 80 ps, along with a general procedure for handling biological samples under the harsh experimental conditions that transient X-ray experiments entail. The XTA spectra of (Fe(II)CO-Mb) exhibit significant XANES and XAFS alterations following 527 nm excitation, which remain unchanged for >47 μs. These spectral changes indicate loss of the CO ligand, resulting in a five-coordinate, domed heme, and significant energetic reorganization of the 3d orbitals of the Fe center. With the current experimental setup, each X-ray pulse in the pulse train, separated by ~153 ns, can be separately discriminated, yielding snapshots of the myoglobin evolution over time. These methods can be easily applied to other biological systems, allowing for simultaneous structural and electronic measurements of any biological system with both ultrafast and slow time resolutions, effectively mapping out all of the samples' relevant physiological processes.

Triplet-State Dissolved Organic Matter Quantum Yields and Lifetimes from Direct Observation of Aromatic Amine Oxidation.

PubMed

Schmitt, Markus; Erickson, Paul R; McNeill, Kristopher

2017-11-21

Excited triplet state chromophoric dissolved organic matter ( 3 CDOM*) is a short-lived mixture of excited-state species that plays important roles in aquatic photochemical processes. Unlike the study of the triplet states of well-defined molecules, which are amenable to transient absorbance spectroscopy, the study of 3 CDOM* is hampered by it being a complex mixture and its low average intersystem crossing quantum yield (Φ ISC ). This study is an alternative approach to investigating 3 CDOM* using transient absorption laser spectroscopy. The radical cation of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD), formed through oxidation by 3 CDOM*, was directly observable by transient absorption spectroscopy and was used to probe basic photophysical properties of 3 CDOM*. Quenching and control experiments verified that TMPD •+ was formed from 3 CDOM* under anoxic conditions. Model triplet sensitizers with a wide range of excited triplet state reduction potentials and CDOM oxidized TMPD at near diffusion-controlled rates. This gives support to the idea that a large cross-section of 3 CDOM* moieties are able to oxidize TMPD and that the complex mixture of 3 CDOM* can be simplified to a single signal. Using the TMPD •+ transient, the natural triplet lifetime and Φ ISC for different DOM isolates and natural waters were quantified; values ranged from 12 to 26 μs and 4.1-7.8%, respectively.

Observation of two distinct negative trions in tungsten disulfide monolayers

NASA Astrophysics Data System (ADS)

Boulesbaa, Abdelaziz; Huang, Bing; Wang, Kai; Lin, Ming-Wei; Mahjouri-Samani, Masoud; Rouleau, Christopher; Xiao, Kai; Yoon, Mina; Sumpter, Bobby; Puretzky, Alexander; Geohegan, David

2015-09-01

Ultrafast pump-probe spectroscopy of two-dimensional tungsten disulfide monolayers (2 D W S2) grown on sapphire substrates revealed two transient absorption spectral peaks that are attributed to distinct negative trions at ˜2.02 eV (T1) and ˜1.98 eV (T2) . The dynamics measurements indicate that trion formation by the probe is enabled by photodoped 2D WS2 crystals with electrons remaining after trapping of holes from excitons or free electron-hole pairs at defect sites in the crystal or on the substrate. Dynamics of the characteristic absorption bands of excitons XA and XB at ˜2.03 and ˜2.40 eV , respectively, were separately monitored and compared to the photoinduced absorption features. Selective excitation of the lowest exciton level XA using λpump<2.4 eV forms only trion T1, implying that the electron remaining from dissociation of exciton XA is involved in the creation of this trion with a binding energy ˜10 meV with respect to XA. The absorption peak corresponding to trion T2 appears when λpump<2.4 eV , which is just sufficient to excite exciton XB. The dynamics of trion T2 formation are found to correlate with the disappearance of the bleach of the XB exciton, indicating the involvement of holes participating in the bleach dynamics of exciton XB. Static electrical-doping photoabsorption measurements confirm the presence of an induced absorption peak similar to that of T2. Since the proposed trion formation process here involves exciton dissociation through hole trapping by defects in the 2D crystal or substrate, this discovery highlights the strong role of defects in defining optical and electrical properties of 2D metal chalcogenides, which is relevant to a broad spectrum of basic science and technological applications.

Mediterranean Workshop and Topical Meeting. Novel Optical Materials and Applications NOMA 󈧅 (5th) Held in Cetraro (Italy) on May 20-26, 2001

DTIC Science & Technology

2002-09-12

low power dissipation, and low cost. Excited state absorption and reorientation in polymethine and squarylium dyes . David J. Hagana, Olga V...describe a detailed theoretical and experimental study of the excited states of polymethine and squarylium dyes . Picosecond, polarization-resolved...transient absorption and anisotropy excitation measurements were performed in several polymethine and squarylium dyes in ethanol solutions and

Excitation energy dependence of excited states dynamics in all- trans-carotenes determined by femtosecond absorption and fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Kosumi, Daisuke; Yanagi, Kazuhiro; Nishio, Tomohiro; Hashimoto, Hideki; Yoshizawa, Masayuki

2005-06-01

Ultrafast relaxation kinetics in β-carotene and lycopene has been investigated by femtosecond absorption and fluorescence spectroscopies using tunable excitation pulses. The transient signals induced by the photoexcitation with larger excess energy have broader bands and longer lifetimes both in the 11Bu+and21Ag- excited states. The excess vibrational energy remains longer than several picoseconds and slows the relaxation kinetics in carotenoids.

Visual scan-path analysis with feature space transient fixation moments

NASA Astrophysics Data System (ADS)

Dempere-Marco, Laura; Hu, Xiao-Peng; Yang, Guang-Zhong

2003-05-01

The study of eye movements provides useful insight into the cognitive processes underlying visual search tasks. The analysis of the dynamics of eye movements has often been approached from a purely spatial perspective. In many cases, however, it may not be possible to define meaningful or consistent dynamics without considering the features underlying the scan paths. In this paper, the definition of the feature space has been attempted through the concept of visual similarity and non-linear low dimensional embedding, which defines a mapping from the image space into a low dimensional feature manifold that preserves the intrinsic similarity of image patterns. This has enabled the definition of perceptually meaningful features without the use of domain specific knowledge. Based on this, this paper introduces a new concept called Feature Space Transient Fixation Moments (TFM). The approach presented tackles the problem of feature space representation of visual search through the use of TFM. We demonstrate the practical values of this concept for characterizing the dynamics of eye movements in goal directed visual search tasks. We also illustrate how this model can be used to elucidate the fundamental steps involved in skilled search tasks through the evolution of transient fixation moments.

SPATIALLY RESOLVED HCN ABSORPTION FEATURES IN THE CIRCUMNUCLEAR REGION OF NGC 1052

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sawada-Satoh, Satoko; Roh, Duk-Gyoo; Oh, Se-Jin

We present the first VLBI detection of HCN molecular absorption in the nearby active galactic nucleus NGC 1052. Utilizing the 1 mas resolution achieved by the Korean VLBI Network, we have spatially resolved the HCN absorption against a double-sided nuclear jet structure. Two velocity features of HCN absorption are detected significantly at the radial velocity of 1656 and 1719 km s{sup −1}, redshifted by 149 and 212 km s{sup −1} with respect to the systemic velocity of the galaxy. The column density of the HCN molecule is estimated to be 10{sup 15}–10{sup 16} cm{sup −2}, assuming an excitation temperature ofmore » 100–230 K. The absorption features show high optical depth localized on the receding jet side, where the free–free absorption occurred due to the circumnuclear torus. The size of the foreground absorbing molecular gas is estimated to be on approximately one-parsec scales, which agrees well with the approximate size of the circumnuclear torus. HCN absorbing gas is likely to be several clumps smaller than 0.1 pc inside the circumnuclear torus. The redshifted velocities of the HCN absorption features imply that HCN absorbing gas traces ongoing infall motion inside the circumnuclear torus onto the central engine.« less

Tuning the Direction of Intramolecular Charge Transfer and the Nature of the Fluorescent State in a T-Shaped Molecular Dyad.

PubMed

Felouat, Abdellah; D'Aléo, Anthony; Charaf-Eddin, Azzam; Jacquemin, Denis; Le Guennic, Boris; Kim, Eunsun; Lee, Kwang Jin; Woo, Jae Heun; Ribierre, Jean-Charles; Wu, Jeong Weon; Fages, Frédéric

2015-06-18

Controlling photoinduced intramolecular charge transfer at the molecular scale is key to the development of molecular devices for nanooptoelectronics. Here, we describe the design, synthesis, electronic characterization, and photophysical properties of two electron donor-acceptor molecular systems that consist of tolane and BF2-containing curcuminoid chromophoric subunits connected in a T-shaped arrangement. The two π-conjugated segments intersect at the electron acceptor dioxaborine core. From steady-state electronic absorption and fluorescence emission, we find that the photophysics of the dialkylamino-substituted analogue is governed by the occurrence of two closely lying excited states. From DFT calculations, we show that excitation in either of these two states results in a distinct shift of the electron density, whether it occurs along the curcuminoid or tolane moiety. Femtosecond transient absorption spectroscopy confirmed these findings. As a consequence, the nature of the emitting state and the photophysical properties are strongly dependent on solvent polarity. Moreover, these characteristics can also be switched by protonation or complexation at the nitrogen atom of the amino group. These features set new approaches toward the construction of a three-terminal molecular system in which the lateral branch would transduce a change of electronic state and ultimately control charge transport in a molecular-scale device.

Rapid-Response Low Infrared Emission Broadband Ultrathin Plasmonic Light Absorber

PubMed Central

Tagliabue, Giulia; Eghlidi, Hadi; Poulikakos, Dimos

2014-01-01

Plasmonic nanostructures can significantly advance broadband visible-light absorption, with absorber thicknesses in the sub-wavelength regime, much thinner than conventional broadband coatings. Such absorbers have inherently very small heat capacity, hence a very rapid response time, and high light power-to-temperature sensitivity. Additionally, their surface emissivity can be spectrally tuned to suppress infrared thermal radiation. These capabilities make plasmonic absorbers promising candidates for fast light-to-heat applications, such as radiation sensors. Here we investigate the light-to-heat conversion properties of a metal-insulator-metal broadband plasmonic absorber, fabricated as a free-standing membrane. Using a fast IR camera, we show that the transient response of the absorber has a characteristic time below 13 ms, nearly one order of magnitude lower than a similar membrane coated with a commercial black spray. Concurrently, despite the small thickness, due to the large absorption capability, the achieved absorbed light power-to-temperature sensitivity is maintained at the level of a standard black spray. Finally, we show that while black spray has emissivity similar to a black body, the plasmonic absorber features a very low infra-red emissivity of almost 0.16, demonstrating its capability as selective coating for applications with operating temperatures up to 400°C, above which the nano-structure starts to deform. PMID:25418040

A charge-stabilizing, multimodular, ferrocene-bis(triphenylamine)-zinc-porphyrin-fullerene polyad.

PubMed

Wijesinghe, Channa A; El-Khouly, Mohamed E; Zandler, Melvin E; Fukuzumi, Shunichi; D'Souza, Francis

2013-07-15

A novel multimodular donor-acceptor polyad featuring zinc porphyrin, fullerene, ferrocene, and triphenylamine entities was designed, synthesized, and studied as a charge-stabilizing, photosynthetic-antenna/reaction-center mimic. The ferrocene and fullerene entities, covalently linked to the porphyrin ring, were distantly separated to accomplish the charge-separation/hole-migration events leading to the creation of a long-lived charge-separated state. The geometry and electronic structures of the newly synthesized compound was deduced by B3LYP/3-21G(*) optimization, while the energy levels for different photochemical events was established using data from the optical absorption and emission, and electrochemical studies. Excitation of the triphenylamine entities revealed singlet-singlet energy transfer to the appended zinc porphyrin. As predicted from the energy levels, photoinduced electron transfer from both the singlet and triplet excited states of the zinc porphyrin to fullerene followed by subsequent hole migration involving ferrocene was witnessed from the transient absorption studies. The charge-separated state persisted for about 8.5 μs and was governed by the distance between the final charge-transfer product, that is, a species involving a ferrocenium cation and a fullerene radical anion, with additional influence from the charge-stabilizing triphenylamine entities located on the zinc-porphyrin macrocycle. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Coherent Optical Transients and Spectral Line Narrowing Phenomena in Four Wave Mixing Spectroscopies: Theoretical and Experimental Studies.

NASA Astrophysics Data System (ADS)

Dugan, Mark Allen

1990-08-01

The theoretical basis for new signal transients and spectral features generated in field correlated four wave mixing (4WM) spectroscopies is developed. Special attention is given to those signal responses that are sensitive to phase/amplitude correlation among the input driving fields and not simply their intensity correlation. Thus, the cases of incoherent broadband excitation and of coherent short pulsed excitation will be discussed and compared. Applications to the coherent Raman spectroscopies, both electronically nonresonant and fully resonant, are analyzed. Novel interferometric oscillatory behavior is exposed in terms of field-matter detuning beats and matter-matter bi-level and tri-level quantum beats. In addition new detuning resonances are found that have sub-material linewidths and lock onto the mode frequency of the driven chromophore. These spectral features are a member of a class of bichromophore resonant lineshapes arising from nonlinear mixing with correlated driving fields. The origin of such bichromophore resonances can be based on a coupling between two field-matter superposition states driven by correlated fields on separate chromophores. Analytic results are presented and modelled to anticipate the experimental results presented in a following chapter. The onset of resolvable homogeneous electronic memory is reported in room temperature solutions of dye molecules. A narrowing of the homogeneous linewidths with increasing concentration of these dye solutions is observed in sub-picosecond photon echo experiments. This effect is attributed to aggregation which results in a delocalization of the electronic states over several molecules. Ultra -fast spectral diffusion in these dye aggregates is observed in stimulated photon echo measurements. Aggregate bands, seen in the linear absorption spectrum only at high concentrations, can be probed in more dilute solutions with nonlinear four wave mixing.

Iron oxide bands in the visible and near-infrared reflectance spectra of primitive asteroids

NASA Technical Reports Server (NTRS)

Jarvis, Kandy S.; Vilas, Faith; Gaffey, Michael J.

1993-01-01

High resolution reflectance spectra of primitive asteroids (C, P, and D class and associated subclasses) have commonly revealed an absorption feature centered at 0.7 microns attributed to an Fe(2+)-Fe(3+) charge transfer transition in iron oxides and/or oxidized iron in phyllosilicates. A smaller feature identified at 0.43 microns has been attributed to an Fe(3+) spin-forbidden transition in iron oxides. In the spectra of the two main-belt primitive asteroids 368 Haidea (D) and 877 Walkure (F), weak absorption features which were centered near the location of 0.60-0.65 microns and 0.80-0.90 microns prompted a search for features at these wavelengths and an attempt to identify their origin(s). The CCD reflectance spectra obtained between 1982-1992 were reviewed for similar absorption features located near these wavelengths. The spectra of asteroids in which these absorption features have been identified are shown. These spectra are plotted in order of increasing heliocentric distance. No division of the asteroids by class has been attempted here (although the absence of these features in the anhydrous S-class asteroids, many of which have presumably undergone full heating and differentiation should be noted). For this study, each spectrum was treated as a continuum with discrete absorption features superimposed on it. For each object, a linear least squares fit to the data points defined a simple linear continuum. The linear continuum was then divided into each spectrum, thus removing the sloped continuum and permitting the intercomparison of residual spectral features.

Effect of nonlinear absorption on self focusing of short laser pulse in a plasma

NASA Astrophysics Data System (ADS)

Kumar, Ashok

2012-06-01

Paraxial theory of self focusing of short pulse laser in a plasma under transient and saturating effects of nonlinearity and nonlinear absorption is developed. The absorption is averaged over the cross-section of the beam and is different for different time segments of the pulse. The electron temperature includes cumulative effect of previous history of temporal profile of pulse intensity, however, the ambipolar diffusion is taken to be faster than the heating time. The relaxation effect causes self-distortion of the pulse temporal profile where as the nonlinear absorption weakens self focusing. For the pulses of duration comparable to the electron ion collision time, the front part of the pulse gets defocused where as the latter part undergoes periodic self focusing.

Kinetics of drug release from ointments: Role of transient-boundary layer.

PubMed

Xu, Xiaoming; Al-Ghabeish, Manar; Krishnaiah, Yellela S R; Rahman, Ziyaur; Khan, Mansoor A

2015-10-15

In the current work, an in vitro release testing method suitable for ointment formulations was developed using acyclovir as a model drug. Release studies were carried out using enhancer cells on acyclovir ointments prepared with oleaginous, absorption, and water-soluble bases. Kinetics and mechanism of drug release was found to be highly dependent on the type of ointment bases. In oleaginous bases, drug release followed a unique logarithmic-time dependent profile; in both absorption and water-soluble bases, drug release exhibited linearity with respect to square root of time (Higuchi model) albeit differences in the overall release profile. To help understand the underlying cause of logarithmic-time dependency of drug release, a novel transient-boundary hypothesis was proposed, verified, and compared to Higuchi theory. Furthermore, impact of drug solubility (under various pH conditions) and temperature on drug release were assessed. Additionally, conditions under which deviations from logarithmic-time drug release kinetics occur were determined using in situ UV fiber-optics. Overall, the results suggest that for oleaginous ointments containing dispersed drug particles, kinetics and mechanism of drug release is controlled by expansion of transient boundary layer, and drug release increases linearly with respect to logarithmic time. Published by Elsevier B.V.

Rotamer-Specific Photoisomerization of Difluorostilbenes from Transient Absorption and Transient Raman Spectroscopy.

PubMed

Quick, M; Dobryakov, A L; Ioffe, I N; Berndt, F; Mahrwald, R; Ernsting, N P; Kovalenko, S A

2018-01-25

Photoisomerization of 2,2'-, 3,3'-, and 4,4'-difluorostilbene (F2, F3, F4, respectively) in n-hexane, perfluoro-n-hexane, and acetonitrile is studied with broadband transient absorption (TA) and femtosecond stimulated Raman (FSR) spectroscopy and by DFT/TDDFT calculations. F2 and F3 possess three rotamers (rotational isomers) each, while F4 has one single conformation only. These differences are reflected in TA and FSR spectra. Thus F4 reveals a monoexponential decay of TA with τ 1 = 172 ps in n-hexane, as expected for a single species. For F2 and F3, the decays are biexponential in all solvents, corresponding to two distinctly discerned rotamers or rotamer fractions. Specifically, for F2 in n-hexane, τ 1 = 357 ps (83%) and τ 2 = 62 ps (17%), and for F3 in the same solvent, τ 1 = 222 ps (57%), and τ 2 = 81 ps (43%). The weights in brackets agree with theoretically estimated ground-state abundances of the rotamers. Furthermore, a global fit of the TA and FSR data allows us to extract the spectra of the pure rotamers. The Raman spectra of S 0 and S 1 are in qualitative agreement with calculations.

Vibrational coherence in polar solutions of Zn(II) tetrakis(N-methylpyridyl)porphyrin with Soret-band excitation: rapidly damped intermolecular modes with clustered solvent molecules and slowly damped intramolecular modes from the porphyrin macrocycle.

PubMed

Dillman, Kevin L; Shelly, Katherine R; Beck, Warren F

2009-04-30

Ground-state coherent wavepacket motions arising from intermolecular modes with clustered, first-shell solvent molecules were observed using the femtosecond dynamic absorption technique in polar solutions of Zn(II) meso-tetrakis(N-methylpyridyl)porphyrin (ZnTMPyP) with excitation in the Soret absorption band. As was observed previously in bacteriochlorophyll a solution, the pump-probe transients in ZnTMPyP solutions are weakly modulated by slowly damped (effective damping time gamma > 1 ps) features that are assigned to intramolecular modes, the skeletal normal modes of vibration of the porphyrin. The 40 cm(-1) and 215 cm(-1) modes from the metal-doming and metal-solvent-ligand modes, respectively, are members of this set of modulation components. A slowly damped 2-4 cm(-1) component is assigned to the internal rotation of the N-methylpyridyl rings with respect to the porphyrin macrocycle; this mode obtains strong resonance Raman intensity enhancement from an extensive delocalization of pi-electron density from the porphyrin in the ground state onto the rings in the pi* excited states. The dominant features observed in the pump-probe transients are a pair of rapidly damped (gamma < 250 fs) modulation components arising from intermolecular modes with solvent molecules. This structural assignment is supported by an isotope-dependent shift of the average mode frequencies in methanol and perdeuterated methanol. The solvent dependence of the mean intermolecular mode frequency is consistent with a van der Waals intermolecular potential that has significant contributions only from the London dispersion and induction interactions; ion-dipole or ion-induced-dipole terms do not make large contributions because the pi-electron density is not extensively delocalized onto the N-methylpyridyl rings. The modulation depth associated with the intermolecular modes exhibits a marked dependence on the electronic structure of the solvent that is probably related to the degree of covalency; the strongest modulations are observed in acetonitrile and dimethylsulfoxide. The results strongly support a structural assignment of the low-frequency modes that are coupled to the primary and secondary electron-transfer reactions in photosynthetic reaction centers to intermolecular modes between the redox-active chromophores and first-solvation shell groups from the surrounding protein, and an important additional function of the intermolecular modes in the stabilization of charged intermediates is suggested.

Modeling of thermoplastic composites laser welding - A ray tracing method associated to thermal simulation

NASA Astrophysics Data System (ADS)

Dauphin, Myriam; Cosson, Benoit

2016-10-01

The importance of the absorption phenomenon occurring into the semi-transparent substrate of reinforced fiber thermoplastic, during the Laser Transmission Welding process (LTW), was examined. A (3D) transient thermal model of LTW was developed. First, the energy distribution coming from the laser irradiation was assessed. Ray tracing techniques allowed us to deal with both absorption and a strong light-scattering caused by the heterogeneity of composite. Then, the energy balance equation was solved in order to study the heating stage. This paper proposes a comparison of the welding area obtained with a model for which absorption was neglected and a second model where absorption was considered. The interest to consider absorption was shown for process optimization purposes and for the use of reinforced composites colored or filled with additives.

Pseudo-transient heat transfer in vertical Bridgman crystal growth of semi-transparent materials

NASA Astrophysics Data System (ADS)

Barvinschi, F.; Nicoara, I.; Santailler, J. L.; Duffar, T.

1998-11-01

The temperature distribution and the solid-liquid interface shape during semi-transparent crystal growth have been studied by modelling a vertical Bridgman technique, using a pseudo-transient approximation in an ideal configuration. The heat transfer equation and the boundary conditions have been solved by the finite-element method. It has been pointed out that the optical absorption coefficients of the liquid and solid phases have a major effect on the thermal field, especially on the shape and location of the crystallization interface.

The origin of absorptive features in the two-dimensional electronic spectra of rhodopsin.

PubMed

Farag, Marwa H; Jansen, Thomas L C; Knoester, Jasper

2018-05-09

In rhodopsin, the absorption of a photon causes the isomerization of the 11-cis isomer of the retinal chromophore to its all-trans isomer. This isomerization is known to occur through a conical intersection (CI) and the internal conversion through the CI is known to be vibrationally coherent. Recently measured two-dimensional electronic spectra (2DES) showed dramatic absorptive spectral features at early waiting times associated with the transition through the CI. The common two-state two-mode model Hamiltonian was unable to elucidate the origin of these features. To rationalize the source of these features, we employ a three-state three-mode model Hamiltonian where the hydrogen out-of plane (HOOP) mode and a higher-lying electronic state are included. The 2DES of the retinal chromophore in rhodopsin are calculated and compared with the experiment. Our analysis shows that the source of the observed features in the measured 2DES is the excited state absorption to a higher-lying electronic state and not the HOOP mode.

Investigations on the photoreactions of phenothiazine and phenoxazine in presence of 9-cyanoanthracene by using steady state and time resolved spectroscopic techniques.

PubMed

Bardhan, Munmun; Mandal, Paulami; Tzeng, Wen-Bih; Ganguly, Tapan

2010-09-01

By using electrochemical, steady state and time resolved (fluorescence lifetime and transient absorption) spectroscopic techniques, detailed investigations were made to reveal the mechanisms of charge separation or forward electron transfer reactions within the electron donor phenothiazine (PTZH) or phenoxazine (PXZH) and well known electron acceptor 9-cyanoanthracene (CNA). The transient absorption spectra suggest that the charge separated species formed in the excited singlet state resulted from intermolecular photoinduced electron transfer reactions within the donor PTZH (or PXZH) and CNA acceptor relaxes to the corresponding triplet state. Though alternative mechanisms of via formations of contact neutral radical by H-transfer reaction have been proposed but the observed results obtained from the time resolved measurements indicate that the regeneration of ground state reactants is primarily responsible due to direct recombination of triplet contact ion-pair (CIP) or solvent-separated ion-pair (SSIP).

Electron beam irradiation induced changes in liquid-crystal compound 5CB

NASA Astrophysics Data System (ADS)

Rath, M. C.; Sarkar, S. K.; Wadhawan, V. K.; Verma, R.; Das, I. M. L.; Dąbrowski, R.; Tykarska, M.; Dhar, R.

2008-12-01

Electron beam irradiation studies on liquid crystal material 5CB have been carried out at a temperature where the compound exists in the isotropic liquid phase. In situ time-resolved spectroscopic characterization was carried out during the irradiation. Three different transients were observed during the 2-μs electron pulse. After about 50 μs, only one transient species was found to be present, which has an absorption peak at 360 nm. Radiolysed sample exhibits a broad absorption at ˜400 nm. The dielectric measurements show that even a low level of irradiation results in a dramatic increase in the component of dielectric permittivity normal to the long axes of the molecules ɛ⊥', and a corresponding decrease in the dielectric anisotropy (Δɛ'=ɛ∥'-ɛ⊥' ). These studies show that 5CB is prone to substantial radiation damage on exposure to the beam of high-energy electrons.

An Attosecond Transient Absorption Spectroscopy Setup with a Water Window Attosecond source

NASA Astrophysics Data System (ADS)

Chew, Andrew; Yin, Yanchun; Li, Jie; Ren, Xiaoming; Wang, Yang; Wu, Yi; Chang, Zenghu

2017-04-01

Attosecond transient absorption, or time-resolved pump-probe spectroscopy, are excellent tools that can be used to investigate fast electron dynamics for a given atomic or molecular system. Recent push for high energy long wavelength few cycle laser sources has resulted in the production of x-ray spectra that would allow the probing of electron dynamics at the carbon k-edge in molecules such as CH4 and CO2. The motion of charges can be caused by photo-dissociation and charge migration. We present here the first results from our experimental setup where we produce a broadband attosecond pulse with spectra that stretches into the water window. National Science Foundation (1068604), Army Research Oce (W911NF-14-1-0383), Air Force Oce of Scientic Research (FA9550-15-1-0037, FA9550-16-1-0013) and the DARPA PULSE program by a Grant from AMRDEC (W31P4Q1310017).

Ultrafast Dynamics in DNA and RNA Derivatives Monitored by Broadband Transient Absorption Spectrscopy

NASA Astrophysics Data System (ADS)

Brister, Matthew M.; Crespo-Hernández, Carlos E.

2015-06-01

The ultrafast dynamics of nucleic acids have been under scrutiny for the past couple of decades because of the role that the high-energy electronic states play in mutagenesis and carcinogenesis. Kinetic models have been proposed, based on both experimental and theoretical discoveries. Direct experimental evidence of the intersystem crossing rate and population of the triplet state for most nucleic acid bases has yet to be reported, even though the triplet state is thought to be the most reactive species. Utilizing broadband femtosecond transient absorption spectroscopy, we reveal the time scale at which singlet-to-triplet population transfer occurs in several nucleic acid derivatives in the condensed phase. The implication of these results to the current understanding of the DNA and RNA photochemistry will be discussed. The authors acknowledge the CAREER program of the National Science Foundation (Grant No. CHE-1255084) for financial support.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Beard, Matthew C; Chen, Xihan; Lu, Haipeng

The exciton binding energy in methylammonium lead iodide (MAPbI3) is about 10 meV, around 1/3 of the available thermal energy (kBT ~ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination,more » and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.« less

Thermal conductance of interfaces with molecular layers - low temperature transient absorption study on gold nanorods supported on self assembled monolayers

NASA Astrophysics Data System (ADS)

Wang, Wei; Huang, Jingyu; Murphy, Catherine; Cahill, David; University of Illinois At Urbana Champaign, Department of Materials Science; Engineering Team; Department Collaboration

2011-03-01

While heat transfer via phonons across solid-solid boundary has been a core field in condense matter physics for many years, vibrational energy transport across molecular layers has been less well elucidated. We heat rectangular-shaped gold nanocrystals (nanorods) with Ti-sapphire femtosecond pulsed laser at their longitudinal surface plasmon absorption wavelength to watch how their temperature evolves in picoseconds transient. We observed single exponential decay behavior, which suggests that the heat dissipation is only governed by a single interfacial conductance value. The ``RC'' time constant was 300ps, corresponding to a conductance value of 95MW/ m 2 K. This interfacial conductance value is also a function of ambient temperature since at temperatures as low as 80K, which are below the Debye temperature of organic layers, several phonon modes were quenched, which shut down the dominating channels that conduct heat at room temperature.

Simplification of femtosecond transient absorption microscopy data from CH3NH3PbI3 perovskite thin films into decay associated amplitude maps

NASA Astrophysics Data System (ADS)

Doughty, Benjamin; Simpson, Mary Jane; Yang, Bin; Xiao, Kai; Ma, Ying-Zhong

2016-03-01

This work aims to simplify multi-dimensional femtosecond transient absorption microscopy (TAM) data into decay associated amplitude maps (DAAMs) that describe the spatial distributions of dynamical processes occurring on various characteristic timescales. Application of this method to TAM data obtained from a model methyl-ammonium lead iodide (CH3NH3PbI3) perovskite thin film allows us to simplify the data set comprising 68 time-resolved images into four DAAMs. These maps offer a simple means to visualize the complex electronic excited-state dynamics in this system by separating distinct dynamical processes evolving on characteristic timescales into individual spatial images. This approach provides new insight into subtle aspects of ultrafast relaxation dynamics associated with excitons and charge carriers in the perovskite thin film, which have recently been found to coexist at spatially distinct locations.

Identification of effective exciton-exciton annihilation in squaraine-squaraine copolymers.

PubMed

Hader, Kilian; May, Volkhard; Lambert, Christoph; Engel, Volker

2016-05-11

Ultrafast time-resolved transient absorption spectroscopy is able to monitor the fate of the excited state population in molecular aggregates or polymers. Due to many competing decay processes, the identification of exciton-exciton annihilation (EEA) is difficult. Here, we use a microscopic model to describe exciton annihilation processes in squaraine-squaraine copolymers. Transient absorption time traces measured at different laser powers exhibit an unusual time-dependence. The analysis points towards dynamics taking place on three time-scales. Immediately after laser-excitation a localization of excitons takes place within the femtosecond time-regime. This is followed by exciton-exciton annihilation which is responsible for a fast decay of the exciton population. At later times, excitations being localized on units which are not directly connected remain so that diffusion dominates the dynamics and leads to a slower decay. We thus provide evidence for EEA tracked by time-resolved spectroscopy which has not been reported that clearly before.

The CDRH Helix-I: a physical evaluation.

PubMed

Gopal, M K; Cetas, T C

1990-01-01

The use of a resonant helical coil with predominantly axial electric fields for regional hyperthermia in the abdomen and pelvis is addressed. The Helix-I applicator, which consists of a three-turn, 36-cm-long, oval-wound helical coil measuring 60 and 43 cm along its major and minor axes, respectively, is described, and specific absorption rate (SAR) measurements for the device are reported. Measurements of the E-field are also described. Specific absorption patterns for the Helix, determined by transient temperature measurements using a gel phantom, and by E(2)-field scans using a liquid phantom, are in general agreement. The general agreement of electric power intensity distribution, inside and outside the phantom, with corresponding SAR distributions obtained from transient temperature data, ensures reliability of the distribution patterns. The E(2) contours provide a clear picture of hot and cold spots as well as the nature of the general distribution.

Probing the cytochrome c' folding landscape.

PubMed

Pletneva, Ekaterina V; Zhao, Ziqing; Kimura, Tetsunari; Petrova, Krastina V; Gray, Harry B; Winkler, Jay R

2007-11-01

The folding kinetics of R. palustris cytochrome c' (cyt c') have been monitored by heme absorption and native Trp72 fluorescence at pH 5. The Trp72 fluorescence burst signal suggests early compaction of the polypeptide ensemble. Analysis of heme transient absorption spectra reveals deviations from two-state behavior, including a prominent slow phase that is accelerated by the prolyl isomerase cyclophilin. A nonnative proline configuration (Pro21) likely interferes with the formation of the helical bundle surrounding the heme.

Electronic structure of the benzene dimer cation

NASA Astrophysics Data System (ADS)

Pieniazek, Piotr A.; Krylov, Anna I.; Bradforth, Stephen E.

2007-07-01

The benzene and benzene dimer cations are studied using the equation-of-motion coupled-cluster model with single and double substitutions for ionized systems. The ten lowest electronic states of the dimer at t-shaped, sandwich, and displaced sandwich configurations are described and cataloged based on the character of the constituent fragment molecular orbitals. The character of the states, bonding patterns, and important features of the electronic spectrum are explained using qualitative dimer molecular orbital linear combination of fragment molecular orbital framework. Relaxed ground state geometries are obtained for all isomers. Calculations reveal that the lowest energy structure of the cation has a displaced sandwich structure and a binding energy of 20kcal/mol, while the t-shaped isomer is 6kcal/mol higher. The calculated electronic spectra agree well with experimental gas phase action spectra and femtosecond transient absorption in liquid benzene. Both sandwich and t-shaped structures feature intense charge resonance bands, whose location is very sensitive to the interfragment distance. Change in the electronic state ordering was observed between σ and πu states, which correlate to the B˜ and C˜ bands of the monomer, suggesting a reassignment of the local excitation peaks in the gas phase experimental spectrum.

UV absorption investigation of ferromagnetically filled ultra-thick carbon onions, carriers of the 217.5 nm Interstellar Absorption Feature

NASA Astrophysics Data System (ADS)

Boi, Filippo S.; Zhang, Xiaotian; Ivaturi, Sameera; Liu, Qianyang; Wen, Jiqiu; Wang, Shanling

2017-12-01

Carbon nano-onions (CNOs) are fullerene-like structures which consist of quasi-spherical closed carbon shells. These structures have become a subject of great interest thanks to their characteristic absorption feature of interstellar origin (at 217.5 nm, 4.6 μm-1). An additional extinction peak at 3.8 μm-1 has also been reported and attributed to absorption by graphitic residues between the as-grown CNOs. Here, we report the ultraviolet absorption properties of ultra-thick CNOs filled with FePt3 crystals, which also exhibit two main absorption peaks—features located at 4.58 μm-1 and 3.44 μm-1. The presence of this additional feature is surprising and is attributed to nonmagnetic graphite flakes produced as a by-product in the pyrolysis experiment (as confirmed by magnetic separation methods). Instead, the feature at 4.58 μm-1 is associated with the π-plasmonic resonance of the CNOs structures. The FePt3 filled CNOs were fabricated in situ by an advanced one-step fast process consisting in the direct sublimation and pyrolysis of two molecular precursors, namely, ferrocene and dichloro-cyclooctadiene-platinum in a chemical vapour deposition system. The morphological, structural, and magnetic properties of the as-grown filled CNOs were characterized by a means of scanning and transmission electron microscopy, X-ray diffraction, and magnetometry.

The hot DOA1 degenerate HZ 21 - A search for circumstellar/photospheric metals and peculiar absorption at He II

NASA Technical Reports Server (NTRS)

Fritz, M. L.; Leckenby, H.; Sion, E. M.; Vauclair, G.; Liebert, J.

1990-01-01

A high-resolution IUE spectrum of the hot DO1 degenerate HZ 21 was obtained by combining US1 + European 2 low-background observing shifts. The SWP image reveals a rich spectrum of interstellar absorption lines with an average velocity in the line of sight to HZ 21 of -30 km/s. However, there is no clear evidence of any highly or lowly ionized metal features which could be attributed to circumstellar, wind, or photospheric absorption. There is, however, a broad absorption trough at He II (1640) which was not unexpected, given the clear presence of He II (4686) absorption in this star's optical spectrum. The velocity width of He II (1640) appears consistent with photospheric absorption wings which appear to flank the geocoronal Ly-alpha emission feature. The He II (1640) feature reveals what appears to be a broad (310 km/s) emission reversal. Evidence is provided that the emission reversal is probably real.

The electronic spectra of benzo[b]thiete and transient o-thiobenzoquinonemethide. Spectral assignments on the basis of the electronic spectra of aniline, thiophenol, thioanisole, all-trans-octatetraene and transient o-xylylene in conjunction with quantum-chemical calculations

NASA Astrophysics Data System (ADS)

Schweig, Armin; Diehl, Frank; Kesper, Karl; Meyer, Hermann

1989-07-01

The electronic absorption spectra of benzo[b]thiete ( 1) and of transient o-thiobenzoquinonemethide ( 2) have been obtained. Semiempirical valence-electron calculations using the CNDO/S SECI, CNDO/S PERTCI and LNDO/S PERTCI methods and correlation diagrams using suitable reference compounds ad aniline, thiophenol, thioanisole, all-trans-octatetraene and o-xylylene are applied to the interpretation of the spectra. The results clearly reveal 1 as a typically donor-substituted benzene derivative and 2 as a polyene-like system closely related to o-xylylene.

Tracking coherent population transfer and thermal population relaxation in condensed system by broad-band transient grating spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Wei; Liu, Xiaosong; Wu, Honglin; Song, Yunfei; Liu, Weilong; Yang, Yanqiang

2018-04-01

Broad-band transient grating (BB-TG) spectroscopy was proposed to track both coherent population transfer (CPT) and thermal population relaxation processes in a condensed system of solvated molecules in solution (Rhodamine101 in methanol). A broad band around 1500 cm‑1 and a relative narrow band near 2900 cm‑1 emerge in TG and transient absorption contour plots when pump and probe pulses overlap in the sample. The experimental results matched well with the vibrational modes of Rhodamine101 that were obtained by theoretical calculation. In addition, it was found that the population of CPT particles can be evaluated quantitatively through the intensity of the TG signal.

Single- and double-core-hole ion emission spectroscopy of transient neon plasmas produced by ultraintense x-ray laser pulses

NASA Astrophysics Data System (ADS)

Gao, Cheng; Zeng, Jiaolong; Yuan, Jianmin

2016-02-01

Single-core-hole (SCH) and double-core-hole (DCH) spectroscopy is investigated systematically for neon gas in the interaction with ultraintense x-ray pulses with photon energy from 937 eV to 2000 eV. A time-dependent rate equation, implemented in detailed level accounting approximation, is utilized to study the dynamical evolution of the level population and emission properties of the laser-produced highly transient plasmas. The plasma-density effects on level populations and charge-state distribution are demonstrated with an x-ray photon energy of 2000 eV. It is shown that atomic number density of relevant experiment is about 1 × 1018 cm-3, which is comparable to a recent experiment. At this density, we systematically investigate the emissivity of the transient neon plasmas. For laser photon energy in the range 937-1360 eV, resonant absorptions (RA) of 1s\\to {np} (n≥slant 2) transitions play important roles in time evolution of the population and DCH emission spectroscopy. The RA effects are illustrated in detail for an x-ray pulse of 944 eV photon energy, which creates the 1s\\to 2p RA from the SCH states (1s2{s}22{p}4, 1s2s2p5, and 1s2p6) of Ne3+. After averaging over the space and time distribution of x-ray pulse, DCH emission spectroscopy is studied at x-ray photon energies of 937, 944, 955, 968, 980, and 990 eV, where there exist 1s\\to 2p resonances from SCH states of Ne2+-Ne7+. The processes with producing DCH states are discussed. For x-ray photon energy larger than 1360 eV, no RA exist and transient plasmas show different features in the DCH spectroscopy.

Reverse saturable absorption (RSA) in fluorinated iridium derivatives

NASA Astrophysics Data System (ADS)

Ferry, Michael J.; O'Donnell, Ryan M.; Bambha, Neal; Ensley, Trenton R.; Shensky, William M.; Shi, Jianmin

2017-08-01

The photophysical properties of cyclometallated iridium compounds are beneficial for nonlinear optical (NLO) applications, such as the design of reverse saturable absorption (RSA) materials. We report on the NLO characterization of a family of compounds of the form [Ir(pbt)2(LX)], where pbt is 2-phenylbenzothiazole and LX is a beta-diketonate ligand. In particular, we investigate the effects of trifluoromethylation on compound solubility and photophysics compared to the parent acetylacetonate (acac) version. The NLO properties, such as the singlet and triplet excited-state cross sections, of these compounds were measured using the Z-scan technique. The excited-state lifetimes were determined from visible transient absorption spectroscopy.

Femtosecond spectroscopy of native and carotenoidless purple-bacterial LH2 clarifies functions of carotenoids.

PubMed

Theiss, Christoph; Leupold, Dieter; Moskalenko, Andrei A; Razjivin, Andrei P; Eichler, Hans J; Lokstein, Heiko

2008-06-01

EET between the two circular bacteriochlorophyll compartments B800 and B850 in native (containing the carotenoid rhodopin) and carotenoidless LH2 isolated from the photosynthetic purple sulfur bacterium Allochromatium minutissimum was investigated by femtosecond time-resolved transient absorption spectroscopy. Both samples were excited with 120-fs laser pulses at 800 nm, and spectral evolution was followed in the 720-955 nm range at different delay times. No dependence of transient absorption in the B800 band on the presence of the carotenoid rhodopin was found. Together with the likewise virtually unchanged absorption spectra in the bacteriochlorophyll Q(y) region, these observations suggest that absence of rhodopin does not significantly alter the structure of the pigment-protein complex including interactions between bacteriochlorophylls. Apparently, rhodopin does also not accelerate B800 to B850 EET in LH2, contrary to what has been suggested previously. Moreover, "carotenoid-catalyzed internal conversion" can also be excluded for the bacteriochlorophylls in LH2 of A. minutissimum. Together with previous results obtained with two-photon fluorescence excitation spectroscopy, it can also be concluded that there is neither EET from rhodopin to B800 nor (back-)EET from B800 to rhodopin.

Electronic structures and population dynamics of excited states of xanthione and its derivatives

NASA Astrophysics Data System (ADS)

Fedunov, Roman G.; Rogozina, Marina V.; Khokhlova, Svetlana S.; Ivanov, Anatoly I.; Tikhomirov, Sergei A.; Bondarev, Stanislav L.; Raichenok, Tamara F.; Buganov, Oleg V.; Olkhovik, Vyacheslav K.; Vasilevskii, Dmitrii A.

2017-09-01

A new compound, 1,3-dimethoxy xanthione (DXT), has been synthesized and its absorption (stationary and transient) and luminescence spectra have been measured in n-hexane and compared with xanthione (XT) spectra. The pronounced broadening of xanthione vibronic absorption band related to the electronic transition to the second singlet excited state has been observed. Distinctions between the spectra of xanthione and its methoxy derivatives are discussed. Quantum chemical calculations of these compounds in the ground and excited electronic states have been accomplished to clarify the nature of electronic spectra changes due to modification of xanthione by methoxy groups. Appearance of a new absorption band of DXT caused by symmetry changes has been discussed. Calculations of the second excited state structure of xanthione and its methoxy derivatives confirm noticeable charge transfer (about 0.1 of the charge of an electron) from the methoxy group to thiocarbonyl group. Fitting of the transient spectra of XT and DXT has been fulfilled and the time constants of internal conversion S2 →S1 and intersystem crossing S1 →T1 have been determined. A considerable difference between the time constants of internal conversion S2 →S1 in XT and DXT is uncovered.

Ultrafast light matter interaction in CdSe/ZnS core-shell quantum dots

NASA Astrophysics Data System (ADS)

Yadav, Rajesh Kumar; Sharma, Rituraj; Mondal, Anirban; Adarsh, K. V.

2018-04-01

Core-shell quantum dot are imperative for carrier (electron and holes) confinement in core/shell, which provides a stage to explore the linear and nonlinear optical phenomena at the nanoscalelimit. Here we present a comprehensive study of ultrafast excitation dynamics and nonlinear optical absorption of CdSe/ZnS core shell quantum dot with the help of ultrafast spectroscopy. Pump-probe and time-resolved measurements revealed the drop of trapping at CdSe surface due to the presence of the ZnS shell, which makes more efficient photoluminescence. We have carried out femtosecond transient absorption studies of the CdSe/ZnS core-shell quantum dot by irradiation with 400 nm laser light, monitoring the transients in the visible region. The optical nonlinearity of the core-shell quantum dot studied by using the Z-scan technique with 120 fs pulses at the wavelengths of 800 nm. The value of two photon absorption coefficients (β) of core-shell QDs extracted as80cm/GW, and it shows excellent benchmark for the optical limiting onset of 2.5GW/cm2 with the low limiting differential transmittance of 0.10, that is an order of magnitude better than graphene based materials.

Clinical- and imaging-based prediction of stroke risk after transient ischemic attack: the CIP model.

PubMed

Ay, Hakan; Arsava, E Murat; Johnston, S Claiborne; Vangel, Mark; Schwamm, Lee H; Furie, Karen L; Koroshetz, Walter J; Sorensen, A Gregory

2009-01-01

Predictive instruments based on clinical features for early stroke risk after transient ischemic attack suffer from limited specificity. We sought to combine imaging and clinical features to improve predictions for 7-day stroke risk after transient ischemic attack. We studied 601 consecutive patients with transient ischemic attack who had MRI within 24 hours of symptom onset. A logistic regression model was developed using stroke within 7 days as the response criterion and diffusion-weighted imaging findings and dichotomized ABCD(2) score (ABCD(2) >/=4) as covariates. Subsequent stroke occurred in 25 patients (5.2%). Dichotomized ABCD(2) score and acute infarct on diffusion-weighted imaging were each independent predictors of stroke risk. The 7-day risk was 0.0% with no predictor, 2.0% with ABCD(2) score >/=4 alone, 4.9% with acute infarct on diffusion-weighted imaging alone, and 14.9% with both predictors (an automated calculator is available at http://cip.martinos.org). Adding imaging increased the area under the receiver operating characteristic curve from 0.66 (95% CI, 0.57 to 0.76) using the ABCD(2) score to 0.81 (95% CI, 0.74 to 0.88; P=0.003). The sensitivity of 80% on the receiver operating characteristic curve corresponded to a specificity of 73% for the CIP model and 47% for the ABCD(2) score. Combining acute imaging findings with clinical transient ischemic attack features causes a dramatic boost in the accuracy of predictions with clinical features alone for early risk of stroke after transient ischemic attack. If validated in relevant clinical settings, risk stratification by the CIP model may assist in early implementation of therapeutic measures and effective use of hospital resources.

Molecular specificity in photoacoustic microscopy by time-resolved transient absorption.

PubMed

Shelton, Ryan L; Mattison, Scott P; Applegate, Brian E

2014-06-01

We have recently harnessed transient absorption, a resonant two-photon process, for ultrahigh resolution photoacoustic microscopy, achieving nearly an order of magnitude improvement in axial resolution. The axial resolution is optically constrained due to the two-photon process unlike traditional photoacoustic microscopy where the axial resolution is inversely proportional to the frequency bandwidth of the detector. As a resonant process, the arrival time of the two photons need not be instantaneous. Systematically recording the signal as a function of the delay between two pulses will result in the measurement of an exponential decay whose time constant is related to the molecular dynamics. This time constant, analogous to the fluorescence lifetime, but encompassing nonradiative decay as well, can be used to differentiate between molecular systems with overlapping absorption spectra. This is frequently the situation for closely related yet distinct molecules such as redox pairs. In order to enable the measure of the exponential decay, we have reconfigured our transient absorption ultrasonic microscopy (TAUM) system to incorporate two laser sources with precisely controlled pulse trains. The system was tested by measuring Rhodamine 6G, an efficient laser dye where the molecular dynamics are dominated by the fluorescence pathway. As expected, the measured exponential time constant or ground state recovery time, 3.3±0.7  ns, was similar to the well-known fluorescence lifetime, 4.11±0.05  ns. Oxy- and deoxy-hemoglobin are the quintessential pair whose relative concentration is related to the local blood oxygen saturation. We have measured the ground state recovery times of these two species in fully oxygenated and deoxygenated bovine whole blood to be 3.7±0.8  ns and 7.9±1.0  ns, respectively. Hence, even very closely related pairs of molecules may be differentiated with this technique.

IUE's View of Callisto: Detection of an SO2 Absorption Correlated to Possible Torus Neutral Wind Alterations

NASA Technical Reports Server (NTRS)

Lane, Arthur L.; Domingue, Deborah L.

1997-01-01

Observations taken with the International Ultraviolet Explorer (IUE) detected a 0.28 micron absorption feature on Callisto's leading and Jupiter-facing hemispheres. This feature is similar to Europa's 0.28 micron feature, however it shows no correlation with magnetospheric ion bombardment. The strongest 0.28 micron signature is seen in the region containing the Valhalla impact. This absorption feature also shows some spatial correlation to possible neutral wind interactions, suggestive of S implantation (rather than S(sub x)) into Callisto's water ice surface, Indications of possible temporal variations (on the 10% level) are seen at other wavelengths between the 1984-1986 and the 1996 observations.

Transient Infrared Emission Spectroscopy

NASA Astrophysics Data System (ADS)

Jones, Roger W.; McClelland, John F.

1989-12-01

Transient Infrared Emission Spectroscopy (TIRES) is a new technique that reduces the occurrence of self-absorption in optically thick solid samples so that analytically useful emission spectra may be observed. Conventional emission spectroscopy, in which the sample is held at an elevated, uniform temperature, is practical only for optically thin samples. In thick samples the emission from deep layers of the material is partially absorbed by overlying layers.1 This self-absorption results in emission spectra from most optically thick samples that closely resemble black-body spectra. The characteristic discrete emission bands are severely truncated and altered in shape. TIRES bypasses this difficulty by using a laser to heat only an optically thin surface layer. The increased temperature of the layer is transient since the layer will rapidly cool and thicken by thermal diffusion; hence the emission collection must be correlated with the laser heating. TIRES may be done with both pulsed and cw lasers.2,3 When a pulsed laser is used, the spectrometer sampling must be synchronized with the laser pulsing so that only emission during and immediately after each laser pulse is observed.3 If a cw laser is used, the sample must move rapidly through the beam. The hot, transient layer is then in the beam track on the sample at and immediately behind the beam position, so the spectrometer field of view must be limited to this region near the beam position.2 How much self-absorption the observed emission suffers depends on how thick the heated layer has grown by thermal diffusion when the spectrometer samples the emission. Use of a pulsed laser synchronized with the spectrometer sampling readily permits reduction of the time available for heat diffusion to about 100 acs .3 When a cw laser is used, the heat-diffusion time is controlled by how small the spectrometer field of view is and by how rapidly the sample moves past within this field. Both a very small field of view and a very high sample speed would be required to attain a diffusion time of 100 μs. Accordingly, pulsed-laser TIRES generally produces spectra suffering from less self-absorption than cw-laser TIRES does, but the cw-laser technique is technically much simpler since no synchronization is required.

Energy transfer in purple bacterial photosynthetic units from cells grown in various light intensities.

PubMed

Niedzwiedzki, Dariusz M; Gardiner, Alastair T; Blankenship, Robert E; Cogdell, Richard J

2018-05-03

Three photosynthetic membranes, called intra-cytoplasmic membranes (ICMs), from wild-type and the ∆pucBA abce mutant of the purple phototrophic bacterium Rps. palustris were investigated using optical spectroscopy. The ICMs contain identical light-harvesting complex 1-reaction centers (LH1-RC) but have various spectral forms of light-harvesting complex 2 (LH2). Spectroscopic studies involving steady-state absorption, fluorescence, and femtosecond time-resolved absorption at room temperature and at 77 K focused on inter-protein excitation energy transfer. The studies investigated how energy transfer is affected by altered spectral features of the LH2 complexes as those develop under growth at different light conditions. The study shows that LH1 → LH2 excitation energy transfer is strongly affected if the LH2 complex alters its spectroscopic signature. The LH1 → LH2 excitation energy transfer rate modeled with the Förster mechanism and kinetic simulations of transient absorption of the ICMs demonstrated that the transfer rate will be 2-3 times larger for ICMs accumulating LH2 complexes with the classical B800-850 spectral signature (grown in high light) compared to the ICMs from the same strain grown in low light. For the ICMs from the ∆pucBA abce mutant, in which the B850 band of the LH2 complex is blue-shifted and almost degenerate with the B800 band, the LH1 → LH2 excitation energy transfer was not observed nor predicted by calculations.

Evaluation of Fourier transform coefficients for the diagnosis of rheumatoid arthritis from diffuse optical tomography images

NASA Astrophysics Data System (ADS)

Montejo, Ludguier D.; Jia, Jingfei; Kim, Hyun K.; Hielscher, Andreas H.

2013-03-01

We apply the Fourier Transform to absorption and scattering coefficient images of proximal interphalangeal (PIP) joints and evaluate the performance of these coefficients as classifiers using receiver operator characteristic (ROC) curve analysis. We find 25 features that yield a Youden index over 0.7, 3 features that yield a Youden index over 0.8, and 1 feature that yields a Youden index over 0.9 (90.0% sensitivity and 100% specificity). In general, scattering coefficient images yield better one-dimensional classifiers compared to absorption coefficient images. Using features derived from scattering coefficient images we obtain an average Youden index of 0.58 +/- 0.16, and an average Youden index of 0.45 +/- 0.15 when using features from absorption coefficient images.

The effect of Se/Te ratio on transient absorption behavior and nonlinear absorption properties of CuIn0.7Ga0.3(Se1-xTex)2 (0 ≤ x ≤ 1) amorphous semiconductor thin films

NASA Astrophysics Data System (ADS)

Karatay, Ahmet; Küçüköz, Betül; Çankaya, Güven; Ates, Aytunc; Elmali, Ayhan

2017-11-01

The characterization of the CuInSe2 (CIS), CuInGaSe (CIGS) and CuGaSe2 (CGS) based semiconductor thin films are very important role for solar cell and various nonlinear optical applications. In this paper, the amorphous CuIn0.7Ga0.3(Se1-xTex)2 semiconductor thin films (0 ≤ x ≤ 1) were prepared with 60 nm thicknesses by using vacuum evaporation technique. The nonlinear absorption properties and ultrafast transient characteristics were investigated by using open aperture Z-scan and ultrafast pump-probe techniques. The energy bandgap values were calculated by using linear absorption spectra. The bandgap values are found to be varying from 0.67 eV to 1.25 eV for CuIn0.7Ga0.3Te2, CuIn0.7Ga0.3Se1.6Te0.4, CuIn0.7Ga0.3Se0.4Te1.6 and CuIn0.7Ga0.3Se2 thin films. The energy bandgap values decrease with increasing telluride (Te) doping ratio in mixed CuIn0.7Ga0.3(Se1-xTex)2 films. This affects nonlinear characteristics and ultrafast dynamics of amorphous thin films. Ultrafast pump-probe experiments indicated that decreasing of bandgap values with increasing the Te amount switches from the excited state absorption signals to ultrafast bleaching signals. Open aperture Z-scan experiments show that nonlinear absorption properties enhance with decreasing bandgaps values for 65 ps pulse duration at 1064 nm. Highest nonlinear absorption coefficient was found for CuIn0.7Ga0.3Te2 thin film due to having the smallest energy bandgap.

Reflectance spectroscopy (0.35-8 μm) of ammonium-bearing minerals and qualitative comparison to Ceres-like asteroids

NASA Astrophysics Data System (ADS)

Berg, Breanne L.; Cloutis, Edward A.; Beck, Pierre; Vernazza, Pierre; Bishop, Janice L.; Takir, Driss; Reddy, Vishnu; Applin, Daniel; Mann, Paul

2016-02-01

Ammonium-bearing minerals have been suggested to be present on Mars, Ceres, and various asteroids and comets. We undertook a systematic study of the spectral reflectance properties of ammonium-bearing minerals and compounds that have possible planetary relevance (i.e., ammonium carbonates, chlorides, nitrates, oxalates, phosphates, silicates, and sulfates). Various synthetic and natural NH4+-bearing minerals were analyzed using reflectance spectroscopy in the long-wave ultraviolet, visible, near-infrared, and mid-infrared regions (0.35-8 μm) in order to identify spectral features characteristic of the NH4+ molecule, and to evaluate if and how these features vary among different species. Mineral phases were confirmed through structural and compositional analyses using X-ray diffraction, X-ray fluorescence, and elemental combustion analysis. Characteristic absorption features associated with NH4 can be seen in the reflectance spectra at wavelengths as short as ∼1 μm. In the near-infrared region, the most prominent absorption bands are located near 1.6, 2.0, and 2.2 μm. Absorption features characteristic of NH4+ occurred at slightly longer wavelengths in the mineral-bound NH4+ spectra than for free NH4+ for most of the samples. Differences in wavelength position are attributable to various factors, including differences in the type and polarizability of the anion(s) attached to the NH4+, degree and type of hydrogen bonding, molecule symmetry, and cation substitutions. Multiple absorption features, usually three absorption bands, in the mid-infrared region between ∼2.8 and 3.8 μm were seen in all but the most NH4-poor sample spectra, and are attributed to fundamentals, combinations, and overtones of stretching and bending vibrations of the NH4+ molecule. These features appear even in reflectance spectra of water-rich samples which exhibit a strong 3 μm region water absorption feature. While many of the samples examined in this study have NH4 absorption bands at unique wavelength positions, in order to discriminate between different NH4+-bearing phases, absorption features corresponding to molecules other than NH4+ should be included in spectral analysis. A qualitative comparison of the laboratory results to telescopic spectra of Asteroids 1 Ceres, 10 Hygiea, and 324 Bamberga for the 3 μm region demonstrates that a number of NH4-bearing phases are consistent with the observational data in terms of exhibiting an absorption band in the 3.07 μm region.

Reflectance spectroscopy (0.35–8 μm) of ammonium-bearing minerals and qualitative comparison to Ceres-like asteroids

USGS Publications Warehouse

Berg, Breanne L.; Cloutis, Edward A.; Beck, P.; Vernazza, P.; Bishop, Janice L; Takir, Driss; Reddy, V.; Applin, D.; Mann, Paul

2016-01-01

Ammonium-bearing minerals have been suggested to be present on Mars, Ceres, and various asteroids and comets. We undertook a systematic study of the spectral reflectance properties of ammonium-bearing minerals and compounds that have possible planetary relevance (i.e., ammonium carbonates, chlorides, nitrates, oxalates, phosphates, silicates, and sulfates). Various synthetic and natural NH4+-bearing minerals were analyzed using reflectance spectroscopy in the long-wave ultraviolet, visible, near-infrared, and mid-infrared regions (0.35–8 μm) in order to identify spectral features characteristic of the NH4+ molecule, and to evaluate if and how these features vary among different species. Mineral phases were confirmed through structural and compositional analyses using X-ray diffraction, X-ray fluorescence, and elemental combustion analysis. Characteristic absorption features associated with NH4 can be seen in the reflectance spectra at wavelengths as short as ∼1 μm. In the near-infrared region, the most prominent absorption bands are located near 1.6, 2.0, and 2.2 μm. Absorption features characteristic of NH4+ occurred at slightly longer wavelengths in the mineral-bound NH4+ spectra than for free NH4+ for most of the samples. Differences in wavelength position are attributable to various factors, including differences in the type and polarizability of the anion(s) attached to the NH4+, degree and type of hydrogen bonding, molecule symmetry, and cation substitutions. Multiple absorption features, usually three absorption bands, in the mid-infrared region between ∼2.8 and 3.8 μm were seen in all but the most NH4-poor sample spectra, and are attributed to fundamentals, combinations, and overtones of stretching and bending vibrations of the NH4+ molecule. These features appear even in reflectance spectra of water-rich samples which exhibit a strong 3 μm region water absorption feature. While many of the samples examined in this study have NH4 absorption bands at unique wavelength positions, in order to discriminate between different NH4+-bearing phases, absorption features corresponding to molecules other than NH4+ should be included in spectral analysis. A qualitative comparison of the laboratory results to telescopic spectra of Asteroids 1 Ceres, 10 Hygiea, and 324 Bamberga for the 3 μm region demonstrates that a number of NH4-bearing phases are consistent with the observational data in terms of exhibiting an absorption band in the 3.07 μm region.

In Search of the Perfect Photocage: Structure-Reactivity Relationships in meso-Methyl BODIPY Photoremovable Protecting Groups.

PubMed

Slanina, Tomáš; Shrestha, Pradeep; Palao, Eduardo; Kand, Dnyaneshwar; Peterson, Julie A; Dutton, Andrew S; Rubinstein, Naama; Weinstain, Roy; Winter, Arthur H; Klán, Petr

2017-10-25

A detailed investigation of the photophysical parameters and photochemical reactivity of meso-methyl BODIPY photoremovable protecting groups was accomplished through systematic variation of the leaving group (LG) and core substituents as well as substitutions at boron. Efficiencies of the LG release were evaluated using both steady-state and transient absorption spectroscopies as well as computational analyses to identify the optimal structural features. We find that the quantum yields for photorelease with this photocage are highly sensitive to substituent effects. In particular, we find that the quantum yields of photorelease are improved with derivatives with higher intersystem crossing quantum yields, which can be promoted by core heavy atoms. Moreover, release quantum yields are dramatically improved by boron alkylation, whereas alkylation in the meso-methyl position has no effect. Better LGs are released considerably more efficiently than poorer LGs. We find that these substituent effects are additive, for example, a 2,6-diiodo-B-dimethyl BODIPY photocage features quantum yields of 28% for the mediocre LG acetate and a 95% quantum yield of release for chloride. The high chemical and quantum yields combined with the outstanding absorption properties of BODIPY dyes lead to photocages with uncaging cross sections over 10 000 M -1 cm -1 , values that surpass cross sections of related photocages absorbing visible light. These new photocages, which absorb strongly near the second harmonic of an Nd:YAG laser (532 nm), hold promise for manipulating and interrogating biological and material systems with the high spatiotemporal control provided by pulsed laser irradiation, while avoiding the phototoxicity problems encountered with many UV-absorbing photocages. More generally, the insights gained from this structure-reactivity relationship may aid in the development of new highly efficient photoreactions.

Accretion and Structure in the SW Sextantis Stars

NASA Astrophysics Data System (ADS)

Hoard, Donald Wayne

1998-09-01

The SW Sextantis stars are cataclysmic variables (CVs) sharing properties that set them apart from other CVs. These include: strong He II λ4686 emission, velocity curves implying asymmetric disk emission, and variable line profiles displaying a transient absorption feature at specific orbital phases. A number of mechanisms have been proposed to explain these characteristics including (non-disk) circumstellar material, a bipolar disk wind, a white dwarf magnetic field, and coherent accretion stream overflow across the disk, but none has been completely satisfying. I present the results of new photometric and spectroscopic observations of seven SW Sex stars, including Doppler tomogram mapping of emission regions in these systems. These observations, along with recent advances in simulations of accretion disks, suggest a scenario in which the accretion stream undergoes a violent impact with the disk edge. Depending on the mass transfer rate in the stream, the impact site will either cool efficiently (low M) and allow substantial material to flow directly over the disk, or will cool inefficiently (high M) and form a prominent bright spot at the impact site with hot stream material swept 'downstream' along the disk edge. In the former case, non-axisymmetric vertical structure develops in the disk at the terminus of the stream overflow (accounting for absorption seen at φapprox0.5), while in the latter case vertical structure is built up along the disk edge (accounting for absorption at φapprox0.8). The absorption feature phasing in different SW Sex stars implies M decreases as P orb decreases (as expected during CV evolution), but it is not clear whether normal CV evolution can drive changes in M rapidly enough to generate the onset of the SW Sex phenomenon in the narrow range of orbital period they occupy (P orb=3[-]4 hr). I present a gallery of new and archived IUE spectra of the SW Sex stars that display the typically strong UV resonant scattering lines seen in these CVs. The orbital-phase dependence of UV spectral characteristics in UU Aquarii is investigated through a time series of archived IUE spectra, and provides additional evidence of asymmetric structure in this system. The scBINSYN light curve and spectrum modeling package for binary stars has been modified for application to CVs. First results for several SW Sex stars are shown and planned future improvements to the scBINSYN routines are described.

[Analysis of UV-visible absorption spectrum on the decolorization of industrial wastewater by disinfection].

PubMed

Huang, Xin; Wang, Long-Yong; Gao, Nai-Yun; Li, Wei-Guo

2012-10-01

The UV-Visible absorption spectrum of industrial wastewater was explored to introduce a substituting method determining the color of water, and to compare the decolorization efficacy of different disinfectants. The results show that the visible absorption spectrum(350-600 nm), instead of ultraviolet absorption spectrum, should be applied to characterize the color of wastewater. There is a good correlation between the features of visible absorption spectrum and the true color of wastewater. Both ozone and chlorine dioxide has a better decolorization performance than chlorine. However, the color of chlorine dioxide itself has a negative effect on decolorization. The changes in the features of visible absorption spectrum effectively reflect the variations in the color of wastewater after disinfection.

Detection of absorption lines in the spectra of X-ray bursts from X1608-52

NASA Astrophysics Data System (ADS)

Nakamura, Norio; Inoue, Hajime; Tanaka, Yasuo

X-ray bursts from X 1608-52 were observed with the gas scintillation proportional counters on the Tenma satellite. Absorption features were detected in the spectra of three bursts among 17 bursts observed. These absorption features are consistent with a common absorption line at 4.1 keV. The energy and the properties of the absorption lines of the X 1608-52 bursts are very similar to those observed from the X 1636-53 bursts by Waki et al. (1984). Near equality of the absorption-line energies for X 1636-53 and X 1608-52 would imply that mass and radius of the neutron stars in these two systems are very similar to each other.

Intravenous injection of indocyanine green results in an artificial transient desaturation by pulse oximetry.

PubMed

Ediriwickrema, Lilangi S; Francis, Jasmine H; Arslan-Carlon, Vittoria; Dalecki, Paul H; Brodie, Scott E; Marr, Brian P; Abramson, David H

2015-01-01

To describe a case series of transient oxygen desaturation measured by pulse oximetry during the intravenous infusion of indocyanine green to enhance transpupillary thermotherapy in treating retinoblastoma after ophthalmic artery chemosurgery. Retrospective descriptive case series. The intravenous administration of indocyanine green for ophthalmic angiography resulted in a transient drop in oxygen saturation as measured by Nellcor fingertip pulse oximetry in three children with retinoblastoma receiving indocyanine green-guided transpupillary thermotherapy. The magnitude of reduction ranged from 92% to 94% from an initial reading of 99% to 100% in each case, with an average duration of 3 minutes. Concurrent measurement of blood pressure, pulse, and expired CO2 showed no changes during this process. Administration of intravenous indocyanine green resulted in a transient desaturation by oximetry during transpupillary thermotherapy for children with retinoblastoma under anesthesia because of the fluorescent dye's absorption of red light in a manner similar to that of deoxygenated hemoglobin, thereby leading to transient instrument misinterpretation and miscalculation of arterial oxygenation.

Search for volatiles on icy satellites. I. Europa

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, R.H.; Cruikshank, D.P.; Tokunaga, A.T.

1988-05-01

NASA IRTF reflectance spectra of unprecedented precision, obtained for the leading and trailing sides of Europa, are presently noted to no longer show the apparent absorptions seen in 1980 and 1985. It is presently suggested that if the weak absorptions seen in the 1980 and 1985 data are real, they may indicate the transient spectroscopic presence of a molecular component on Europa's trailing side that differs from the water ice known to be the dominant constituent of the surface. 33 references.

Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

NASA Technical Reports Server (NTRS)

Haugen, H. K.; Weitz, E.; Leone, S. R.

1985-01-01

Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

Combined infrared and ultraviolet-visible spectroscopy matrix-isolated carbon vapor

NASA Technical Reports Server (NTRS)

Kurtz, Joe; Huffman, Donald R.

1990-01-01

Infrared and UV-visible absorption spectra have been measured on the same sample of matrix-isolated carbon vapor in order to establish correlations between absorption intensities of vibrational and electronic transitions as a function of sample annealing. A high degree of correlation has been found between the IR feature at 1998/cm recently assigned to C8 and a UV absorption feature at about 3100 A. Thus, for the first time, direct evidence is given for the assignment of one of the unknown UV-visible features of the long-studied matrix-isolated carbon vapor spectrum.

Rapid Swept-Wavelength External Cavity Quantum Cascade Laser for Open Path Sensing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brumfield, Brian E.; Phillips, Mark C.

2015-07-01

A rapidly tunable external cavity quantum cascade laser system is used for open path sensing. The system permits acquisition of transient absorption spectra over a 125 cm-1 tuning range in less than 0.01 s.

A theory of post-stall transients in multistage axial compression systems

NASA Technical Reports Server (NTRS)

Moore, F. K.; Greitzer, E. M.

1985-01-01

A theory is presented for post stall transients in multistage axial compressors. The theory leads to a set of coupled first-order ordinary differential equations capable of describing the growth and possible decay of a rotating-stall cell during a compressor mass-flow transient. These changing flow features are shown to have a significant effect on the instantaneous compressor pumping characteristic during unsteady operation, and henace on the overall system behavior. It is also found from the theory that the ultimate mode of system response, stable rotating stall or surge, depends not only on the B parameter but also on other parameters, such as the compressor length-to-diameter ratio. Small values of this latter quantity tend to favor the occurrence of surge, as do large values of B. A limited parametric study is carried out to show the impact of the different system features on transient behavior. Based on analytical and numerical results, several specific topics are suggested for future research on post-stall transients.

Near-infrared spectra of the Martian surface: Reading between the lines

NASA Technical Reports Server (NTRS)

Crisp, D.; Bell, J. F., III

1993-01-01

Moderate-resolution near-infrared (NIR) spectra of Mars have been widely used in studies of the Martian surface because many candidate surface materials have distinctive absorption features at these wavelengths. Recent advances in NIR detector technology and instrumentation have also encouraged studies in this spectral region. The use of moderate spectral resolution has often been justified for NIR surface observations because the spectral features produced by most surface materials are relatively broad, and easily discriminated at this resolution. In spite of this, NIR spectra of Mars are usually very difficult to interpret quantitatively. One problem is that NIR surface absorption features are often only a few percent deep, requiring observations with great signal-to-noise ratios. A more significant problem is that gases in the Martian atmosphere contribute numerous absorption features at these wavelengths. Ground-based observers must also contend with variable absorption by several gases in the Earth's atmosphere (H2O, CO2, O3, N2O, CH4, O2). The strong CO2 bands near 1.4, 1.6, 2.0, 2.7, 4.3, and 4.8 micrometers largely preclude the analysis of surface spectral features at these wavelengths. Martian atmospheric water vapor also contributes significant absorption near 1.33, 1.88, and 2.7 micrometers, but water vapor in the Earth's atmosphere poses a much larger problem to ground-based studies of these spectral regions. The third most important NIR absorber in the Martian atmosphere is CO. This gas absorbs most strongly in the relatively-transparent spectral windows near 4.6 and 2.3 micrometers. It also produces 1-10 percent absorption in the solar spectrum at these NIR wavelengths. This solar CO absorption cannot be adequately removed by dividing the Martian spectrum by that of a star, as is commonly done to calibrate ground-based spectroscopic observations, because most stars do not have identical amounts of CO absorption in their spectra. Here, we describe tow effective methods for eliminating contamination of Martian surface spectra by absorption in the solar, terrestrial, and Martian atmospheres. Both methods involve the use of very-high-resolution spectra that completely resolve the narrow atmospheric absorption lines.

A Suzaku View of Cyclotron Line Sources and Candidates

NASA Technical Reports Server (NTRS)

Pottschmidt, K.; Suchy, S.; Rivers, E.; Rothschild, R. E.; Marcu, D. M.; Barragan, L.; Kuehnel, M.; Fuerst, F.; Schwarm, F.; Kreykenbohm, I.;

The Discovery Outburst of the X-Ray Transient IGR J17497-2821 Observed with RXTE and ATCA

NASA Technical Reports Server (NTRS)

Rodriquez, Jerome; Bel, Marion Cadolle; Tomsick, John A.; Corbel, Stephane; Brocksopp, Catherine; Paizis, Ada; Shaw, Simon E.; Bodaghee, Arash

2007-01-01

We report the results of a series of RXTE and ATCA observations of the recently discovered X-ray transient IGR J17497-2821. Our 3-200 keV PCA+HEXTE spectral analysis shows very little variations over a period of approx.10 days around the maximum of the outburst. IGR J17497-2821 is found in a typical low-hard state (LHS) of X-ray binaries (XRBs), well represented by an absorbed Comptonized spectrum with an iron edge at about 7 keV. The high value of the absorption (approx.4 x 10(exp 22/sq cm suggests that the source is located at a large distance, either close to the Galactic center or beyond. The timing analysis shows no particular features, while the shape of the power density spectra is also typical of the LHS of XRBs, with apprrox.36% rms variability. No radio counterpart is found down to a limit of 0.21 mJy at 4.80 and 8.64 GHz. Although the position of IGR J17497-2821 in the radio to X-ray flux diagram is well below the correlation usually observed in the LHS of black holes, the comparison of its X-ray properties with those of other sources leads us to suggest that it is a black hole candidate.

Radiolytic degradation of 4-nitrophenol in aqueous solutions: Pulse and steady state radiolysis study

NASA Astrophysics Data System (ADS)

Biswal, Jayashree; Paul, Jhimli; Naik, D. B.; Sarkar, S. K.; Sabharwal, S.

2013-04-01

The radiation induced degradation of 4-nitrophenol (4-NP) has been studied by gamma irradiation, while the reactivity and spectral features of the short lived transients formed by reaction with primary transient radicals at different pHs has been investigated by pulse radiolysis technique. In steady state radiolysis a dose of 4.4 k Gy is able to degrade 98% of 1×10-4 mol dm-3 4-NP. 4-NP has pKa at 7.1, above which it is present in the anionic form. At pH 5.2, •OH and N3• radicals were found to react with 4-NP with rate constants of 4.1×109 dm3 mol-1 s-1 and 2.8×108 dm3 mol-1 s-1, respectively. Differences in the absorption spectra of species formed in the reactions of 4-NP with •OH and N3• radicals suggested that •OH radicals add to the aromatic ring of 4-NP along with electron transfer reaction, whereas N3• radicals undergo only electron transfer reaction. At pH 9.2, rate constants for the reaction of •OH radicals with 4-NP was found to be higher by a factor of 2 compared to that at pH 5.2. This has been assigned to the deprotonation of 4-NP at pH 9.2.

Simultaneous infrared and UV-visible absorption spectra of matrix-isolated carbon vapor

NASA Technical Reports Server (NTRS)

Kurtz, Joe; Huffman, Donald R.

1989-01-01

Carbon molecules were suggested as possible carriers of the diffuse interstellar bands. In particular, it was proposed that the 443 nm diffuse interstellar band is due to the same molecule which gives rise to the 447 nm absorption feature in argon matrix-isolated carbon vapor. If so, then an associated C-C stretching mode should be seen in the IR. By doing spectroscopy in both the IR and UV-visible regions on the same sample, the present work provides evidence for correlating UV-visible absorption features with those found in the IR. Early data indicates no correlation between the strongest IR feature (1997/cm) and the 447 nm band. Correlation with weaker IR features is being investigated.

Exploring the Time Evolution of Cool Metallic Absorption Features in UV Burst Spectra

NASA Astrophysics Data System (ADS)

Belmes, K.; Madsen, C. A.; DeLuca, E.

2017-12-01

UV bursts are compact brightenings in active regions that appear in UV images. They are identified through three spectroscopic features: (1) broadening and intensification of NUV/FUV emission lines, (2) the presence of optically thin Si IV emission, and (3) the presence of absorption features from cool metallic ions. Properties (2) and (3) imply that bursts exist at transition region temperatures (≥ 80,000 K) but are located in the cooler lower chromosphere ( 5,000 K). Their energetic and dynamical properties remain poorly constrained. Improving our understanding of this phenomena could help us further constrain the energetic and dynamical properties of the chromosphere, as well as give us insight into whether or not UV bursts contribute to chromospheric and/or coronal heating. We analyzed the time evolution of UV bursts using spectral data from the Interface Region Imaging Spectrograph (IRIS). We inspected Si IV 1393.8 Å line profiles for Ni II 1393.3 Å absorption features to look for signs of heating. Weakening of absorption features over time could indicate heating of the cool ions above the burst, implying that thermal energy from the burst could rapidly conduct upward through the chromosphere. To detect the spectral profiles corresponding to bursts, we applied a four-parameter Gaussian fit to every profile in each observation and took cuts in parameter space to isolate the bursts. We then manually reviewed the remaining profiles by looking for a statistically significant appearance of Ni II 1393.3 Å absorption. We quantified these absorption features by normalizing the Si IV 1393.8 Å emission profiles and measuring the maximum fractional extinction in each. Our preliminary results indicate that Ni II 1393.3 Å absorption may undergo a cycle of strengthening and weakening throughout a burst's lifetime. However, further investigation is needed for confirmation. This work is supported by the NSF-REU solar physics program at SAO, grant number AGS-1560313.

Radiative interactions in transient energy transfer in gaseous systems

NASA Technical Reports Server (NTRS)

Tiwari, S. N.

1985-01-01

Analyses and numerical procedures are presented to investigate the radiative interactions in transient energy transfer processes in gaseous systems. The nongray radiative formulations are based on the wide-band model correlations for molecular absorption. Various relations for the radiative flux are developed; these are useful for different flow conditions and physical problems. Specific plans for obtaining extensive results for different cases are presented. The methods presented in this study can be extended easily to investigate the radiative interactions in realistic flows of hydrogen-air species in the scramjet engine.

Real Time Quantification of Ultrafast Photoinduced Bimolecular Electron Transfer Rate: Direct Probing of the Transient Intermediate.

PubMed

Mukherjee, Puspal; Biswas, Somnath; Sen, Pratik

2015-08-27

Fluorescence quenching studies through steady-state and time-resolved measurements are inadequate to quantify the bimolecular electron transfer rate in bulk homogeneous solution due to constraints from diffusion. To nullify the effect of diffusion, direct evaluation of the rate of formation of a transient intermediate produced upon the electron transfer is essential. Methyl viologen, a well-known electron acceptor, produces a radical cation after accepting an electron, which has a characteristic strong and broad absorption band centered at 600 nm. Hence it is a good choice to evaluate the rate of photoinduced electron transfer reaction employing femtosecond broadband transient absorption spectroscopy. The time constant of the aforementioned process between pyrene and methyl viologen in methanol has been estimated to be 2.5 ± 0.4 ps using the same technique. The time constant for the backward reaction was found to be 14 ± 1 ps. These values did not change with variation of concentration of quencher, i.e., methyl viologen. Hence, we can infer that diffusion has no contribution in the estimation of rate constants. However, on changing the solvent from methanol to ethanol, the time constant of the electron transfer reaction has been found to increase and has accounted for the change in solvent reorganization energy.

Nonlinear absorption dynamics using field-induced surface hopping: zinc porphyrin in water.

PubMed

Röhr, Merle I S; Petersen, Jens; Wohlgemuth, Matthias; Bonačić-Koutecký, Vlasta; Mitrić, Roland

2013-05-10

We wish to present the application of our field-induced surface-hopping (FISH) method to simulate nonlinear absorption dynamics induced by strong nonresonant laser fields. We provide a systematic comparison of the FISH approach with exact quantum dynamics simulations on a multistate model system and demonstrate that FISH allows for accurate simulations of nonlinear excitation processes including multiphoton electronic transitions. In particular, two different approaches for simulating two-photon transitions are compared. The first approach is essentially exact and involves the solution of the time-dependent Schrödinger equation in an extended manifold of excited states, while in the second one only transiently populated nonessential states are replaced by an effective quadratic coupling term, and dynamics is performed in a considerably smaller manifold of states. We illustrate the applicability of our method to complex molecular systems by simulating the linear and nonlinear laser-driven dynamics in zinc (Zn) porphyrin in the gas phase and in water. For this purpose, the FISH approach is connected with the quantum mechanical-molecular mechanical approach (QM/MM) which is generally applicable to large classes of complex systems. Our findings that multiphoton absorption and dynamics increase the population of higher excited states of Zn porphyrin in the nonlinear regime, in particular in solution, provides a means for manipulating excited-state properties, such as transient absorption dynamics and electronic relaxation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highlights of Transient Plume Impingement Model Validation and Applications

NASA Technical Reports Server (NTRS)

Woronowicz, Michael

2011-01-01

This paper describes highlights of an ongoing validation effort conducted to assess the viability of applying a set of analytic point source transient free molecule equations to model behavior ranging from molecular effusion to rocket plumes. The validation effort includes encouraging comparisons to both steady and transient studies involving experimental data and direct simulation Monte Carlo results. Finally, this model is applied to describe features of two exotic transient scenarios involving NASA Goddard Space Flight Center satellite programs.

Energy transfer mechanisms in layered 2D perovskites.

PubMed

Williams, Olivia F; Guo, Zhenkun; Hu, Jun; Yan, Liang; You, Wei; Moran, Andrew M

2018-04-07

Two-dimensional (2D) perovskite quantum wells are generating broad scientific interest because of their potential for use in optoelectronic devices. Recently, it has been shown that layers of 2D perovskites can be grown in which the average thicknesses of the quantum wells increase from the back to the front of the film. This geometry carries implications for light harvesting applications because the bandgap of a quantum well decreases as its thickness increases. The general structural formula for the 2D perovskite systems under investigation in this work is (PEA) 2 (MA) n-1 [Pb n I 3n+1 ] (PEA = phenethyl ammonium, MA = methyl ammonium). Here, we examine two layered 2D perovskites with different distributions of quantum well thicknesses. Spectroscopic measurements and model calculations suggest that both systems funnel electronic excitations from the back to the front of the film through energy transfer mechanisms on the time scales of 100's of ps (i.e., energy transfer from thinner to thicker quantum wells). In addition, the model calculations demonstrate that the transient absorption spectra are composed of a progression of single exciton and biexciton resonances associated with the individual quantum wells. We find that exciton dissociation and/or charge transport dynamics make only minor contributions to the transient absorption spectra within the first 1 ns after photo-excitation. An analysis of the energy transfer kinetics indicates that the transitions occur primarily between quantum wells with values of n that differ by 1 because of the spectral overlap factor that governs the energy transfer rate. Two-dimensional transient absorption spectra reveal a pattern of resonances consistent with the dominance of sequential energy transfer dynamics.

Energy transfer mechanisms in layered 2D perovskites

NASA Astrophysics Data System (ADS)

Williams, Olivia F.; Guo, Zhenkun; Hu, Jun; Yan, Liang; You, Wei; Moran, Andrew M.

2018-04-01

Two-dimensional (2D) perovskite quantum wells are generating broad scientific interest because of their potential for use in optoelectronic devices. Recently, it has been shown that layers of 2D perovskites can be grown in which the average thicknesses of the quantum wells increase from the back to the front of the film. This geometry carries implications for light harvesting applications because the bandgap of a quantum well decreases as its thickness increases. The general structural formula for the 2D perovskite systems under investigation in this work is (PEA)2(MA)n-1[PbnI3n+1] (PEA = phenethyl ammonium, MA = methyl ammonium). Here, we examine two layered 2D perovskites with different distributions of quantum well thicknesses. Spectroscopic measurements and model calculations suggest that both systems funnel electronic excitations from the back to the front of the film through energy transfer mechanisms on the time scales of 100's of ps (i.e., energy transfer from thinner to thicker quantum wells). In addition, the model calculations demonstrate that the transient absorption spectra are composed of a progression of single exciton and biexciton resonances associated with the individual quantum wells. We find that exciton dissociation and/or charge transport dynamics make only minor contributions to the transient absorption spectra within the first 1 ns after photo-excitation. An analysis of the energy transfer kinetics indicates that the transitions occur primarily between quantum wells with values of n that differ by 1 because of the spectral overlap factor that governs the energy transfer rate. Two-dimensional transient absorption spectra reveal a pattern of resonances consistent with the dominance of sequential energy transfer dynamics.

The 4.5 micron Sulfate Absorption Feature on Mars and Its Relationship to Formation Environment

NASA Technical Reports Server (NTRS)

Blaney, D. L.

2001-01-01

The 4.5 micron sulfate absorption feature on Mars is spatially variable. It is a sensitive composition and hydration state and can be used to identify different types of aqueous environments. Additional information is contained in the original extended abstract.

The UV to Near-IR Optical Properties of PAHs: A Semi-Empirical Model

NASA Technical Reports Server (NTRS)

Mattioda, A. L.; Allamandola, L. J.; Hudgins, D. M.

2005-01-01

Interstellar Polycyclic Aromatic Hydrocarbon (PAH) infrared emission features represent an important and unique diagnostic tool of the chemical and physical conditions throughout the universe. However, one challenge facing the widely accepted PAH emission model has been the detection of infrared features in regions of low UV flux. Utilizing recently published laboratory Near Infrared VIR) PAH ion absorption data measured in our laboratory, we build upon previous models for PAH ion absorption in the UV-Vis to extrapolate a new model which incorporates PAH ion absorption in the NIR. This model provides a basis for comparing the relative energy absorption of PAH ions in the UV-Vis and NIR regions for a wide variety of stellar types. This model demonstrates that the radiation from late-type stars can pump the mid-IR PAH features.

Deep-HiTS: Rotation Invariant Convolutional Neural Network for Transient Detection

NASA Astrophysics Data System (ADS)

Cabrera-Vives, Guillermo; Reyes, Ignacio; Förster, Francisco; Estévez, Pablo A.; Maureira, Juan-Carlos

2017-02-01

We introduce Deep-HiTS, a rotation-invariant convolutional neural network (CNN) model for classifying images of transient candidates into artifacts or real sources for the High cadence Transient Survey (HiTS). CNNs have the advantage of learning the features automatically from the data while achieving high performance. We compare our CNN model against a feature engineering approach using random forests (RFs). We show that our CNN significantly outperforms the RF model, reducing the error by almost half. Furthermore, for a fixed number of approximately 2000 allowed false transient candidates per night, we are able to reduce the misclassified real transients by approximately one-fifth. To the best of our knowledge, this is the first time CNNs have been used to detect astronomical transient events. Our approach will be very useful when processing images from next generation instruments such as the Large Synoptic Survey Telescope. We have made all our code and data available to the community for the sake of allowing further developments and comparisons at https://github.com/guille-c/Deep-HiTS. Deep-HiTS is licensed under the terms of the GNU General Public License v3.0.

Ultrafast photophysics of pi-conjugated polymers for organic light emitting diode applications

NASA Astrophysics Data System (ADS)

Olejnik, Ella

In this work we used the pump-probe photomodulation (PM) spectroscopy technique to measure the transient PM spectrum and decay kinetics in various pi -- conjugated polymers (PCPs) films and blends. Using two ultrafast laser systems, we covered a broad spectral range from 0.25 -- 2.5 eV in the time domain from 200 fs to 1 ns with 150 fs time resolution. We also used continuous wave (CW) photomodulation spectroscopy, photoluminescence (PL), electro-absorption and doping-induced absorption to study the photoexcitations and other optical properties of PCPs and guest/ host blends. In particular we studied two different types of Poly(thienylenevinylene) polymer derivatives. One polymer type is the ordered regio-regular (RR) and regio-random (RRa) -- PTV in which the dark exciton, 2Ag is the lowest excited state. In these polymers the photoexcited exciton shows very fast decay kinetics due to the internal conversion to the dark exciton, which results in weak PL emission; thus these two polymers are non-luminescent. The other PTV derivative is the imide -- PTV which is more luminescent due to the proximity of 1Bu and 2Ag states, that results in longer decay kinetics and a difference between the calculated value of the QEPL (9%) and the measured one (1%). We also demonstrate transient strain spectroscopy in RR -- PTV thin films, where the ultrafast energy release associated with the exciton decay gives rise to substantial static and dynamic strains in the film that dramatically influences the film's transient PM response. We also study the photophysics of poly(dioctyloxy) phenylenevinylene polymer with different isotopes, where we substituted hydrogen (H-polymer) by deuterium (D-polymer), and 12C by 13C isotopes. From the transient decay kinetics measurements we found that the exciton recombination in DOO -- PPV consists of two processes. These are: intrinsic monomolecular, and exciton-exciton annihilation (bimolecular). In the D -- polymer, different probe frequencies of the main exciton photoinduced absorption band (PA1) show a variety of decay kinetics that result from various photoexcitations that contribute to the spectrum. Comparing the transient PM spectrum at 1 ns time delay to the CW PM shows the formation of triplet excitons, which is possible due to singlet fission of mAg (at 2.9 eV) into two triplets (2 X 1.4 eV). In the last part of this thesis we summarize our studies of organic light emitting diodes (OLED) devices based on a host/guest blend of Polyfluorene polymer that is mixed with various percentages of Ir(btp)2acac molecules. In this mixture the PFO (host) shows blue fluorescence, whereas the Ir-complex (guest) has red phosphorescence emission; thus OLED based on this mixture can serve as a `white OLED'. Since the PFO emission spectrum perfectly matches the absorption band of the Ir-complex, it induces an efficient energy transfer from the PFO host to the Ir-complex guest molecules, which we tried to time resolve by the transient PM method.

O2 on ganymede: Spectral characteristics and plasma formation mechanisms

USGS Publications Warehouse

Calvin, W.M.; Johnson, R.E.; Spencer, J.R.

1996-01-01

Weak absorption features in the visible reflectance spectrum of Jupiter's satellite Ganymede have been correlated to those observed in the spectrum of molecular oxygen. We examine the spectral characteristics of these absorption features in all phases of O2 and conclude that the molecular oxygen is most likely present at densities similar to the liquid or solid ??-phase. The contribution of O2 to spectral features observed on Ganymede in the near-infrared wavelength region affects the previous estimates of photon pathlength in ice. The concentration of the visible absorption features on the trailing hemisphere of Ganymede suggests an origin due to bombardment by magneto-spheric ions. We derive an approximate O2 formation rate from this mechanism and consider the state of O2 within the surface.

Temporal and spatial adaptation of transient responses to local features

PubMed Central

O'Carroll, David C.; Barnett, Paul D.; Nordström, Karin

2012-01-01

Interpreting visual motion within the natural environment is a challenging task, particularly considering that natural scenes vary enormously in brightness, contrast and spatial structure. The performance of current models for the detection of self-generated optic flow depends critically on these very parameters, but despite this, animals manage to successfully navigate within a broad range of scenes. Within global scenes local areas with more salient features are common. Recent work has highlighted the influence that local, salient features have on the encoding of optic flow, but it has been difficult to quantify how local transient responses affect responses to subsequent features and thus contribute to the global neural response. To investigate this in more detail we used experimenter-designed stimuli and recorded intracellularly from motion-sensitive neurons. We limited the stimulus to a small vertically elongated strip, to investigate local and global neural responses to pairs of local “doublet” features that were designed to interact with each other in the temporal and spatial domain. We show that the passage of a high-contrast doublet feature produces a complex transient response from local motion detectors consistent with predictions of a simple computational model. In the neuron, the passage of a high-contrast feature induces a local reduction in responses to subsequent low-contrast features. However, this neural contrast gain reduction appears to be recruited only when features stretch vertically (i.e., orthogonal to the direction of motion) across at least several aligned neighboring ommatidia. Horizontal displacement of the components of elongated features abolishes the local adaptation effect. It is thus likely that features in natural scenes with vertically aligned edges, such as tree trunks, recruit the greatest amount of response suppression. This property could emphasize the local responses to such features vs. those in nearby texture within the scene. PMID:23087617

Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations

DOE PAGES

Zheng, Kaibo; Chen, Yani; Sun, Yong; ...

2018-01-01

Photo-generated charge carrier dynamics in Ruddlesden–Popper 2D perovskites with linear ( n -BA) and branched (iso-BA) butylamine as spacing cations have been studied by using transient absorption and time-resolved photoluminescence spectroscopies.

Inter-phase charge and energy transfer in Ruddlesden–Popper 2D perovskites: critical role of the spacing cations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Kaibo; Chen, Yani; Sun, Yong

Photo-generated charge carrier dynamics in Ruddlesden–Popper 2D perovskites with linear ( n -BA) and branched (iso-BA) butylamine as spacing cations have been studied by using transient absorption and time-resolved photoluminescence spectroscopies.

Use of airborne imaging spectrometer data to map minerals associated with hydrothermally altered rocks in the northern grapevine mountains, Nevada, and California

USGS Publications Warehouse

Kruse, F.A.

1988-01-01

Three flightlines of Airborne Imaging Spectrometer (AIS) data, acquired over the northern Grapevine Mountains, Nevada, and California, were used to map minerals associated with hydrothermally altered rocks. The data were processed to remove vertical striping, normalized using an equal area normalization, and reduced to reflectance relative to an average spectrum derived from the data. An algorithm was developed to automatically calculate the absorption band parameters band position, band depth, and band width for the strongest absorption feature in each pixel. These parameters were mapped into an intensity, hue, saturation (IHS) color system to produce a single color image that summarized the absorption band information, This image was used to map areas of potential alteration based upon the predicted relationships between the color image and mineral absorption band. Individual AIS spectra for these areas were then examined to identify specific minerals. Two types of alteration were mapped with the AIS data. Areas of quartz-sericite-pyrite alteration were identified based upon a strong absorption feature near 2.21 ??m, a weak shoulder near 2.25 ??m, and a weak absorption band near 2.35 ??m caused by sericite (fine-grained muscovite). Areas of argillic alteration were defined based on the presence of montmorillonite, identified by a weak to moderate absorption feature near 2.21 ??m and the absence of the 2.35 ??m band. Montmorillonite could not be identified in mineral mixtures. Calcite and dolomite were identified based on sharp absorption features near 2.34 and 2.32 ??m, respectively. Areas of alteration identified using the AIS data corresponded well with areas mapped using field mapping, field reflectance spectra, and laboratory spectral measurements. ?? 1988.

Derivative Analysis of Absorption Features in Hyperspectral Remote Sensing Data of Carbonate Sediments

DTIC Science & Technology

2002-12-30

reflectance of carbonate sediments and application to shallow water benthic habitat classification,” Doctoral Dissertation, University of Miami. Chap.3...resolve overlapping features. A primary application has been to analyze pigment and chemical composition of leaves in order to track physiological...final absorption feature was observed at 630 nm, in a region associated with the biliprotein, phycocyanin [16,17]. As biliproteins are water soluble

Ultrafast studies of the excited-state dynamics of copper and nickel phthalocyanine tetrasulfonates: potential sensitizers for the two-photon photodynamic therapy of tumors.

PubMed

Fournier, Michel; Pépin, Claude; Houde, Daniel; Ouellet, René; van Lier, Johan E

2004-01-01

In order to evaluate the potential of copper and nickel phthalocyanine tetrasulfonates as sensitizers for two-photon photodynamic therapy, we conducted kinetic femtosecond measurements of transient absorption and bleaching of their excited state dynamics in aqueous solution. Samples were pumped with 620 nm and 310 nm laser light, which allowed us to study relaxation processes from both the first and second singlet (or doublet for the copper phthalocyanine) excited states. A second excitation from the first excited triplet state, approximately 685 and 105 ps after the first excitation for copper and nickel phthalocyanine tetrasulfonate respectively, was the most efficient way to bring the molecules to an upper triplet state. Presumably this highest triplet state can inflict molecular damage on adjacent biomolecules int eh absence of oxygen, resulting in the desired cytotoxic cellular response. Transient absorption spectra at different fixed delays indicate that optimum efficiency would require that the second photon has a wavelength of approximately 750 nm.

Simplification of femtosecond transient absorption microscopy data from CH 3NH 3PbI 3 perovskite thin films into decay associated amplitude maps

DOE PAGES

Doughty, Benjamin; Simpson, Mary Jane; Yang, Bin; ...

2016-02-16

Our work aims to simplify multi-dimensional femtosecond transient absorption microscopy (TAM) data into decay associated amplitude maps that describe the spatial distributions of dynamical processes occurring on various characteristic timescales. Application of this method to TAM data obtained from a model methyl-ammonium lead iodide (CH 3NH 3PbI 3) perovskite thin film allows us to simplify the dataset consisting of a 68 time-resolved images into 4 decay associated amplitude maps. Furthermore, these maps provide a simple means to visualize the complex electronic excited-state dynamics in this system by separating distinct dynamical processes evolving on characteristic timescales into individual spatial images. Thismore » approach provides new insight into subtle aspects of ultrafast relaxation dynamics associated with excitons and charge carriers in the perovskite thin film, which have recently been found to coexist at spatially distinct locations.« less

Analytical model for atomic resonant attosecond transient absorption

NASA Astrophysics Data System (ADS)

Cariker, C.; Kjellson, T.; Lindroth, E.; Argenti, L.

2017-04-01

Recent advancements in ultrafast laser technology have made it possible to probe electron dynamics in highly excited atomic states that autoionize on a femtosecond timescale, thus giving insight into the dynamics of Auger decay and its interference with the continuum. These experiments provide a stringent test for time-resolved analytical models of autoionization. Here we present a finite-pulse, multi-photon perturbative model which is used in conjunction with ab-initio structure calculations to predict the attosecond transient absorption spectrum (ATAS) of an atom above the ionization threshold. We apply this model to compute the ATAS of argon in the vicinity of the 3s-1 4 p resonance as a function of the time delay between an extreme ultraviolet (XUV) and an infrared (IR) pulse, as well as of the angle between their polarization. We show that by modulating the parameters of the IR pulse it is possible to control the dipolar coupling between neighboring states and hence the lineshape of the 3s-1 4 p resonance. NSF Grant No. 1607588.

Excitonic Effects in Methylammonium Lead Halide Perovskites.

PubMed

Chen, Xihan; Lu, Haipeng; Yang, Ye; Beard, Matthew C

2018-05-17

The exciton binding energy in methylammonium lead iodide (MAPbI 3 ) is about 10 meV, around 1/3 of the available thermal energy ( k B T ∼ 26 meV) at room temperature. Thus, exciton populations are not stable at room temperature at moderate photoexcited carrier densities. However, excitonic resonances dominate the absorption onset. Furthermore, these resonances determine the transient absorbance and transient reflectance spectra. The exciton binding energy is a reflection of the Coulomb interaction energy between photoexcited electrons and holes. As such, it serves as a marker for the strength of electron/hole interactions and impacts a variety of phenomena, such as, absorption, radiative recombination, and Auger recombination. In this Perspective, we discuss the role of excitons and excitonic resonances in the optical properties of lead-halide perovskite semiconductors. Finally, we discuss how the strong light-matter interactions induce an optical stark effect splitting the doubly spin degenerate ground exciton states and are easily observed at room temperature.

Apparatus and method for transient thermal infrared spectrometry

DOEpatents

McClelland, John F.; Jones, Roger W.

1991-12-03

A method and apparatus for enabling analysis of a material (16, 42) by applying a cooling medium (20, 54) to cool a thin surface layer portion of the material and to transiently generate a temperature differential between the thin surface layer portion and the lower portion of the material sufficient to alter the thermal infrared emission spectrum of the material from the black-body thermal infrared emission spectrum of the material. The altered thermal infrared emission spectrum of the material is detected by a spectrometer/detector (28, 50) while the altered thermal infrared emission spectrum is sufficiently free of self-absorption by the material of the emitted infrared radiation. The detection is effected prior to the temperature differential propagating into the lower portion of the material to an extent such that the altered thermal infrared emission spectrum is no longer sufficiently free of self-absorption by the material of emitted infrared radiation, so that the detected altered thermal infrared emission spectrum is indicative of the characteristics relating to the molecular composition of the material.

Ultrafast Hole Trapping and Relaxation Dynamics in p-Type CuS Nanodisks

DOE PAGES

Ludwig, John; An, Li; Pattengale, Brian; ...

2015-06-22

CuS nanocrystals are potential materials for developing low-cost solar energy conversion devices. Understanding the underlying dynamics of photoinduced carriers in CuS nanocrystals is essential to improve their performance in these devices. In this work, we investigated the photoinduced hole dynamics in CuS nanodisks (NDs) using the combination of transient optical (OTA) and X-ray (XTA) absorption spectroscopy. OTA results show that the broad transient absorption in the visible region is attributed to the photoinduced hot and trapped holes. The hole trapping process occurs on a subpicosecond time scale, followed by carrier recombination (~100 ps). The nature of the hole trapping sites,more » revealed by XTA, is characteristic of S or organic ligands on the surface of CuS NDs. Lastly, these results not only suggest the possibility to control the hole dynamics by tuning the surface chemistry of CuS but also represent the first time observation of hole dynamics in semiconductor nanocrystals using XTA.« less

Optical spectroscopy of nanoscale and heterostructured oxides

NASA Astrophysics Data System (ADS)

Senty, Tess R.

Through careful analysis of a material's properties, devices are continually getting smaller, faster and more efficient each day. Without a complete scientific understanding of material properties, devices cannot continue to improve. This dissertation uses optical spectroscopy techniques to understand light-matter interactions in several oxide materials with promising uses mainly in light harvesting applications. Linear absorption, photoluminescence and transient absorption spectroscopy are primarily used on europium doped yttrium vanadate nanoparticles, copper gallium oxide delafossites doped with iron, and cadmium selenide quantum dots attached to titanium dioxide nanoparticles. Europium doped yttrium vanadate nanoparticles have promising applications for linking to biomolecules. Using Fourier-transform infrared spectroscopy, it was shown that organic ligands (benzoic acid, 3-nitro 4-chloro-benzoic acid and 3,4-dihydroxybenzoic acid) can be attached to the surface of these molecules using metal-carboxylate coordination. Photoluminescence spectroscopy display little difference in the position of the dominant photoluminescence peaks between samples with different organic ligands although there is a strong decrease in their intensity when 3,4-dihydroxybenzoic acid is attached. It is shown that this strong quenching is due to the presence of high-frequency hydroxide vibrational modes within the organic linker. Ultraviolet/visible linear absorption measurements on delafossites display that by doping copper gallium oxide with iron allows for the previously forbidden fundamental gap transition to be accessed. Using tauc plots, it is shown that doping with iron lowers the bandgap from 2.8 eV for pure copper gallium oxide, to 1.7 eV for samples with 1 -- 5% iron doping. Using terahertz transient absorption spectroscopy measurements, it was also determined that doping with iron reduces the charge mobility of the pure delafossite samples. A comparison of cadmium selenide quantum dots, both with and without capping ligands, attached to titanium dioxide nanoparticles is performed using a new transient absorption analysis technique. Multiple exponential fit models were applied to the system and compared with the new inversion analysis technique. It is shown how the new inversion analysis can map out the charge carrier dynamics, providing carrier recombination rates and lifetimes as a function of carrier concentration, where the multiple exponential fit technique is not dependent on the carrier concentration. With the inversion analysis technique it is shown that capping ligands allow for increased charge transfer due to traps being passivated on the quantum dot surface.

Impact of metal ions in porphyrin-based applied materials for visible-light photocatalysis: key information from ultrafast electronic spectroscopy.

PubMed

Kar, Prasenjit; Sardar, Samim; Alarousu, Erkki; Sun, Jingya; Seddigi, Zaki S; Ahmed, Saleh A; Danish, Ekram Y; Mohammed, Omar F; Pal, Samir Kumar

2014-08-11

Protoporphyrin IX-zinc oxide (PP-ZnO) nanohybrids have been synthesized for applications in photocatalytic devices. High-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), and steady-state infrared, absorption, and emission spectroscopies have been used to analyze the structural details and optical properties of these nanohybrids. Time-resolved fluorescence and transient absorption techniques have been applied to study the ultrafast dynamic events that are key to photocatalytic activities. The photocatalytic efficiency under visible-light irradiation in the presence of naturally abundant iron(III) and copper(II) ions has been found to be significantly retarded in the former case, but enhanced in the latter case. More importantly, femtosecond (fs) transient absorption data have clearly demonstrated that the residence of photoexcited electrons from the sensitizer PP in the centrally located iron moiety hinders ground-state bleach recovery of the sensitizer, affecting the overall photocatalytic rate of the nanohybrid. The presence of copper(II) ions, on the other hand, offers additional stability against photobleaching and eventually enhances the efficiency of photocatalysis. In addition, we have also explored the role of UV light in the efficiency of photocatalysis and have rationalized our observations from femtosecond- to picosecond-resolved studies. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The low-lying {pi}{sigma}* state and its role in the intramolecular charge transfer of aminobenzonitriles and aminobenzethyne

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Jae-Kwang; Fujiwara, Takashige; Kofron, William G.

2008-04-28

Electronic absorption spectra of the low-lying {pi}{pi}* and {pi}{sigma}* states of several aminobenzonitriles and 4-dimethylaminobenzethyne have been studied by time-resolved transient absorption and time-dependent density functional theory calculation. In acetonitrile, the lifetime of the {pi}{sigma}*-state absorption is very short (picoseconds or subpicosecond) for molecules that exhibit intramolecular charge transfer (ICT), and very long (nanoseconds) for those that do not. Where direct comparison of the temporal characteristics of the {pi}{sigma}*-state and the ICT-state transients could be made, the formation rate of the ICT state is identical to the decay rate of the {pi}{sigma}* state within the experimental uncertainty. These results aremore » consistent with the {pi}{sigma}*-mediated ICT mechanism, L{sub a} ({pi}{pi}*){yields}{pi}{sigma}*{yields}ICT, in which the decay rate of the {pi}{sigma}* state is determined by the rate of the solvent-controlled {pi}{sigma}*{yields}ICT charge-shift reaction. The {pi}{pi}*{yields}{pi}{sigma}* state crossing does not occur in 3-dimethylaminobenzonitrile or 2-dimethylaminobenzonitrile, as predicted by the calculation, and 4-aminobenzonitrile and 4-dimethylaminobenzethyne does not exhibit the ICT reaction, consistent with the higher energy of the ICT state relative to the {pi}{sigma}* state.« less

Attosecond transient absorption instrumentation for thin film materials: Phase transitions, heat dissipation, signal stabilization, timing correction, and rapid sample rotation.

PubMed

Jager, Marieke F; Ott, Christian; Kaplan, Christopher J; Kraus, Peter M; Neumark, Daniel M; Leone, Stephen R

2018-01-01

We present an extreme ultraviolet (XUV) transient absorption apparatus tailored to attosecond and femtosecond measurements on bulk solid-state thin-film samples, specifically when the sample dynamics are sensitive to heating effects. The setup combines methodology for stabilizing sub-femtosecond time-resolution measurements over 48 h and techniques for mitigating heat buildup in temperature-dependent samples. Single-point beam stabilization in pump and probe arms and periodic time-zero reference measurements are described for accurate timing and stabilization. A hollow-shaft motor configuration for rapid sample rotation, raster scanning capability, and additional diagnostics are described for heat mitigation. Heat transfer simulations performed using a finite element analysis allow comparison of sample rotation and traditional raster scanning techniques for 100 Hz pulsed laser measurements on vanadium dioxide, a material that undergoes an insulator-to-metal transition at a modest temperature of 340 K. Experimental results are presented confirming that the vanadium dioxide (VO 2 ) sample cannot cool below its phase transition temperature between laser pulses without rapid rotation, in agreement with the simulations. The findings indicate the stringent conditions required to perform rigorous broadband XUV time-resolved absorption measurements on bulk solid-state samples, particularly those with temperature sensitivity, and elucidate a clear methodology to perform them.

Reaction CH3 + OH studied over the 294-714 K temperature and 1-100 bar pressure ranges.

PubMed

Sangwan, Manuvesh; Chesnokov, Evgeni N; Krasnoperov, Lev N

2012-08-30

Reaction of methyl radicals with hydroxyl radicals, CH(3) + OH → products (1) was studied using pulsed laser photolysis coupled to transient UV-vis absorption spectroscopy over the 294-714 K temperature and 1-100 bar pressure ranges (bath gas He). Methyl radicals were produced by photolysis of acetone at 193.3 nm. Hydroxyl radicals were generated in reaction of electronically excited oxygen atoms O((1)D), produced in the photolysis of N(2)O at 193.3 nm, with H(2)O. Temporal profiles of CH(3) were recorded via absorption at 216.4 nm using xenon arc lamp and a spectrograph; OH radicals were monitored via transient absorption of light from a dc discharge H(2)O/Ar low pressure resonance lamp at ca. 308 nm. The absolute intensity of the photolysis light inside the reactor was determined by an accurate in situ actinometry based on the ozone formation in the presence of molecular oxygen. The results of this study indicate that the rate constant of reaction 1 is pressure independent within the studied pressure and temperature ranges and has slight negative temperature dependence, k(1) = (1.20 ± 0.20) × 10(-10)(T/300)(-0.49) cm(3) molecule(-1) s(-1).

Attosecond transient absorption instrumentation for thin film materials: Phase transitions, heat dissipation, signal stabilization, timing correction, and rapid sample rotation

NASA Astrophysics Data System (ADS)

Jager, Marieke F.; Ott, Christian; Kaplan, Christopher J.; Kraus, Peter M.; Neumark, Daniel M.; Leone, Stephen R.

2018-01-01

We present an extreme ultraviolet (XUV) transient absorption apparatus tailored to attosecond and femtosecond measurements on bulk solid-state thin-film samples, specifically when the sample dynamics are sensitive to heating effects. The setup combines methodology for stabilizing sub-femtosecond time-resolution measurements over 48 h and techniques for mitigating heat buildup in temperature-dependent samples. Single-point beam stabilization in pump and probe arms and periodic time-zero reference measurements are described for accurate timing and stabilization. A hollow-shaft motor configuration for rapid sample rotation, raster scanning capability, and additional diagnostics are described for heat mitigation. Heat transfer simulations performed using a finite element analysis allow comparison of sample rotation and traditional raster scanning techniques for 100 Hz pulsed laser measurements on vanadium dioxide, a material that undergoes an insulator-to-metal transition at a modest temperature of 340 K. Experimental results are presented confirming that the vanadium dioxide (VO2) sample cannot cool below its phase transition temperature between laser pulses without rapid rotation, in agreement with the simulations. The findings indicate the stringent conditions required to perform rigorous broadband XUV time-resolved absorption measurements on bulk solid-state samples, particularly those with temperature sensitivity, and elucidate a clear methodology to perform them.

Modeling and analysis of the chip formation and transient cutting force during elliptical vibration cutting process

NASA Astrophysics Data System (ADS)

Lin, Jieqiong; Guan, Liang; Lu, Mingming; Han, Jinguo; Kan, Yudi

2017-12-01

In traditional diamond cutting, the cutting force is usually large and it will affect tool life and machining quality. Elliptical vibration cutting (EVC) as one of the ultra-precision machining technologies has a lot of advantages, such as reduces cutting force, extend tool life and so on. It's difficult to predict the transient cutting force of EVC due to its unique elliptical motion trajectory. Study on chip formation will helpfully to predict cutting force. The geometric feature of chip has important effects on cutting force, however, few scholars have studied the chip formation. In order to investigate the time-varying cutting force of EVC, the geometric feature model of chip is established based on analysis of chip formation, and the effects of cutting parameters on the geometric feature of chip are analyzed. To predict transient force quickly and effectively, the geometric feature of chip is introduced into the cutting force model. The calculated results show that the error between the predicted cutting force in this paper and that in the literature is less than 2%, which proves its feasibility.

Plant phenolics and absorption features in vegetation reflectance spectra near 1.66 μm

NASA Astrophysics Data System (ADS)

Kokaly, Raymond F.; Skidmore, Andrew K.

2015-12-01

Past laboratory and field studies have quantified phenolic substances in vegetative matter from reflectance measurements for understanding plant response to herbivores and insect predation. Past remote sensing studies on phenolics have evaluated crop quality and vegetation patterns caused by bedrock geology and associated variations in soil geochemistry. We examined spectra of pure phenolic compounds, common plant biochemical constituents, dry leaves, fresh leaves, and plant canopies for direct evidence of absorption features attributable to plant phenolics. Using spectral feature analysis with continuum removal, we observed that a narrow feature at 1.66 μm is persistent in spectra of manzanita, sumac, red maple, sugar maple, tea, and other species. This feature was consistent with absorption caused by aromatic Csbnd H bonds in the chemical structure of phenolic compounds and non-hydroxylated aromatics. Because of overlapping absorption by water, the feature was weaker in fresh leaf and canopy spectra compared to dry leaf measurements. Simple linear regressions of feature depth and feature area with polyphenol concentration in tea resulted in high correlations and low errors (% phenol by dry weight) at the dry leaf (r2 = 0.95, RMSE = 1.0%, n = 56), fresh leaf (r2 = 0.79, RMSE = 2.1%, n = 56), and canopy (r2 = 0.78, RMSE = 1.0%, n = 13) levels of measurement. Spectra of leaves, needles, and canopies of big sagebrush and evergreens exhibited a weak absorption feature centered near 1.63 μm, short ward of the phenolic compounds, possibly consistent with terpenes. This study demonstrates that subtle variation in vegetation spectra in the shortwave infrared can directly indicate biochemical constituents and be used to quantify them. Phenolics are of lesser abundance compared to the major plant constituents but, nonetheless, have important plant functions and ecological significance. Additional research is needed to advance our understanding of the spectral influences of plant phenolics and terpenes relative to dominant leaf biochemistry (water, chlorophyll, protein/nitrogen, cellulose, and lignin).

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

PubMed Central

Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; van Driel, Tim B.; Adachi, Shin-ichi; Bordage, Amélie; Bressler, Christian; Chabera, Pavel; Christensen, Morten; Dohn, Asmus O.; Galler, Andreas; Gawelda, Wojciech; Gosztola, David; Haldrup, Kristoffer; Harlang, Tobias; Liu, Yizhu; Møller, Klaus B.; Németh, Zoltán; Nozawa, Shunsuke; Pápai, Mátyás; Sato, Tokushi; Sato, Takahiro; Suarez-Alcantara, Karina; Togashi, Tadashi; Tono, Kensuke; Uhlig, Jens; Vithanage, Dimali A.; Wärnmark, Kenneth; Yabashi, Makina; Zhang, Jianxin; Sundström, Villy; Nielsen, Martin M.

2015-01-01

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances. Experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined. PMID:25727920

Visualizing the non-equilibrium dynamics of photoinduced intramolecular electron transfer with femtosecond X-ray pulses

DOE PAGES

Canton, Sophie E.; Kjær, Kasper S.; Vankó, György; ...

2015-03-02

Ultrafast photoinduced electron transfer preceding energy equilibration still poses many experimental and conceptual challenges to the optimization of photoconversion since an atomic-scale description has so far been beyond reach. Here we combine femtosecond transient optical absorption spectroscopy with ultrafast X-ray emission spectroscopy and diffuse X-ray scattering at the SACLA facility to track the non-equilibrated electronic and structural dynamics within a bimetallic donor–acceptor complex that contains an optically dark centre. Exploiting the 100-fold increase in temporal resolution as compared with storage ring facilities, these measurements constitute the first X-ray-based visualization of a non-equilibrated intramolecular electron transfer process over large interatomic distances.more » Thus experimental and theoretical results establish that mediation through electronically excited molecular states is a key mechanistic feature. The present study demonstrates the extensive potential of femtosecond X-ray techniques as diagnostics of non-adiabatic electron transfer processes in synthetic and biological systems, and some directions for future studies, are outlined.« less

Spectroscopic and theoretical investigations on intramolecular charge transfer phenomenon in 1-3-dioxolane derivative

NASA Astrophysics Data System (ADS)

Zhang, Zhiyong; Zhang, Zhongzhi; Luo, Yijing; Sun, Shanshan; Zhang, Guangqing

2018-02-01

High fluorescence quantum yield (FQY) and large Stokes shift (SS) cannot be easily achieved simultaneously by traditional PICT or TICT fluorescent probe. However, an 1-3-dioxolane derivative named 5-methyl-8,9-dihydro-5H-[1,3]dioxolo[4,5-b]carbazol-6(7H)-one (MDDCO) features both high FQY and large SS. The purpose of this study is to search the mechanism behind this phenomenon by theoretical method. Simulated structure changes and charge transfer suggest ICT process in MDDCO is similar to PLICT (Planarized Intramolecular Charge Transfer) process. Calculated UV-Vis spectra and fluorescence spectra show that PLICT-like state (S1 state) of MDDCO leads to large SS. Computed transient-absorption spectra and radiative decay rates indicate that PLICT-like state is key factor for high FQY of MDDCO. These findings suggest that PLICT-like state in 1,3-dioxolane derivatives can achieve both large SS and high FQY, which presents a new method for high-performance fluorescent probe design.

Tuning pentacene based dye-sensitized solar cells.

PubMed

Kunzmann, Andreas; Gruber, Marco; Casillas, Rubén; Tykwinski, Rik R; Costa, Rubén D; Guldi, Dirk M

2018-05-10

We report on the synthesis, as well as photophysical and electrochemical characterization of a new family of pentacene derivatives, which are applied in n-type dye-sensitized solar cells (DSSCs). As far as the molecular structure of the pentacene is concerned, the synthetic design focuses on cyano acrylic tethered at the 13-position of the pentacene chromophore. The electrolyte composition features increasing amounts of Li+ ions as an additive. In general, the increase of Li+ concentrations extrinsically reduces the quasi Fermi level of the photoanode and as such facilitates the electron injection process. We demonstrate that pentacene derivatives give rise to a unique charge injection process, which is controlled by the positioning of the quasi Fermi level energies as a function of the Li+ concentration. As a result of the enhanced charge injection, device efficiencies as high as 1.5% are achieved, representing a 3-fold increase from previously reported efficiencies in pentacene-based DSSCs. These findings are supported by device analysis in combination with transient absorption and electrochemical impedance spectroscopy assays.

Isomerization Intermediates In Solution Phase Photochemistry Of Stilbenes

NASA Astrophysics Data System (ADS)

Doany, F. E.; Hochstrasser, R. M.; Greene, B. I.

1985-04-01

Picosecond and subpicosecond spectroscopic studies have revealed evidence for an isomerization intermediate between cis and trans in the photoinduced isomerism of both stilbene and biindanyledene ("stiff" stilbene). In stiff stilbene, a transient absorption at 351 nm displays time evolution and viscosity dependence consistent with absorption by a twisted intermediate ("phantom" state) with a lOps lifetime. An analagous bottleneck state with a life-time of 4ps is also consistent with the ground state recovery dynamics of t-stilbene following excitation of c-stilbene when monitored with 0.1ps resolution.

The theory of the anti-maser: coherent perfect absorption of RF

NASA Astrophysics Data System (ADS)

Aviles, Michael; Mazzocco, Anthony; Andrews, Jim; Dawson, Nathan; Crescimanno, Michael

2012-10-01

The radio frequency (RF)-analogue of the anti-laser is developed using four terminal network theory combined with the telegrapher's equation. We describe solutions of the Coherent Perfect Absorption (CPA) condition that are interpretable as the slab dielectric anti-laser. We find a host of other solutions, some of which have no simple optical analogue. Broadband solutions are found which hint at the possibility of a new type of asymmetric transient CPA phenomenon, and point out that this study suggests a potentially new low loss, reversible RF devices.

An electrochemical and photophysical study of a covalently linked inorganic-organic dyad.

PubMed

Kahnt, Axel; Heiniger, Leo-Philipp; Liu, Shi-Xia; Tu, Xiaoyan; Zheng, Zhiping; Hauser, Andreas; Decurtins, Silvio; Guldi, Dirk M

2010-02-22

A molecular donor-acceptor dyad comprising a hexarhenium cluster core, [Re(6)(mu(3)-Se)(8)](2+), and a fullerene moiety which are covalently linked through a pyridine ligand was synthesized and fully characterized. The electrochemical and photophysical properties are reported. The detailed study includes cyclic voltammetry, steady-state absorption and fluorescence spectroscopy, radiation chemistry and transient absorption spectroscopy. A light-induced electron transfer between the inorganic cluster moiety and the fullerene can be excluded. However, a light-induced energy transfer from the rhenium cluster to the fullerene is proposed.

Solid methane on Triton and Pluto - 3- to 4-micron spectrophotometry

NASA Technical Reports Server (NTRS)

Spencer, John R.; Buie, Marc W.; Bjoraker, Gordon L.

1990-01-01

Methane has been identified in the Pluto/Charon system on the basis of absorption features in the reflectance spectrum at 1.5 and 2.3 microns; attention is presently given to observations of a 3.25 micron-centered deep absorption feature in Triton and Pluto/Charon system reflectance spectra. This absorption may indicate the presence of solid methane, constituting either the dominant surface species or a mixture with a highly transparent substance, such as N2 frost.

Reactivity Initiated Accident Simulation to Inform Transient Testing of Candidate Advanced Cladding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Nicholas R; Wysocki, Aaron J; Terrani, Kurt A

2016-01-01

Abstract. Advanced cladding materials with potentially enhanced accident tolerance will yield different light water reactor performance and safety characteristics than the present zirconium-based cladding alloys. These differences are due to different cladding material properties and responses to the transient, and to some extent, reactor physics, thermal, and hydraulic characteristics. Some of the differences in reactors physics characteristics will be driven by the fundamental properties (e.g., absorption in iron for an iron-based cladding) and others will be driven by design modifications necessitated by the candidate cladding materials (e.g., a larger fuel pellet to compensate for parasitic absorption). Potential changes in thermalmore » hydraulic limits after transition from the current zirconium-based cladding to the advanced materials will also affect the transient response of the integral fuel. This paper leverages three-dimensional reactor core simulation capabilities to inform on appropriate experimental test conditions for candidate advanced cladding materials in a control rod ejection event. These test conditions are using three-dimensional nodal kinetics simulations of a reactivity initiated accident (RIA) in a representative state-of-the-art pressurized water reactor with both nuclear-grade iron-chromium-aluminum (FeCrAl) and silicon carbide based (SiC-SiC) cladding materials. The effort yields boundary conditions for experimental mechanical tests, specifically peak cladding strain during the power pulse following the rod ejection. The impact of candidate cladding materials on the reactor kinetics behavior of RIA progression versus reference zirconium cladding is predominantly due to differences in: (1) fuel mass/volume/specific power density, (2) spectral effects due to parasitic neutron absorption, (3) control rod worth due to hardened (or softened) spectrum, and (4) initial conditions due to power peaking and neutron transport cross sections in the equilibrium cycle cores due to hardened (or softened) spectrum. This study shows minimal impact of SiC-based cladding configurations on the transient response versus reference zirconium-based cladding. However, the FeCrAl cladding response indicates similar energy deposition, but with significantly shorter pulses of higher magnitude. Therefore the FeCrAl-based cases have a more rapid fuel thermal expansion rate and the resultant pellet-cladding interaction occurs more rapidly.« less

Real-Time Gas Identification by Analyzing the Transient Response of Capillary-Attached Conductive Gas Sensor

PubMed Central

Bahraminejad, Behzad; Basri, Shahnor; Isa, Maryam; Hambli, Zarida

2010-01-01

In this study, the ability of the Capillary-attached conductive gas sensor (CGS) in real-time gas identification was investigated. The structure of the prototype fabricated CGS is presented. Portions were selected from the beginning of the CGS transient response including the first 11 samples to the first 100 samples. Different feature extraction and classification methods were applied on the selected portions. Validation of methods was evaluated to study the ability of an early portion of the CGS transient response in target gas (TG) identification. Experimental results proved that applying extracted features from an early part of the CGS transient response along with a classifier can distinguish short-chain alcohols from each other perfectly. Decreasing time of exposition in the interaction between target gas and sensing element improved the reliability of the sensor. Classification rate was also improved and time of identification was decreased. Moreover, the results indicated the optimum interval of the early transient response of the CGS for selecting portions to achieve the best classification rates. PMID:22219666

Electrocardiogram ST-Segment Morphology Delineation Method Using Orthogonal Transformations

PubMed Central

2016-01-01

Differentiation between ischaemic and non-ischaemic transient ST segment events of long term ambulatory electrocardiograms is a persisting weakness in present ischaemia detection systems. Traditional ST segment level measuring is not a sufficiently precise technique due to the single point of measurement and severe noise which is often present. We developed a robust noise resistant orthogonal-transformation based delineation method, which allows tracing the shape of transient ST segment morphology changes from the entire ST segment in terms of diagnostic and morphologic feature-vector time series, and also allows further analysis. For these purposes, we developed a new Legendre Polynomials based Transformation (LPT) of ST segment. Its basis functions have similar shapes to typical transient changes of ST segment morphology categories during myocardial ischaemia (level, slope and scooping), thus providing direct insight into the types of time domain morphology changes through the LPT feature-vector space. We also generated new Karhunen and Lo ève Transformation (KLT) ST segment basis functions using a robust covariance matrix constructed from the ST segment pattern vectors derived from the Long Term ST Database (LTST DB). As for the delineation of significant transient ischaemic and non-ischaemic ST segment episodes, we present a study on the representation of transient ST segment morphology categories, and an evaluation study on the classification power of the KLT- and LPT-based feature vectors to classify between ischaemic and non-ischaemic ST segment episodes of the LTST DB. Classification accuracy using the KLT and LPT feature vectors was 90% and 82%, respectively, when using the k-Nearest Neighbors (k = 3) classifier and 10-fold cross-validation. New sets of feature-vector time series for both transformations were derived for the records of the LTST DB which is freely available on the PhysioNet website and were contributed to the LTST DB. The KLT and LPT present new possibilities for human-expert diagnostics, and for automated ischaemia detection. PMID:26863140

Optical detection of tracer species in strongly scattering media.

PubMed

Brauser, Eric M; Rose, Peter E; McLennan, John D; Bartl, Michael H

2015-03-01

A combination of optical absorption and scattering is used to detect tracer species in a strongly scattering medium. An optical setup was developed, consisting of a dual-beam scattering detection scheme in which sample scattering beam overlaps with the characteristic absorption feature of quantum dot tracer species, while the reference scattering beam is outside any absorption features of the tracer. This scheme was successfully tested in engineered breakthrough tests typical of wastewater and subsurface fluid analysis, as well as in batch analysis of oil and gas reservoir fluids and biological samples. Tracers were detected even under highly scattering conditions, conditions in which conventional absorption or fluorescence methods failed.

Multiplexed absorption tomography with calibration-free wavelength modulation spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cai, Weiwei; Kaminski, Clemens F., E-mail: cfk23@cam.ac.uk

2014-04-14

We propose a multiplexed absorption tomography technique, which uses calibration-free wavelength modulation spectroscopy with tunable semiconductor lasers for the simultaneous imaging of temperature and species concentration in harsh combustion environments. Compared with the commonly used direct absorption spectroscopy (DAS) counterpart, the present variant enjoys better signal-to-noise ratios and requires no baseline fitting, a particularly desirable feature for high-pressure applications, where adjacent absorption features overlap and interfere severely. We present proof-of-concept numerical demonstrations of the technique using realistic phantom models of harsh combustion environments and prove that the proposed techniques outperform currently available tomography techniques based on DAS.

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

PubMed

Stuhldreier, Mayra C; Temps, Friedrich

2013-01-01

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

Infrared absorption of CH3OSO detected with time-resolved Fourier-transform spectroscopy.

PubMed

Chen, Jin-Dah; Lee, Yuan-Pern

2011-03-07

A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to detect temporally resolved infrared absorption spectra of CH(3)OSO produced upon irradiation of a flowing gaseous mixture of CH(3)OS(O)Cl in N(2) or CO(2) at 248 nm. Two intense transient features with origins near 1152 and 994 cm(-1) are assigned to syn-CH(3)OSO; the former is attributed to overlapping bands at 1154 ± 3 and 1151 ± 3 cm(-1), assigned to the S=O stretching mixed with CH(3) rocking (ν(8)) and the S=O stretching mixed with CH(3) wagging (ν(9)) modes, respectively, and the latter to the C-O stretching (ν(10)) mode at 994 ± 6 cm(-1). Two weak bands at 2991 ± 6 and 2956 ± 3 cm(-1) are assigned as the CH(3) antisymmetric stretching (ν(2)) and symmetric stretching (ν(3)) modes, respectively. Observed vibrational transition wavenumbers agree satisfactorily with those predicted with quantum-chemical calculations at level B3P86∕aug-cc-pVTZ. Based on rotational parameters predicted at that level, the simulated rotational contours of these bands agree satisfactorily with experimental results. The simulation indicates that the S=O stretching mode of anti-CH(3)OSO near 1164 cm(-1) likely makes a small contribution to the observed band near 1152 cm(-1). A simple kinetic model of self-reaction is employed to account for the decay of CH(3)OSO and yields a second-order rate coefficient k=(4 ± 2)×10(-10) cm(3)molecule(-1)s(-1). © 2011 American Institute of Physics.

Du pompage optique laser à l'absorption saturée résolue en temps

NASA Astrophysics Data System (ADS)

Dumont, M.

The first part is a brief historical account of the beginning of lasers at the « Laboratoire de Spectroscopie Hertzienne de l'ENS » and, more precisely, of the first experiments of optical pumping with multimode lasers. The three new features (stimulated emission, coherence and saturation) are emphasized. Paragraphes 2 and 3 outline the special behaviour of monomode optical pumping (velocity selection) and of timeresolved saturated absorption. This last technique is applied to study elastic collisions (determination of the « collision Kernel ») and Raman coherence between metastable levels. The last paragraphe summarizes a semi-perturbative calculation of transients in Velocity Selective Optical Pumping (VSOP). La première partie est un survol historique de l'introduction des lasers au laboratoire de Spectroscopie Hertzienne de l'ENS et particulièrement des premières expériences de pompage optique avec un laser multimode. Les trois caractéristiques nouvelles (émission stimulée, cohérence de la lumière et saturations) sont mises en lumière. Les paragraphes 2 et 3 présentent les particularités du pompage optique par un laser monomode (sélection des vitesses atomiques) et de la technique d'absorption saturée résolue en temps. Cette dernière technique est appliquée à l'étude des collisions élastiques (détermination du « noyau de collision ») et de la cohérence Raman entre niveaux métastables. La dernière partie présente, de façon résumée, un calcul semiperturbatif des transitoires de pompage optique sélectif en vitesse (VSOP).

Fourier Transform Infrared Absorption Spectroscopy of Gas-Phase and Surface Reaction Products during Si Etching in Inductively Coupled Cl2 Plasmas

NASA Astrophysics Data System (ADS)

Miyata, Hiroki; Tsuda, Hirotaka; Fukushima, Daisuke; Takao, Yoshinori; Eriguchi, Koji; Ono, Kouichi

2011-10-01

A better understanding of plasma-surface interactions is indispensable during etching, including the behavior of reaction or etch products, because the products on surfaces and in the plasma are important in passivation layer formation through their redeposition on surfaces. In practice, the nanometer-scale control of plasma etching would still rely largely on such passivation layer formation as well as ion-enhanced etching on feature surfaces. This paper presents in situ Fourier transform infrared (FTIR) absorption spectroscopy of gas-phase and surface reaction products during inductively coupled plasma (ICP) etching of Si in Cl2. The observation was made in the gas phase by transmission absorption spectroscopy (TAS), and also on the substrate surface by reflection absorption spectroscopy (RAS). The quantum chemical calculation was also made of the vibrational frequency of silicon chloride molecules. The deconvolution of the TAS spectrum revealed absorption features of Si2Cl6 and SiClx (x = 1-3) as well as SiCl4, while that of the RAS spectrum revealed relatively increased absorption features of unsaturated silicon chlorides. A different behavior was also observed in bias power dependence between the TAS and RAS spectra.

Near-infrared diode laser absorption diagnostic for temperature and water vapor in a scramjet combustor

NASA Astrophysics Data System (ADS)

Liu, Jonathan T. C.; Rieker, Gregory B.; Jeffries, Jay B.; Gruber, Mark R.; Carter, Campbell D.; Mathur, Tarun; Hanson, Ronald K.

2005-11-01

Tunable diode laser absorption measurements of gas temperature and water concentration were made at the exit of a model scramjet combustor fueled on JP-7. Multiplexed, fiber-coupled, near-infrared distributed feedback lasers were used to probe three water vapor absorption features in the 1.34 1.47 μm spectral region (2v1 and v1+v3 overtone bands). Ratio thermometry was performed using direct-absorption wavelength scans of isolated features at a 4-kHz repetition rate, as well as 2f wavelength modulation scans at a 2-kHz scan rate. Large signal-to-noise ratios demonstrate the ability of the optimally engineered optical hardware to reject beam steering and vibration noise. Successful measurements were made at full combustion conditions for a variety of fuel/air equivalence ratios and at eight vertical positions in the duct to investigate spatial uniformity. The use of three water vapor absorption features allowed for preliminary estimates of temperature distributions along the line of sight. The improved signal quality afforded by 2f measurements, in the case of weak absorption, demonstrates the utility of a scanned wavelength modulation strategy in such situations.

Spectra of Particulate Backscattering in Natural Waters

NASA Technical Reports Server (NTRS)

Gordon, Howard, R.; Lewis, Marlon R.; McLean, Scott D.; Twardowski, Michael S.; Freeman, Scott A.; Voss, Kenneth J.; Boynton, Chris G.

2009-01-01

Hyperspectral profiles of downwelling irradiance and upwelling radiance in natural waters (oligotrophic and mesotrophic) are combined with inverse radiative transfer to obtain high resolution spectra of the absorption coefficient (a) and the backscattering coefficient (bb) of the water and its constituents. The absorption coefficient at the mesotrophic station clearly shows spectral absorption features attributable to several phytoplankton pigments (Chlorophyll a, b, c, and Carotenoids). The backscattering shows only weak spectral features and can be well represented by a power-law variation with wavelength (lambda): b(sub b) approx. Lambda(sup -n), where n is a constant between 0.4 and 1.0. However, the weak spectral features in b(sub b), suggest that it is depressed in spectral regions of strong particle absorption. The applicability of the present inverse radiative transfer algorithm, which omits the influence of Raman scattering, is limited to lambda < 490 nm in oligotrophic waters and lambda < 575 nm in mesotrophic waters.

Femtosecond stimulated Raman evidence for charge-transfer character in pentacene singlet fission† †Electronic supplementary information (ESI) available: Actinic pump spectrum, discussion on ground state addition process, peak fitting procedure, transient absorption data, power dependence measurements, etalon pulse shaping, TIPS-pentacene FSRS data, and optimized geometry and frequency calculation results. See DOI: 10.1039/c7sc03496b

PubMed Central

Hart, Stephanie M.; Silva, W. Ruchira

2017-01-01

Singlet fission is a spin-allowed process in which an excited singlet state evolves into two triplet states. We use femtosecond stimulated Raman spectroscopy, an ultrafast vibrational technique, to follow the molecular structural evolution during singlet fission in order to determine the mechanism of this process. In crystalline pentacene, we observe the formation of an intermediate characterized by pairs of excited state peaks that are red- and blue-shifted relative to the ground state features. We hypothesize that these features arise from the formation of cationic and anionic species due to partial transfer of electron density from one pentacene molecule to a neighboring molecule. These observations provide experimental evidence for the role of states with significant charge-transfer character which facilitate the singlet fission process in pentacene. Our work both provides new insight into the singlet fission mechanism in pentacene and demonstrates the utility of structurally-sensitive time-resolved spectroscopic techniques in monitoring ultrafast processes. PMID:29675170

A search for ultraviolet circumstellar gas absorption features in alpha Piscis Austrinus (Fomalhaut), a possible Beta Pictoris-like system

NASA Technical Reports Server (NTRS)

Cheng, K.-P.; Bruhweiler, Fred C.; Kondo, Yoji

1994-01-01

Archival high-dispersion International Ultraviolet Explorer (IUE) spectra have been used to search for circumstellar gas absorption features in alpha PsA (A3 V), a nearby (6.7 pc) proto-planetary system candidate. Recent sub-millimeter mapping observations around the region of alpha PsA indicate a spatially resolved dust disk like the one seen around Beta Pic. To determine how closely this putative disk resembles that of Beta Pic, we have searched for signatures of circumstellar gaseous absorption in all the available IUE high-dispersion data of alpha PsA. Examination of co-added IUE spectra shows weak circumstellar absorptions from excited levels in the resonance multiplet of Fe II near 2600 A. We also conclude that the sharp C I feature near 1657 A, previously identified as interstellar absorption toward alpha PsA, likely has a circumstellar origin. However, because the weakness of these absorption features, we will consider the presence of circumstellar gas as tentative and should be verified by using the Goddard High-Resolution Spectrograph aboard the Hubble Space Telescope. No corresponding circumstellar absorption is detected in higher ionization Fe III and Al III. Since the collisionally ionized nonphotospheric Al III resonance absorption seen in Beta Pic is likely formed close to the stellar surface, its absence in the UV spectra of alpha PsA could imply that, in contrast with Beta Pic, there is no active gaseous disk infall onto the central star. In the alpha PsA gaseous disk, if we assume a solar abundance for iron and all the iron is in the form of Fe II, plus a disk temperature of 5000 K, the Fe II UV1 absorption at 2611.8743 A infers a total hydrogen column density along the line of sight through the circumstellar disk of N(H) approximately equals 3.8 x 10(exp 17)/cm.

Characterization of absorption and degradation on optical components for high power excimer lasers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mann, K.; Eva, E.; Granitza, B.

1996-12-31

At Laser-Laboratorium Goettingen, the performance of UV optical components for high power excimer lasers is characterized, aiming to employ testing procedures that meet industrial conditions, i.e. very high pulse numbers and repetition rates. Measurements include determination of single and multiple pulse damage thresholds, absorption loss and degradation of optical properties under long-term irradiation. Absorption of excimer laser pulses is investigated by a calorimetric technique which provides greatly enhanced sensitivity compared to transmissive measurements. Thus, it allows determining both single and two photon absorption coefficients at intensities of standard excimer lasers. Results of absorption measurements at 248nm are presented for baremore » substrates (CaF{sub 2}, BaF{sub 2}, z-cut quartz and fused silica). UV calorimetry is also employed to investigate laser induced aging phenomena, e.g. color center formation in fused silica. A separation of transient and cumulative effects as a function of intensity is achieved, giving insight into various loss mechanisms.« less

Isothermal absorption of soluble gases by atmospheric nanoaerosols

NASA Astrophysics Data System (ADS)

Elperin, T.; Fominykh, A.; Krasovitov, B.; Lushnikov, A.

2013-01-01

We investigate mass transfer during the isothermal absorption of atmospheric trace soluble gases by a single droplet whose size is comparable to the molecular mean free path in air at normal conditions. It is assumed that the trace reactant diffuses to the droplet surface and then reacts with the substances inside the droplet according to the first-order rate law. Our analysis applies a flux-matching theory of transport processes in gases and assumes constant thermophysical properties of the gases and liquids. We derive an integral equation of Volterra type for the transient molecular flux density to a liquid droplet and solve it numerically. Numerical calculations are performed for absorption of sulfur dioxide (SO2), dinitrogen trioxide (N2O3), and chlorine (Cl2) by liquid nanoaerosols accompanied by chemical dissociation reaction. It is shown that during gas absorption by nanoaerosols, the kinetic effects play a significant role, and neglecting kinetic effects leads to a significant overestimation of the soluble gas flux into a droplet during the entire period of gas absorption.

Isothermal absorption of soluble gases by atmospheric nanoaerosols.

PubMed

Elperin, T; Fominykh, A; Krasovitov, B; Lushnikov, A

2013-01-01

We investigate mass transfer during the isothermal absorption of atmospheric trace soluble gases by a single droplet whose size is comparable to the molecular mean free path in air at normal conditions. It is assumed that the trace reactant diffuses to the droplet surface and then reacts with the substances inside the droplet according to the first-order rate law. Our analysis applies a flux-matching theory of transport processes in gases and assumes constant thermophysical properties of the gases and liquids. We derive an integral equation of Volterra type for the transient molecular flux density to a liquid droplet and solve it numerically. Numerical calculations are performed for absorption of sulfur dioxide (SO(2)), dinitrogen trioxide (N(2)O(3)), and chlorine (Cl(2)) by liquid nanoaerosols accompanied by chemical dissociation reaction. It is shown that during gas absorption by nanoaerosols, the kinetic effects play a significant role, and neglecting kinetic effects leads to a significant overestimation of the soluble gas flux into a droplet during the entire period of gas absorption.

The examination of berberine excited state by laser flash photolysis

NASA Astrophysics Data System (ADS)

Cheng, Lingli; Wang, Mei; Zhao, Ping; Zhu, Hui; Zhu, Rongrong; Sun, Xiaoyu; Yao, Side; Wang, Shilong

2009-07-01

The property of the excited triplet state of berberine (BBR) was investigated by using time-resolved laser flash photolysis of 355 nm in acetonitrile. The transient absorption spectra of the excited triplet BBR were obtained in acetonitrile, which have an absorption maximum at 420 nm. And the ratio of excitation to ionization of BBR in acetonitrile solvent was calculated. The self-decay and self-quenching rate constants, and the absorption coefficient of 3BBR* were investigated and the excited state quantum yield was determined. Furthermore utilizing the benzophenone (BEN) as a triplet sensitizer, and the β-carotene (Car) as an excited energy transfer acceptor, the assignment of 3BBR* was further confirmed and the related energy transfer rate constants were also determined.

Photosensitive function of encapsulated dye in carbon nanotubes.

PubMed

Yanagi, Kazuhiro; Iakoubovskii, Konstantin; Matsui, Hiroyuki; Matsuzaki, Hiroyuki; Okamoto, Hiroshi; Miyata, Yasumitsu; Maniwa, Yutaka; Kazaoui, Said; Minami, Nobutsugu; Kataura, Hiromichi

2007-04-25

Single-wall carbon nanotubes (SWCNTs) exhibit resonant absorption localized in specific spectral regions. To expand the light spectrum that can be utilized by SWCNTs, we have encapsulated squarylium dye into SWCNTs and clarified its microscopic structure and photosensitizing function. X-ray diffraction and polarization-resolved optical absorption measurements revealed that the encapsulated dye molecules are located at an off center position inside the tubes and aligned to the nanotube axis. Efficient energy transfer from the encapsulated dye to SWCNTs was clearly observed in the photoluminescence spectra. Enhancement of transient absorption saturation in the S1 state of the semiconducting SWCNTs was detected after the photoexcitation of the encapsulated dye, which indicates that ultrafast (<190 fs) energy transfer occurred from the dye to the SWCNTs.

Time-resolved spectroscopy of dye-labeled photoactive yellow protein suggests a pathway of light-induced structural changes in the N-terminal cap.

PubMed

Hoersch, Daniel; Otto, Harald; Cusanovich, Michael A; Heyn, Maarten P

2009-07-14

The photoreceptor PYP responds to light activation with global conformational changes. These changes are mainly located in the N-terminal cap of the protein, which is approximately 20 A away from the chromophore binding pocket and separated from it by the central beta-sheet. The question of the propagation of the structural change across the central beta-sheet is of general interest for the superfamily of PAS domain proteins, for which PYP is the structural prototype. Here we measured the kinetics of the structural changes in the N-terminal cap by transient absorption spectroscopy on the ns to second timescale. For this purpose the cysteine mutants A5C and N13C were prepared and labeled with thiol reactive 5-iodoacetamidofluorescein (IAF). A5 is located close to the N-terminus, while N13 is part of helix alpha1 near the functionally important salt bridge E12-K110 between the N-terminal cap and the central anti-parallel beta-sheet. The absorption spectrum of the dye is sensitive to its environment, and serves as a sensor for conformational changes near the labeling site. In both labeled mutants light activation results in a transient red-shift of the fluorescein absorption spectrum. To correlate the conformational changes with the photocycle intermediates of the protein, we compared the kinetics of the transient absorption signal of the dye with that of the p-hydroxycinnamoyl chromophore. While the structural change near A5 is synchronized with the rise of the I(2) intermediate, which is formed in approximately 200 mus, the change near N13 is delayed and rises with the next intermediate I(2)', which forms in approximately 2 ms. This indicates that different parts of the N-terminal cap respond to light activation with different kinetics. For the signaling pathway of photoactive yellow protein we propose a model in which the structural signal propagates from the chromophore binding pocket across the central beta-sheet via the N-terminal region to helix alpha1, resulting in a large change in the protein conformation.

Unravelling the mechanisms of vibrational relaxation in solution† †All experimental data are archived in the University of Bristol's Research Data Storage Facility (DOI: 10.5523/bris.2vk036f35m5aq2dnlb79c0wcsh). ‡ ‡Electronic supplementary information (ESI) available: Further discussion of spectral lineshapes, concentration dependence of transient absorption data, theoretical calculations, IR-pump IR-probe spectra, transient absorption spectra including animation of spectra. See DOI: 10.1039/c6sc05234g Click here for additional data file. Click here for additional data file.

PubMed Central

Grubb, Michael P.; Coulter, Philip M.; Marroux, Hugo J. B.

2017-01-01

We present a systematic study of the mode-specific vibrational relaxation of NO2 in six weakly-interacting solvents (perfluorohexane, perfluoromethylcyclohexane, perfluorodecalin, carbon tetrachloride, chloroform, and d-chloroform), chosen to elucidate the dominant energy transfer mechanisms in the solution phase. Broadband transient vibrational absorption spectroscopy has allowed us to extract quantum state-resolved relaxation dynamics of the two distinct NO2 fragments produced from the 340 nm photolysis of N2O4 → NO2(X) + NO2(A) and their separate paths to thermal equilibrium. Distinct relaxation pathways are observed for the NO2 bending and stretching modes, even at energies as high as 7000 cm–1 above the potential minimum. Vibrational energy transfer is governed by different interaction mechanisms in the various solvent environments, and proceeds with timescales ranging from 20–1100 ps. NO2 relaxation rates in the perfluorocarbon solvents are identical despite differences in acceptor mode state densities, infrared absorption cross sections, and local solvent structure. Vibrational energy is shown to be transferred to non-vibrational solvent degrees of freedom (V-T) through impulsive collisions with the perfluorocarbon molecules. Conversely, NO2 relaxation in chlorinated solvents is reliant on vibrational resonances (V-V) while V-T energy transfer is inefficient and thermal excitation of the surrounding solvent molecules inhibits faster vibrational relaxation through direct complexation. Intramolecular vibrational redistribution allows the symmetric stretch of NO2 to act as a gateway for antisymmetric stretch energy to exit the molecule. This study establishes an unprecedented level of detail for the cooling dynamics of a solvated small molecule, and provides a benchmark system for future theoretical studies of vibrational relaxation processes in solution. PMID:28451375

Magnetized Disk Winds in NGC 3783

NASA Technical Reports Server (NTRS)

Fukumura, Keigo; Kazanas, Demosthenes; Shrader, Chris; Behar, Ehud; Tombesi, Francesco; Contopoulos, Ioannis

2018-01-01

We analyze a 900 kilosecond stacked Chandra/HETG (High-Energy Transmission Grating) spectrum of NGC 3783 in the context of magnetically driven accretion-disk wind models in an effort to provide tight constraints on the global conditions of the underlying absorbers. Motivated by the earlier measurements of its absorption measure distribution (AMD) indicating X-ray-absorbing ionic columns that decrease slowly with decreasing ionization parameter, we employ 2-dimension (2-D) magnetohydrodynamic (MHD) disk wind models to describe the global outflow. We compute its photoionization structure along with the wind kinematic properties, allowing us to further calculate in a self-consistent fashion the shapes of the major X-ray absorption lines. With the wind radial density profile determined by the AMD, the profiles of the ensemble of the observed absorption features are determined by the two global parameters of the MHD wind; i.e., disk inclination theta (sub obs) and wind density normalization n (sub o). Considering the most significant absorption features in the approximately 1.8-20 angstrom range, we show that the MHD wind is best described by n(r) approximately equal to 6.9 times 10 (sup 11) (r/r (sub o)) (sup - 1.15) cubic centimeters and theta (sub obs). We argue that winds launched by X-ray heating or radiation pressure, or even MHD winds but with steeper radial density profiles, are strongly disfavored by data. Considering the properties of Fe K-band absorption features (i.e., Fe XXV and Fe XXVI), while typically prominent in the active galactic nucleus X-ray spectra, they appear to be weak in NGC 3783. For the specific parameters of our model obtained by fitting the AMD and the rest of the absorption features, these features are found to be weak, in agreement with observations.

Magnetized Disk Winds in NGC 3783

NASA Astrophysics Data System (ADS)

Fukumura, Keigo; Kazanas, Demosthenes; Shrader, Chris; Behar, Ehud; Tombesi, Francesco; Contopoulos, Ioannis

2018-01-01

We analyze a 900 ks stacked Chandra/HETG spectrum of NGC 3783 in the context of magnetically driven accretion-disk wind models in an effort to provide tight constraints on the global conditions of the underlying absorbers. Motivated by the earlier measurements of its absorption measure distribution (AMD) indicating X-ray-absorbing ionic columns that decrease slowly with decreasing ionization parameter, we employ 2D magnetohydrodynamic (MHD) disk wind models to describe the global outflow. We compute its photoionization structure along with the wind kinematic properties, allowing us to further calculate in a self-consistent fashion the shapes of the major X-ray absorption lines. With the wind radial density profile determined by the AMD, the profiles of the ensemble of the observed absorption features are determined by the two global parameters of the MHD wind; i.e., disk inclination {θ }{obs} and wind density normalization n o . Considering the most significant absorption features in the ∼1.8–20 Å range, we show that the MHD wind is best described by n{(r)∼ 6.9× {10}11(r/{r}o)}-1.15 cm‑3 and {θ }{obs}=44^\\circ . We argue that winds launched by X-ray heating or radiation pressure, or even MHD winds but with steeper radial density profiles, are strongly disfavored by data. Considering the properties of Fe K-band absorption features (i.e., Fe XXV and Fe XXVI), while typically prominent in the active galactic nucleus X-ray spectra, they appear to be weak in NGC 3783. For the specific parameters of our model obtained by fitting the AMD and the rest of the absorption features, these features are found to be weak, in agreement with observations.

Lithographically fabricated silicon microreactor for operando QEXAFS studies in exhaust gas catalysis during simulation of a standard driving cycle

NASA Astrophysics Data System (ADS)

Doronkin, D. E.; Baier, S.; Sheppard, T.; Benzi, F.; Grunwaldt, J.-D.

2016-05-01

Selective catalytic reduction of NOx by ammonia over Cu-ZSM-5 was monitored by operando QEXAFS during simulation of the New European Driving Cycle. The required fast temperature transients were realized using a novel silicon microreactor, enabling simultaneous spectroscopic and kinetic analysis by X-ray absorption spectroscopy (XAS) and mass spectrometry (MS). Periods of high temperature were correlated to an increase in both N2 production and change of coordination of Cu sites. This operando approach using Si microreactors can be applied to other heterogeneous catalytic systems involving fast temperature transients.

Direct observation of back energy transfer in blue phosphorescent materials for organic light emitting diodes by time-resolved optical waveguide spectroscopy.

PubMed

Hirayama, H; Sugawara, Y; Miyashita, Y; Mitsuishi, M; Miyashita, T

2013-02-25

We demonstrate a high-sensitive transient absorption technique for detection of excited states in an organic thin film by time-resolved optical waveguide spectroscopy. By using a laser beam as a probe light, we detect small change in the transient absorbance which is equivalent to 10 -7 absorbance unit in a conventional method. This technique was applied to organic thin films of blue phosphorescent materials for organic light emitting diodes. We directly observed the back energy transfer from emitting guest molecules to conductive host molecules.

Nonlinear femtosecond pump-probe spectroscopy using a power-encoded soliton delay line.

PubMed

Saint-Jalm, Sarah; Andresen, Esben Ravn; Bendahmane, Abdelkrim; Kudlinski, Alexandre; Rigneault, Hervé

2016-01-01

We show femtosecond time-resolved nonlinear pump-probe spectroscopy using a fiber soliton as the probe pulse. Furthermore, we exploit soliton dynamics to record an entire transient trace with a power-encoded delay sweep. The power-encoded delay line takes advantage of the dependency of the soliton trajectory in the (λ,z) space upon input power; the difference in accumulated group delay between trajectories converts a fast power sweep into a fast delay sweep. We demonstrate the concept by performing transient absorption spectroscopy in a test sample and validate it against a conventional pump-probe setup.

Production of Ti-C presolar carbide grain analogies and its infrared spectra

NASA Astrophysics Data System (ADS)

Kimura, Y.; Ikegami, A.; Tanigaki, T.; Ishikawa, M.; Sato, T.; Suzuki, H.; Kido, O.; Kaito, C.

The infrared emission of the circumstellar environment of carbon-rich stars and dense molecular cloud cores is believed to be dominated by the emissivity of carbon dust. The origins of absorption peaks will be identified on the basis of laboratory studies. Important factors in the determination of absorption features are size, shape and structure of the grain (Bohren and Huffman, 1983). Therefore, the production of presolar grain analogy is important for the identification of the observation spectra. Recently, we succeeded in the formation of Si-, Ti- and Zr-C grains of the order of 50 nm by advanced gas evaporation method. We have started to obtain characteristic data of carbide grains in laboratory experiments. The spectra from ultraviolet to infrared of samples embedded in KBr pellets are presented. In the present study, we will elucidate the correlation between the size of TiC grain or thickness of the carbon mantle layer and spectra of TiC core-carbon mantle grains. Because TiC is one of the candidates of 21 micron feature. The absorption peaks of TiC core (50 nm)-carbon mantle (2 nm) grains were found to be at 9.5 and 12.5 microns. When the thickness of the mantle layer increased to 15 nm, the peak at 12.5 microns disappeared and the peak at 9.5 microns was significantly weakened. These results are similar to the calculated result for SiC core-carbon mantle grains, i.e., increased thickness of the mantle layer weakens the spectrum intensity (Kozasa et al., 1996). The 20.1 micron absorption feature never appeared, even if the same size grains seen in meteorites were produced. Moreover, the infrared spectra were observed when the size of TiC grains was smaller than presolar grain. Carbon was deposited on the surface of Ti grains. Then, TiC nanocrystallites with the size of 2-3 nm were produced by the diffusion of Ti and/or carbon. The new absorption feature was appeared at 14 microns. The 12.5 micron absorption was hardly seen. If the samples are heated at 700circC for 1h, crystallites size of TiC was increased to about 5 nm. The absorption feature at 14 microns was weaken. It was concluded that the infrared absorption feature was depend on the crystallites size.

Optical properties of an inhomogeneously broadened ΛV-system with multiple excited states

NASA Astrophysics Data System (ADS)

Kaur, Paramjit; Bharti, Vineet; Wasan, Ajay

2014-09-01

We present a theoretical model using a density matrix approach to show the influence of multiple excited states on the optical properties of an inhomogeneously broadened ?V-system of the ?Rb D2 line. These closely spaced multiple excited states cause asymmetry in absorption and dispersion profiles. We observe the reduced absorption profiles, due to dressed state interactions of the applied electromagnetic fields, which results the Mollow sideband-like transparency windows. In a room temperature vapor, we obtain a narrow enhanced absorption and steep positive dispersion at the line center when the strengths of control and pump fields are equal. Here, we show how the probe transmittance varies when it passes through the atomic medium. We also discuss the transient behavior of our system which agrees well with the corresponding absorption and dispersion profiles. This study has potential applications in controllability of group velocity, and for optical and quantum information processing.

Analysis of Shuttle Multispecral Infrared Radiometer measurements of the western Saudi Arabian shield.

USGS Publications Warehouse

Rowan, Lawrence C.; Goetz, Alexander F.H.; Abbott, Elsa

1987-01-01

During the November 12–14, 1981, mission of the space shuttle Columbia, the Shuttle Multispectral Infrared Radiometer (SMIRR) recorded radiances in ten channels along a 100 m wide groundtrack across the western Saudi Arabian shield. The ten channels are located in the 0.5 to 2.4 μm region, with five positioned between 2.0 and 2.40 μm for measuring absorption features that are diagnostic of OH‐bearing and CO3‐bearing">CO3‐bearing minerals. This exceptionally well exposed area consists of late Proterozoic metamorphic, intermediate to silicic intrusive, and interlayered clastic sedimentary and intermediate silicic volcanic rocks that have not been studied previously using SMIRR data. Plots or traces of unnormalized SMIRR channel ratios were examined before field studies to locate areas with high spectral contrast, especially in the 2.0 μm to 2.40 μm channels. Reflectance spectra were measured in the laboratory for rock and soil samples collected in these areas, and the mineralogic causes of the main absorption features were determined using X‐ray diffraction. Laboratory SMIRR spectra were produced by convolving the ten SMIRR filters with the laboratory spectra. Then, normalized SMIRR reflectance spectra were generated along the groundtrack using normalization coefficients calculated for a field sample representing a uniform, low‐spectral contrast area. Field evaluation shows that unnormalized SMIRR ratio traces are useful, even without specific mineralogic information, for distinguishing rocks that are characterized by Al‐OH, Mg‐OH, and/or CO3">CO3">CO3, Fe3+">Fe3+, and Fe2+ absorption features. Analysis of field samples permits suites of minerals causing absorption features to be identified. However, specific mineral identification cannot be achieved consistently using the SMIRR ratio traces or normalized SMIRR spectra, because the Al‐OH and Mg‐OH absorption features can be caused by more than one of the minerals commonly present. The normalized SMIRR spectra are especially useful for identifying subtle Al‐OH and Mg‐OH absorption features that are difficult to identify in the unnormalized ratio traces and for comparing the relative intensities of absorption features. Al‐OH absorption is related to muscovite, smectite, illite, and kaolinite, whereas Mg‐OH absorption is caused by chlorite, amphibole, and biotite. The principal sources of error in using SMIRR spectral measurements for identifying mineral groups along the orbit 27 groundtrack are inaccuracies in field location and lithologic heterogeneity that is not represented adequately by field samples. Calibration errors may account for systematic albedo and absorption intensity differences between calculated laboratory SMIRR spectra and normalized SMIRR spectra. SMIRR instrument noise and atmospheric factors appear to be less important sources of error. However, as higher spectral and spatial resolution systems are developed for mineral identification, radiometric precision and atmospheric factors will become more important.

Hyperspectral analysis of the ultramafic complex and adjacent lithologies at Mordor, NT, Australia

USGS Publications Warehouse

Rowan, L.C.; Simpson, C.J.; Mars, J.C.

2004-01-01

The Mordor Complex consists of a series of potassic ultramafic rocks which were intruded into Proterozoic felsic gneisses and amphibolite and are overlain by quartzite and unconsolidated deposits. In situ and laboratory 0.4 to 2.5 ??m reflectance spectra show Al-OH absorption features caused by absorption in muscovite, kaolinite, and illite/smectite in syenite, granitic gneiss, quartzite and unconsolidated sedimentary deposits, and Fe,Mg-OH features due to phlogopite, biotite, epidote, and hornblende in the mafic and ultramafic rocks. Ferrous-iron absorption positioned near 1.05 ??m is most intense in peridotite reflectance spectra. Ferric-iron absorption is intense in most of the felsic lithologies. HyMap data were recorded in 126 narrow bands from 0.43 to 2.5 ??m along a 7-km-wide swath with approximately 6-m spatial resolution. Correction of the data to spectral reflectance was accomplished by reference to in situ measurements of an extensive, alluvial plain. Spectral classes for matched filter processing were selected by using the pixel purity index procedure and analysis of in situ and laboratory spectra. Considering the spatial distribution of the resulting 14 classes, some classes were combined, which produced eight classes characterized by Al-OH absorption features, and three Fe,Mg-OH absorption-feature classes. Comparison of the distribution of these 11 spectral classes to a generalized lithologic map of the study area shows that the spectral distinction among the eight Al-OH classes is related to variations in primary lithology, weathering products, and vegetation density. Quartzite is represented in three classes, syenite corresponds to a single scattered class, quartz-muscovite-biotite schist defines a single very coherent class, and unconsolidated sediments are portrayed in four classes. The three mafic-ultramafic classes are distinguished on the basis of generally intense Fe,Mg-OH and ferrous-iron absorption features. A single class represents the main Mordor ultramafic mass. Epidote-bearing rocks define another class, which corresponds to biotite gneiss and, in the southern part of the area, to fracture zones. The third class, which exhibits Al-OH, as well as Fe,Mg-OH features, represents hornblende gneiss and other mafic gneisses. These results indicate the importance of analyzing the VNIR and SWIR spectral shape and albedo, as well as analyzing specific spectral features, for mapping lithologic units in this weathered terrain. ?? 2004 Elsevier Inc. All rights reserved.

Photoexcitation dynamics of NO-bound ferric myoglobin investigated by femtosecond vibrational spectroscopy.

PubMed

Park, Jaeheung; Lee, Taegon; Park, Jaehun; Lim, Manho

2013-03-14

Femtosecond vibrational spectroscopy was used to investigate the photoexcitation dynamics of NO-bound ferric myoglobin (Mb(III)NO) in D2O solution at 294 K after excitation with a 575 nm pulse. The stretching mode of NO in Mb(III)NO consists of a major band at 1922 cm(-1) (97.7%) and a minor band at 1902 cm(-1) (2.3%), suggesting that Mb(III)NO in room temperature solution has two conformational substates. The time-resolved spectra show small but significant new absorption features at the lower-energy side of the main band (1920-1800 cm(-1)). One new absorption feature in the region of 1920-1880 cm(-1) exhibits the (15)NO isotope shift (37 cm(-1)) the same as that of the NO band in the ground electronic state of Mb(III)NO. This absorption shifts toward higher energy and narrows with a time constant of 2.4 ps, indicating that it evolves with rapid electronic and thermal relaxation of the photoexcited Mb(III)NO without photodeligation of the NO from the heme. Absorption features assigned to proteins undergoing thermal relaxation without NO deligation add up to 14 ± 1% of the total bleach, implying that the photolysis quantum yield of Mb(III)NO with a Q-band excitation is ≤0.86 ± 0.01. The remaining absorption bands peaked near 1867, 1845, and 1815 cm(-1), each showing the (15)NO isotope shift the same as that of the free NO radical (33 cm(-1)), were assigned to the vibrational band of the photodeligated NO, the NO band of Mb(III)NO in an intermediate electronic state with low-spin Fe(III)-NO(radical) character (denoted as the R state), and the NO band of the vibrationally excited NO in the R state, respectively. A kinetics model successfully reproducing the time-dependent intensity changes of the transient bands suggests that every rebound NO forms the R state that eventually relaxes into the ground electronic state nonexponentially. Most of the photodissociated NO undergoes fast geminate recombination (GR), and the rebinding kinetics depends on the conformation of the protein. GR of NO to Mb(III) in the major conformation shows highly nonexponential kinetics described by a stretched exponential function, exp(-(t/290 ps)(0.44). The NO rebinding to Mb(III) in the minor conformation is exponential, exp(-t/1.8 ns), suggesting that the distal histidine, the interaction of which dictates the conformation of Mb(III)NO, participates in mediating the binding of NO to Mb(III). In Mb(III)NO, the elusive low-spin Fe(III)-NO(radical) state, proposed in electronic structure calculations, indeed exists at >12 kJ/mol above the ground state and takes part in the bond formation of Fe(III)-NO, suggesting that it plays a significant role in the function of NO-bound ferric protein. Time-resolved vibrational spectra with high sensitivity reveal rich photophysical and photochemical processes of photoexcited Mb(III)NO.

Features of Chaotic Transients in Excitable Media Governed by Spiral and Scroll Waves

NASA Astrophysics Data System (ADS)

Lilienkamp, Thomas; Christoph, Jan; Parlitz, Ulrich

2017-08-01

In excitable media, chaotic dynamics governed by spiral or scroll waves is often not persistent but transient. Using extensive simulations employing different mathematical models we identify a specific type-II supertransient by an exponential increase of transient lifetimes with the system size in 2D and an investigation of the dynamics (number and lifetime of spiral waves, Kaplan-Yorke dimension). In 3D, simulations exhibit an increase of transient lifetimes and filament lengths only above a critical thickness. Finally, potential implications for understanding cardiac arrhythmias are discussed.

Reproducible Crystal Growth Experiments in Microgravity Science Glovebox at the International Space Station (SUBSA Investigation)

NASA Technical Reports Server (NTRS)

Ostrogorsky, A.; Marin, C.; Volz, M. P.; Bonner, W. A.

2005-01-01

Solidification Using a Baffle in Sealed Ampoules (SUBSA) is the first investigation conducted in the Microgravity Science Glovebox (MSG) Facility at the International Space Station (ISS) Alpha. 8 single crystals of InSb, doped with Te and Zn, were directionally solidified in microgravity. The experiments were conducted in a furnace with a transparent gradient section, and a video camera, sending images to the earth. The real time images (i) helped seeding, (ii) allowed a direct measurement of the solidification rate. The post-flight characterization of the crystals includes: computed x-ray tomography, Secondary Ion Mass Spectroscopy (SIMS), Hall measurements, Atomic Absorption (AA), and 4 point probe analysis. For the first time in microgravity, several crystals having nearly identical initial transients were grown. Reproducible initial transients were obtained with Te-doped InSb. Furthermore, the diffusion controlled end-transient was demonstrated experimentally (SUBSA 02). From the initial transients, the diffusivity of Te and Zn in InSb was determined.

Pulse radiolysis studies of mangiferin: A C- glycosyl xanthone isolated from Mangifera indica

NASA Astrophysics Data System (ADS)

Mishra, B.; Priyadarsini, K. Indira; Sudheerkumar, M.; Unnikrishhnan, M. K.; Mohan, H.

2006-01-01

Pulse radiolysis technique has been employed to study the reaction of different oxidizing and reducing radicals with mangiferin. The reaction of rad OH radical showed the formation of transient species absorbing in 380-390 and 470-480 nm region. The reaction with specific one-electron oxidants (N 3rad , CCl 3O 2rad ) also showed the formation of similar transient absorption bands and is assigned to phenoxyl radicals. The p Ka values of the transient species have been determined to be 6.3 and 11.9. One-electron oxidation potential of mangiferin at pH 9 has been found to be 0.62 V vs. NHE. The reaction of e aq- showed the formation of transient species with λmax at 340 nm, which is assigned to the ketyl anion radical formed on addition of e aq- at carbonyl site. Reactions of one-electron oxidised mangiferin radicals with ascorbic acid have also been studied.

TRANSIENT AMORPHOUS CALCIUM PHOSPHATE IN FORMING ENAMEL

PubMed Central

Beniash, Elia; Metzler, Rebecca A.; Lam, Raymond S.K.; Gilbert, P.U.P.A.

2009-01-01

Enamel, the hardest tissue in the body, begins as a three-dimensional network of nanometer size mineral particles, suspended in a protein gel. This mineral network serves as a template for mature enamel formation. To further understand the mechanisms of enamel formation we characterized the forming enamel mineral at an early secretory stage using x-ray absorption near-edge structure (XANES) spectromicroscopy, transmission electron microscopy (TEM), FTIR microspectroscopy and polarized light microscopy. We show that the newly formed enamel mineral is amorphous calcium phosphate (ACP), which eventually transforms into apatitic crystals. Interestingly, the size, shape and spatial organization of these amorphous mineral particles and older crystals are essentially the same, indicating that the mineral morphology and organization in enamel is determined prior to its crystallization. Mineralization via transient amorphous phases has been previously reported in chiton teeth, mollusk shells, echinoderm spicules and spines, and recent reports strongly suggest the presence transient amorphous mineral in forming vertebrate bones. The present finding of transient ACP in murine tooth enamel suggests that this strategy might be universal. PMID:19217943

Using the Concept of Transient Complex for Affinity Predictions in CAPRI Rounds 20–27 and Beyond

PubMed Central

Qin, Sanbo; Zhou, Huan-Xiang

2013-01-01

Predictions of protein-protein binders and binding affinities have traditionally focused on features pertaining to the native complexes. In developing a computational method for predicting protein-protein association rate constants, we introduced the concept of transient complex after mapping the interaction energy surface. The transient complex is located at the outer boundary of the bound-state energy well, having near-native separation and relative orientation between the subunits but not yet formed most of the short-range native interactions. We found that the width of the binding funnel and the electrostatic interaction energy of the transient complex are among the features predictive of binders and binding affinities. These ideas were very promising for the five affinity-related targets (T43–45, 55, and 56) of CAPRI rounds 20–27. For T43, we ranked the single crystallographic complex as number 1 and were one of only two groups that clearly identified that complex as a true binder; for T44, we ranked the only design with measurable binding affinity as number 4. For the nine docking targets, continuing on our success in previous CAPRI rounds, we produced 10 medium-quality models for T47 and acceptable models for T48 and T49. We conclude that the interaction energy landscape and the transient complex in particular will complement existing features in leading to better prediction of binding affinities. PMID:23873496

Near-infrared counterparts of three transient very faint neutron star X-ray binaries

NASA Astrophysics Data System (ADS)

Shaw, A. W.; Heinke, C. O.; Degenaar, N.; Wijnands, R.; Kaur, R.; Forestell, L. M.

2017-10-01

We present near-infrared (NIR) imaging observations of three transient neutron star X-ray binaries, SAX J1753.5-2349, SAX J1806.5-2215 and AX J1754.2-2754. All three sources are members of the class of 'very faint' X-ray transients which exhibit X-ray luminosities LX ≲ 1036 erg s-1. The nature of this class of sources is still poorly understood. We detect NIR counterparts for all three systems and perform multiband photometry for both SAX J1753.5-2349 and SAX J1806.5-2215, including narrow-band Br γ photometry for SAX J1806.5-2215. We find that SAX J1753.5-2349 is significantly redder than the field population, indicating that there may be absorption intrinsic to the system, or perhaps a jet is contributing to the infrared emission. SAX J1806.5-2215 appears to exhibit absorption in Br γ, providing evidence for hydrogen in the system. Our observations of AX J1754.2-2754 represent the first detection of an NIR counterpart for this system. We find that none of the measured magnitudes are consistent with the expected quiescent magnitudes of these systems. Assuming that the infrared radiation is dominated by either the disc or the companion star, the observed magnitudes argue against an ultracompact nature for all three systems.

Femtosecond Heterodyne Transient Grating Studies of Nonradiative Decay of the S2 (11Bu+) State of Peridinin: Detection and Spectroscopic Assignment of an Sx Intermediate State

NASA Astrophysics Data System (ADS)

Ghosh, Soumen; Bishop, Michael M.; Roscioli, Jerome D.; Lafountain, Amy M.; Frank, Harry A.; Beck, Warren F.

Femtosecond heterodyne transient grating spectroscopy was employed to investigate the nonradiative relaxation dynamics of peridinin from the S2 state to the S1 (21Ag-) state in methanol. A global target analysis indicates that S2 decays in 12 fs to populate an intermediate state, Sx. The absorption and dispersion components of the transient grating signal exhibit a response that is very similar to that of β-carotene in benzonitrile solution. Numerical simulation of the experimental data indicates that the excited state absorption transition from Sx has a larger oscillator strength than that of S1, which rules out an assignment of Sx to a vibrationally excited S1 state. The lifetime of Sx is found to be strongly dependent on the polar solvation timescale. This result indicates that nonradiative decay from Sx to S1 involves large-amplitude torsional motions and a concomitant formation of intramolecular charge transfer character. The present work provides the first evidence that peridinin has an ultrashort S2 lifetime owing to the onset of torsional motions and shows that the Sx acts as an active state for excitation energy transfer to chlorophyll in light-harvesting proteins. Work supported by the Photosynthetic Systems program of U.S. Department of Energy under Award Number DE-SC0010847.

Correlations between Crystallite Size, Shape, Surface, and Infrared Spectra Using the Ti-C System

NASA Astrophysics Data System (ADS)

Kimura, Y.; Ikegami, A.; Kurumada, M.; Kamitsuji, K.; Kaito, C.

2004-06-01

TiC crystallites less than 10 nm in size showed an absorption feature at 14.3 μm. This 14.3 μm absorption was rarely seen in specimens ranging from bulk material to grains of 50 nm in size. The 14.3 μm feature was weakened as a result of the growth of TiC crystallites by heat treatment. When the carbide grains were covered with a carbon layer, the absorption peaks were considerably weakened, i.e., the absorption intensity depended on the grain surface state. A possible explanation is that the effects of size and shape on the spectra depend on the surface anisotropy.

Composition and structure of fresh ammonia clouds on Jupiter based on quantitative analysis of Galileo/NIMS and New Horizons/LEISA spectra

NASA Astrophysics Data System (ADS)

Sromovsky, L. A.; Fry, P. M.

2018-06-01

Ammonia gas has long been assumed to be the main source of condensables for the upper cloud layer on Jupiter, but distinctive spectral features associated with ammonia have been seen only rarely. Since both ammonia and NH4SH absorb in the 3 μm region, and widespread absorption in the 3 μm region was present (Sromovsky and Fry, 2010), identification of the 2 μm absorption feature of NH3 provided an opportunity to clearly establish its presence in Jovian clouds. Baines et al. (2002) succeeded in finding in Near Infrared Mapping Spectrometer (NIMS) observations one feature that had both 2 μm and 3 μm absorption, and many which were known to have absorption at 2.73 μm. They named these Spectrally Identifiable Ammonia Clouds (SIACs). They also argued that these were fresh ammonia clouds that would eventually succumb to some process that would obscure their absorption features. Detection of many more of the 2 μm features was later achieved by New Horizon's Linear Etalon Imaging Spectral Array (LEISA) instrument, which provided both the spatial and spectral resolution needed to identify these features. Here we report on the first quantitative modeling that uses NIMS spectra over a broad (1-5.2 μm) spectral range and LEISA spectra over a much narrower (1.25-2.5 μm) spectral range to constrain the cloud structure and composition of these rare cloud features and compare them to background clouds. We find that the absorption signature at 2 μm, which is well characterized in LEISA spectra, is relatively subtle and easily matched by model clouds containing spherical particles of ammonia ice with radii of 2-4 μm. The NIMS spectra, which cover both reflected sunlight as well as thermal emission regions are more difficult to model with cloud materials plausibly present in Jupiter's atmosphere. The best signal/noise spectra obtained from NIMS provide a relatively sparse sampling of the spectrum, which does not establish the detailed shape of the 3 μm absorption region. NIMS SIAC spectra with much denser spectral sampling are limited by much higher noise levels that degrade the features that are key to identifying cloud composition. The structure which best matches the wide range NIMS SIAC spectra contains two overlapping NH3 clouds with a bi-modal size distribution over an optically thick NH4SH cloud. The bi-modal distribution may be a result of modeling non-spherical, possibly fractal aggregate, particles with spheres.

Investigating Hydroxyl at Asteroid 951 Gaspra

NASA Astrophysics Data System (ADS)

Granahan, James C.

2015-11-01

Recent investigations [Granahan, 2011; 2014] of Galileo Near Infrared Mapping Spectrometer (NIMS) observations of asteroid 951 Gaspra have detected an infrared absorption feature near 2.8 micrometers. These were detected in NIMS data acquired by the Galileo spacecraft on October 29, 1991 at wavelengths ranging from 0.7 - 5.2 micrometers [Carlson et al., 1992]. This abstract presents a summary of the investigation to identify the material creating the 2.8 micrometer spectral absorption feature. The current best match for the observed 951 Gaspra feature is the phyllosilicate bound hydroxyl signature present in a thermally desiccated QUE 99038 carbonaceous chondrite as measured by Takir et al. [2013].The 951 Gaspra absorption feature has been compared to a variety of hydroxyl bearing signatures. Many phyllosilicates, hydroxyl bearing minerals, have absorption minima at different positions (2.7 or 2.85 micrometers). It also differs from similar absorptions in a potential R chondrite analog, LAP 04840. The spectra LAP 04840 has a 2.7 micrometer feature due to biotite and a 2.9 micrometer feature due to adsorbed water [Klima et al., 2007]. 2.8 micrometer absorption minima have been found for adsorbed hydroxyl on the Moon [McCord et al., 2011] and various carbonaceous chondrites [Calvin and King, 1997; Takir et al., 2013]. The best match, with a minimum Euclidean distance difference to the 951 Gaspra feature, is found in the spectrum of QUE 99038 [Takir et al., 2013]. This spectrum is the product of an infrared measurement of a sample that had its adsorbed water baked off and removed in a vacuum chamber. The remaining hydroxyl in the sample belongs to a mixture of phyllosilicates dominated by the presence of cronstedtite.References: Calvin, W. M., and T. V. King (1997), Met. Planet. Sci., 32, 693-702. Carlson, R. W., et al. (1992), Bull. American Astro. Soc., 24, 932. Granahan, J. C. (2011), Icarus, 213, 265-272. Granahan, J. C. (2014), 45th LPSC, #1092. Klima, R., C. et al. (2007), 38th LPSC, #1710. McCord, T. B., et al. (2011), JGR, 116, E00G05. Takir, D., et al. (2013), Met. Planet. Sci., 48, 1618-1637.

Capturing the radical ion-pair intermediate in DNA guanine oxidation

PubMed Central

Jie, Jialong; Liu, Kunhui; Wu, Lidan; Zhao, Hongmei; Song, Di; Su, Hongmei

2017-01-01

Although the radical ion pair has been frequently invoked as a key intermediate in DNA oxidative damage reactions and photoinduced electron transfer processes, the unambiguous detection and characterization of this species remain formidable and unresolved due to its extremely unstable nature and low concentration. We use the strategy that, at cryogenic temperatures, the transient species could be sufficiently stabilized to be detectable spectroscopically. By coupling the two techniques (the cryogenic stabilization and the time-resolved laser flash photolysis spectroscopy) together, we are able to capture the ion-pair transient G+•⋯Cl− in the chlorine radical–initiated DNA guanine (G) oxidation reaction, and provide direct evidence to ascertain the intricate type of addition/charge separation mechanism underlying guanine oxidation. The unique spectral signature of the radical ion-pair G+•⋯Cl− is identified, revealing a markedly intense absorption feature peaking at 570 nm that is distinctive from G+• alone. Moreover, the ion-pair spectrum is found to be highly sensitive to the protonation equilibria within guanine-cytosine base pair (G:C), which splits into two resolved bands at 480 and 610 nm as the acidic proton transfers along the central hydrogen bond from G+• to C. We thus use this exquisite sensitivity to track the intrabase-pair proton transfer dynamics in the double-stranded DNA oligonucleotides, which is of critical importance for the description of the proton-coupled charge transfer mechanisms in DNA. PMID:28630924

IUE detector saturation and the new 2800 A absorption feature 'discovered' by Karim, Hoyle, and Wickramasinghe

NASA Astrophysics Data System (ADS)

Savage, B. D.; Sitko, M. L.

1984-03-01

The 2800 A feature of Karim et al. (1983) is shown to be the result of IUE detector saturation effects in overexposed spectra. A properly exposed spectrum and an overexposed one are shown. The latter shows a broad absorption peak at 2800 A while the former does not.

Investigations on the 1.7 micron residual absorption feature in the vegetation reflection spectrum

NASA Technical Reports Server (NTRS)

Verdebout, J.; Jacquemoud, S.; Andreoli, G.; Hosgood, B.; Sieber, A.

1993-01-01

The detection and interpretation of the weak absorption features associated with the biochemical components of vegetation is of great potential interest to a variety of applications ranging from classification to global change studies. This recent subject is also challenging because the spectral signature of the biochemicals is only detectable as a small distortion of the infrared spectrum which is mainly governed by water. Furthermore, the interpretation is complicated by complexity of the molecules (lignin, cellulose, starch, proteins) which contain a large number of different and common chemical bonds. In this paper, we present investigations on the absorption feature centered at 1.7 micron; these were conducted both on AVIRIS data and laboratory reflectance spectra of leaves.

Simulating Ru L3-edge X-ray Absorption Spectroscopy with Time-Dependent Density Functional Theory: Model Complexes and Electron Localization in Mixed-Valence Metal Dimers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Kuiken, Benjamin E.; Valiev, Marat; Daifuku, Stephanie L.

2013-05-01

Ruthenium L2,3-edge X-ray absorption (XA) spectroscopy probes transitions from core 2p orbitals to the 4d levels of the atom and is a powerful tool for interrogating the local electronic and molecular structure around the metal atom. However, a molecular-level interpretation of the Ru L2,3-edge spectral lineshapes is often complicated by spin–orbit coupling (SOC) and multiplet effects. In this study, we develop spin-free time-dependent density functional theory (TDDFT) as a viable and predictive tool to simulate the Ru L3-edge spectra. We successfully simulate and analyze the ground state Ru L3-edge XA spectra of a series of RuII and RuIII complexes: [Ru(NH3)6]2+/3+,more » [Ru(CN)6]4-/3-, [RuCl6]4-/3-, and the ground (1A1) and photoexcited (3MLCT) transient states of [Ru(bpy)3]2+ and Ru(dcbpy)2(NCS)2 (termed N3). The TDDFT simulations reproduce all the experimentally observed features in Ru L3-edge XA spectra. The advantage of using TDDFT to assign complicated Ru L3-edge spectra is illustrated by its ability to identify ligand specific charge transfer features in complex molecules. We conclude that the B3LYP functional is the most reliable functional for accurately predicting the location of charge transfer features in these spectra. Experimental and simulated Ru L3-edge XA spectra are presented for the transition metal mixed-valence dimers [(NC)5MII-CN-RuIII(NH3)5]- (where M = Fe or Ru) dissolved in water. We explore the spectral signatures of electron delocalization in Ru L3-edge XA spectroscopy and our simulations reveal that the inclusion of explicit solvent molecules is crucial for reproducing the experimentally determined valencies, highlighting the importance of the role of the solvent in transition metal charge transfer chemistry.« less

Near-Infrared Band Strengths of Molecules Diluted in N2 and H20 Ice Mixtures Relevant to Interstellar and Planetary Ices

NASA Technical Reports Server (NTRS)

Richey, C. R.; Richey, Christina R.

2012-01-01

In order to determine the column density of a component of an ice from its infrared absorption features, the strengths of these features must be known. The peak positions, widths, profiles, and strengths of a certain ice component's infrared absorption features are affected be the overall composition of the ice. Many satellites within the solar system have surfaces that are dominated by H2O or N2 and ices in the interstellar medium (ISM) are primarily composed of H2O. The experiments presented here focus on the near-infrared absorption features of CO, CO2, CH4, and NH3 (nu=10,000-4,000/cm, lambda=1-2.5 microns) and the effects of diluting these molecules in N2 or H2O ice (mixture ratio of 5:1). This is a continuation of previous results published by our research group.

Directing Energy Transfer in Panchromatic Platinum Complexes for Dual Vis-Near-IR or Dual Visible Emission from σ-Bonded BODIPY Dyes.

PubMed

Geist, Fabian; Jackel, Andrej; Irmler, Peter; Linseis, Michael; Malzkuhn, Sabine; Kuss-Petermann, Martin; Wenger, Oliver S; Winter, Rainer F

2017-01-17

We report on the platinum complexes trans-Pt(BODIPY)(8-ethynyl-BODIPY)(PEt 3 ) 2 (EtBPtB) and trans-Pt(BODIPY)(4-ethynyl-1,8-naphthalimide)(PR 3 ) 2 (R = Et, EtNIPtB-1; R = Ph, EtNIPtB-2), which all contain two different dye ligands that are connected to the platinum atom by a direct σ bond. The molecular structures of all complexes were established by X-ray crystallography and show that the different dye ligands are in either a coplanar or an orthogonal arrangement. π-stacking and several CH···F and short CH···π interactions involving protons at the phosphine substituents lead to interesting packing motifs in the crystal. The complexes feature several strong absorptions (ε = 3.2 × 10 5 -5.5 × 10 5 M -1 cm -1 ) that cover the regime from 350 to 480 nm (EtNIPtB-1 and EtNIPtB-2) or from 350 to 580 nm (EtBPtB). Besides the typical absorption bands of both kinds of attached dyes, they also feature an intense band near 400-420 nm, which is assigned by time-dependent density functional theory calculations to a higher-energy transition within the ethynyl-BODIPY (EtB) ligand or to charge transfer between the BODIPY (B) and naphthalimide (NI) chromophores. All complexes show dual fluorescence and phosphorescence emission from either the B (EtNIPtB-1 and EtNIPtB-2) or EtB (EtBPtB) ligand with a maximum phosphorescence quantum yield of 41% for EtNIPtB-1. The latter seems to be the highest reported value for room temperature phosphorescence from a BODIPY dye. The complete quenching of the emission from the chromophore absorbing at the higher energy and the appearance of the corresponding absorption bands in the fluorescence and phosphorescence excitation spectra indicate complete and rapid energy transfer to the chromophore with the lower-energy excited state, i.e., EtNI → B in EtNIPtB-1 and EtNIPtB-2 and B → EtB in EtBPtB. The latter process was further investigated by transient absorption spectroscopy, indicating that energy transfer is complete within 0.6 ns. EtNIPtB-1 catalyzes the photooxidation of 1,5-dihydroxynaphthalene with photogenerated 1 O 2 to Juglone at a much faster rate than methylene blue but with only modest quantum yields of 37% and with the onset of photodegradation after 60 min.

Lifetime Reliability Prediction of Ceramic Structures Under Transient Thermomechanical Loads

NASA Technical Reports Server (NTRS)

Nemeth, Noel N.; Jadaan, Osama J.; Gyekenyesi, John P.

2005-01-01

An analytical methodology is developed to predict the probability of survival (reliability) of ceramic components subjected to harsh thermomechanical loads that can vary with time (transient reliability analysis). This capability enables more accurate prediction of ceramic component integrity against fracture in situations such as turbine startup and shutdown, operational vibrations, atmospheric reentry, or other rapid heating or cooling situations (thermal shock). The transient reliability analysis methodology developed herein incorporates the following features: fast-fracture transient analysis (reliability analysis without slow crack growth, SCG); transient analysis with SCG (reliability analysis with time-dependent damage due to SCG); a computationally efficient algorithm to compute the reliability for components subjected to repeated transient loading (block loading); cyclic fatigue modeling using a combined SCG and Walker fatigue law; proof testing for transient loads; and Weibull and fatigue parameters that are allowed to vary with temperature or time. Component-to-component variation in strength (stochastic strength response) is accounted for with the Weibull distribution, and either the principle of independent action or the Batdorf theory is used to predict the effect of multiaxial stresses on reliability. The reliability analysis can be performed either as a function of the component surface (for surface-distributed flaws) or component volume (for volume-distributed flaws). The transient reliability analysis capability has been added to the NASA CARES/ Life (Ceramic Analysis and Reliability Evaluation of Structures/Life) code. CARES/Life was also updated to interface with commercially available finite element analysis software, such as ANSYS, when used to model the effects of transient load histories. Examples are provided to demonstrate the features of the methodology as implemented in the CARES/Life program.

Wave transience in a compressible atmosphere. I - Transient internal wave, mean-flow interaction. II - Transient equatorial waves in the quasi-biennial oscillation

NASA Technical Reports Server (NTRS)

Dunkerton, T. J.

1981-01-01

Analytical and numerical solutions are obtained in an approximate quasi-linear model, to describe the way in which vertically propagating waves give rise to mean flow accelerations in an atmosphere due to the effects of wave transience. These effects in turn result from compressibility and vertical group velocity feedback, and culminate in the spontaneous formation and descent of regions of strong mean wind shear. The numerical solutions display mean flow accelerations due to Kelvin waves in the equatorial stratosphere, with wave absorption altering the transience mechanism in such significant respects as causing the upper atmospheric mean flow acceleration to be very sensitive to the precise magnitude and distribution of the damping mechanisms. The numerical simulations of transient equatorial waves in the quasi-biennial oscillation are also considered.

Polariton excitation in epsilon-near-zero slabs: Transient trapping of slow light

NASA Astrophysics Data System (ADS)

Ciattoni, Alessandro; Marini, Andrea; Rizza, Carlo; Scalora, Michael; Biancalana, Fabio

2013-05-01

We numerically investigate the propagation of a spatially localized and quasimonochromatic electromagnetic pulse through a slab with a Lorentz dielectric response in the epsilon-near-zero regime, where the real part of the permittivity vanishes at the pulse carrier frequency. We show that the pulse is able to excite a set of virtual polariton modes supported by the slab, with the excitation undergoing a generally slow damping due to absorption and radiation leakage. Our numerical and analytical approaches indicate that in its transient dynamics the electromagnetic field displays the very same enhancement of the field component perpendicular to the slab, as in the monochromatic regime. The transient trapping is inherently accompanied by a significantly reduced group velocity ensuing from the small dielectric permittivity, thus providing an alternative platform for achieving control and manipulation of slow light.

First-principles electron dynamics control simulation of diamond under femtosecond laser pulse train irradiation.

PubMed

Wang, Cong; Jiang, Lan; Wang, Feng; Li, Xin; Yuan, Yanping; Xiao, Hai; Tsai, Hai-Lung; Lu, Yongfeng

2012-07-11

A real-time and real-space time-dependent density functional is applied to simulate the nonlinear electron-photon interactions during shaped femtosecond laser pulse train ablation of diamond. Effects of the key pulse train parameters such as the pulse separation, spatial/temporal pulse energy distribution and pulse number per train on the electron excitation and energy absorption are discussed. The calculations show that photon-electron interactions and transient localized electron dynamics can be controlled including photon absorption, electron excitation, electron density, and free electron distribution by the ultrafast laser pulse train.

Effects of surface and interface traps on exciton and multi-exciton dynamics in core/shell quantum dots

NASA Astrophysics Data System (ADS)

Bozio, Renato; Righetto, Marcello; Minotto, Alessandro

2017-08-01

Exciton interactions and dynamics are the most important factors determining the exceptional photophysical properties of semiconductor quantum dots (QDs). In particular, best performances have been obtained for ingeniously engineered core/shell QDs. We have studied two factors entering in the exciton decay dynamics with adverse effects for the luminescence efficiency: exciton trapping at surface and interface traps, and non-radiative Auger recombination in QDs carrying either net charges or multiple excitons. In this work, we present a detailed study into the optical absorption, fluorescence dynamics and quantum yield, as well as ultrafast transient absorption properties of CdSe/CdS, CdSe/Cd0.5Zn0.5S, and CdSe/ZnS QDs as a function of shell thickness. It turns out that de-trapping processes play a pivotal role in determining steady state emission properties. By studying the excitation dependent photoluminescence quantum yields (PLQY) in different CdSe/CdxZn1-xS (x = 0, 0.5, 1) QDs, we demonstrate the different role played by hot and cold carrier trapping rates in determining fluorescence quantum yields. Finally, the use of global analysis allows us untangling the complex ultrafast transient absorption signals. Smoothing of interface potential, together with effective surface passivation, appear to be crucial factors in slowing down both Auger-based and exciton trapping recombination processes.

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy.

PubMed

Hayes, Dugan; Kohler, Lars; Hadt, Ryan G; Zhang, Xiaoyi; Liu, Cunming; Mulfort, Karen L; Chen, Lin X

2018-01-28

The kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(i) bis(phenanthroline)/ruthenium(ii) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(i)-Ru(ii) analogs of the homodinuclear Cu(i)-Cu(i) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These results suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.

Cooling quasiparticles in A 3C 60 fullerides by excitonic mid-infrared absorption

NASA Astrophysics Data System (ADS)

Nava, Andrea; Giannetti, Claudio; Georges, Antoine; Tosatti, Erio; Fabrizio, Michele

2018-02-01

Long after its discovery, superconductivity in alkali fullerides A3C60 still challenges conventional wisdom. The freshest inroad in such ever-surprising physics is the behaviour under intense infrared excitation. Signatures attributable to a transient superconducting state extending up to temperatures ten times higher than the equilibrium Tc ~ 20 K have been discovered in K3C60 after ultra-short pulsed infrared irradiation--an effect which still appears as remarkable as mysterious. Motivated by the observation that the phenomenon is observed in a broad pumping frequency range that coincides with the mid-infrared electronic absorption peak still of unclear origin, rather than to transverse optical phonons as has been proposed, we advance here a radically new mechanism. First, we argue that this broad absorption peak represents a `super-exciton' involving the promotion of one electron from the t1u half-filled state to a higher-energy empty t1g state, dramatically lowered in energy by the large dipole-dipole interaction acting in conjunction with the Jahn-Teller effect within the enormously degenerate manifold of (t1u)2(t1g)1 states. Both long-lived and entropy-rich because they are triplets, the infrared-induced excitons act as a sort of cooling mechanism that permits transient superconductive signals to persist up to much higher temperatures.

Photoproduction of hydrated electrons from natural organic solutes in aquatic environments

USGS Publications Warehouse

Zepp, R.G.; Braun, A.M.; Hoigne, J.; Leenheer, J.A.

1987-01-01

Laser flash photolysis was used to investigate the transients formed on absorption of 355-nm light by dissolved organic matter (DOM) from natural water bodies and from soil. Absorption spectra and quenching studies of the transients provided confirming evidence that hydrated electrons were formed by all of the DOM that were studied. The DOM from the Suwannee River in Georgia and from the Greifensee, a Swiss lake, exhibited great variability in light-absorbing properties. Despite this high variability in absorption coefficients, the primary quantum yields for electron ejection from the Greifensee and Suwannee DOM fell in a narrow range (0.005-0.008). Steady-state irradiations (355 nm) of the DOM with 2-chloroethanol (0.02 M) present as an electron scavenger produced chloride ions with quantum yields that were about 2 orders of magnitude lower than the primary quantum yields. This result indicates that most of the photoejected electrons recombine with cations before escaping into bulk solution. Irradiations of DOM solutions under sunlight (April, latitude 34?? N) photoproduced electrons at rates falling in the range of 0.2-0.4 ??mol/[(mg of DOC) h]. These results indicate that hydrated electrons can play a significant role in the environmental photoreduction of persistent, electronegative pollutants but may be relatively unimportant in the environmental production of hydrogen peroxide. ?? 1987 American Chemical Society.

In-Situ Probing Plasmonic Energy Transfer in Cu(In, Ga)Se2 Solar Cells by Ultrabroadband Femtosecond Pump-Probe Spectroscopy.

PubMed

Chen, Shih-Chen; Wu, Kaung-Hsiung; Li, Jia-Xing; Yabushita, Atsushi; Tang, Shih-Han; Luo, Chih Wei; Juang, Jenh-Yih; Kuo, Hao-Chung; Chueh, Yu-Lun

2015-12-18

In this work, we demonstrated a viable experimental scheme for in-situ probing the effects of Au nanoparticles (NPs) incorporation on plasmonic energy transfer in Cu(In, Ga)Se2 (CIGS) solar cells by elaborately analyzing the lifetimes and zero moment for hot carrier relaxation with ultrabroadband femtosecond pump-probe spectroscopy. The signals of enhanced photobleach (PB) and waned photoinduced absorption (PIA) attributable to surface plasmon resonance (SPR) of Au NPs were in-situ probed in transient differential absorption spectra. The results suggested that substantial carriers can be excited from ground state to lower excitation energy levels, which can reach thermalization much faster with the existence of SPR. Thus, direct electron transfer (DET) could be implemented to enhance the photocurrent of CIGS solar cells. Furthermore, based on the extracted hot carrier lifetimes, it was confirmed that the improved electrical transport might have been resulted primarily from the reduction in the surface recombination of photoinduced carriers through enhanced local electromagnetic field (LEMF). Finally, theoretical calculation for resonant energy transfer (RET)-induced enhancement in the probability of exciting electron-hole pairs was conducted and the results agreed well with the enhanced PB peak of transient differential absorption in plasmonic CIGS film. These results indicate that plasmonic energy transfer is a viable approach to boost high-efficiency CIGS solar cells.

Plant phenolics and absorption features in vegetation reflectance spectra near 1.66 μm

USGS Publications Warehouse

Kokaly, Raymond F.; Skidmore, Andrew K

2015-01-01

Past laboratory and field studies have quantified phenolic substances in vegetative matter from reflectance measurements for understanding plant response to herbivores and insect predation. Past remote sensing studies on phenolics have evaluated crop quality and vegetation patterns caused by bedrock geology and associated variations in soil geochemistry. We examined spectra of pure phenolic compounds, common plant biochemical constituents, dry leaves, fresh leaves, and plant canopies for direct evidence of absorption features attributable to plant phenolics. Using spectral feature analysis with continuum removal, we observed that a narrow feature at 1.66 μm is persistent in spectra of manzanita, sumac, red maple, sugar maple, tea, and other species. This feature was consistent with absorption caused by aromatic C-H bonds in the chemical structure of phenolic compounds and non-hydroxylated aromatics. Because of overlapping absorption by water, the feature was weaker in fresh leaf and canopy spectra compared to dry leaf measurements. Simple linear regressions of feature depth and feature area with polyphenol concentration in tea resulted in high correlations and low errors (% phenol by dry weight) at the dry leaf (r2 = 0.95, RMSE = 1.0%, n = 56), fresh leaf (r2 = 0.79, RMSE = 2.1%, n = 56), and canopy (r2 = 0.78, RMSE = 1.0%, n = 13) levels of measurement. Spectra of leaves, needles, and canopies of big sagebrush and evergreens exhibited a weak absorption feature centered near 1.63 μm, short ward of the phenolic compounds, possibly consistent with terpenes. This study demonstrates that subtle variation in vegetation spectra in the shortwave infrared can directly indicate biochemical constituents and be used to quantify them. Phenolics are of lesser abundance compared to the major plant constituents but, nonetheless, have important plant functions and ecological significance. Additional research is needed to advance our understanding of the spectral influences of plant phenolics and terpenes relative to dominant leaf biochemistry (water, chlorophyll, protein/nitrogen, cellulose, and lignin).

Wavelength feature mapping as a proxy to mineral chemistry for investigating geologic systems: An example from the Rodalquilar epithermal system

NASA Astrophysics Data System (ADS)

van der Meer, Freek; Kopačková, Veronika; Koucká, Lucie; van der Werff, Harald M. A.; van Ruitenbeek, Frank J. A.; Bakker, Wim H.

2018-02-01

The final product of a geologic remote sensing data analysis using multi spectral and hyperspectral images is a mineral (abundance) map. Multispectral data, such as ASTER, Landsat, SPOT, Sentinel-2, typically allow to determine qualitative estimates of what minerals are in a pixel, while hyperspectral data allow to quantify this. As input to most image classification or spectral processing approach, endmembers are required. An alternative approach to classification is to derive absorption feature characteristics such as the wavelength position of the deepest absorption, depth of the absorption and symmetry of the absorption feature from hyperspectral data. Two approaches are presented, tested and compared in this paper: the 'Wavelength Mapper' and the 'QuanTools'. Although these algorithms use a different mathematical solution to derive absorption feature wavelength and depth, and use different image post-processing, the results are consistent, comparable and reproducible. The wavelength images can be directly linked to mineral type and abundance, but more importantly also to mineral chemical composition and subtle changes thereof. This in turn allows to interpret hyperspectral data in terms of mineral chemistry changes which is a proxy to pressure-temperature of formation of minerals. We show the case of the Rodalquilar epithermal system of the southern Spanish Gabo de Gata volcanic area using HyMAP airborne hyperspectral images.

Optimizing the ionization and energy absorption of laser-irradiated clusters

NASA Astrophysics Data System (ADS)

Kundu, M.; Bauer, D.

2008-03-01

It is known that rare-gas or metal clusters absorb incident laser energy very efficiently. However, due to the intricate dependencies on all the laser and cluster parameters, it is difficult to predict under which circumstances ionization and energy absorption are optimal. With the help of three-dimensional particle-in-cell simulations of xenon clusters (up to 17256 atoms), it is shown that for a given laser pulse energy and cluster, an optimum wavelength exists that corresponds to the approximate wavelength of the transient, linear Mie-resonance of the ionizing cluster at an early stage of negligible expansion. In a single ultrashort laser pulse, the linear resonance at this optimum wavelength yields much higher absorption efficiency than in the conventional, dual-pulse pump-probe setup of linear resonance during cluster expansion.

Classification by diagnosing all absorption features (CDAF) for the most abundant minerals in airborne hyperspectral images

NASA Astrophysics Data System (ADS)

Mobasheri, Mohammad Reza; Ghamary-Asl, Mohsen

2011-12-01

Imaging through hyperspectral technology is a powerful tool that can be used to spectrally identify and spatially map materials based on their specific absorption characteristics in electromagnetic spectrum. A robust method called Tetracorder has shown its effectiveness at material identification and mapping, using a set of algorithms within an expert system decision-making framework. In this study, using some stages of Tetracorder, a technique called classification by diagnosing all absorption features (CDAF) is introduced. This technique enables one to assign a class to the most abundant mineral in each pixel with high accuracy. The technique is based on the derivation of information from reflectance spectra of the image. This can be done through extraction of spectral absorption features of any minerals from their respected laboratory-measured reflectance spectra, and comparing it with those extracted from the pixels in the image. The CDAF technique has been executed on the AVIRIS image where the results show an overall accuracy of better than 96%.

A new transiently chaotic flow with ellipsoid equilibria

NASA Astrophysics Data System (ADS)

Panahi, Shirin; Aram, Zainab; Jafari, Sajad; Pham, Viet-Thanh; Volos, Christos; Rajagopal, Karthikeyan

2018-03-01

In this article, a simple autonomous transiently chaotic flow with cubic nonlinearities is proposed. This system represents some unusual features such as having a surface of equilibria. We shall describe some dynamical properties and behaviours of this system in terms of eigenvalue structures, bifurcation diagrams, time series, and phase portraits. Various behaviours of this system such as periodic and transiently chaotic dynamics can be shown by setting special parameters in proper values. Our system belongs to a newly introduced category of transiently chaotic systems: systems with hidden attractors. Transiently chaotic behaviour of our proposed system has been implemented and tested by the OrCAD-PSpise software. We have found a proper qualitative similarity between circuit and simulation results.

Hydrothermal alteration mapping using ASTER data in Baogutu porphyry deposit, China

NASA Astrophysics Data System (ADS)

Li, Q.; Zhang, B.; Lu, L.; Lin, Q.

2014-03-01

Remote sensing plays an important role in mineral exploration. One of its proven applications is extracting host-rock lithology and alteration zones that are related to porphyry copper deposits. An Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) was used to map the Baogutu porphyry deposit alteration area. A circular alteration mineral zoning pattern was clearly observed in the classification result of potassic, phyllic, argillic, propylitic zones. The potassic is characterized by biotite and anhydrite with an absorption feature centered at 1.94 and 2.1um. The phyllic zone is characterized by illite and sericite that indicates an intense Al-OH absorption feature centered at 2.20um. The narrower argillic zone including kaolinite and alunite displays a secondary Al-OH absorption feature at 2.17 um. The mineral assemblages of the outer propylitic zone are epidote, chlorite and calcite that exhibit absorption features at 2.335um.The performance of Principal Component Analysis(PCA), Minimum Noise Fraction (MNF), band ratio(BR) and Constrained Energy Minimization(CEM) has been evaluated. These techniques identified new prospects of porphyry copper mineralization in the study areas. These results indicate that ASTER is a powerful tool in the initial steps of mineral exploration.

Negative Searches for Evidence of Aqueous Alteration on Asteroid Surfaces

NASA Technical Reports Server (NTRS)

Vilas, F.

2005-01-01

Small bodies in the Solar System preserve evidence of the processes occurring during early Solar System formation, unlike the larger planets that undergo continuous churning of their surfaces. We study these bodies to understand what processes affected different stages of Solar System formation. The action of aqueous alteration (the alteration of material by the interaction of that material with liquid formed by the melting of incorporated ice) of near-subsurface material has been inferred to occur on many asteroids based on the spectrophotometric evidence of phyllosilicates and iron alteration minerals. The definitive indication of aqueous alteration is the 3.0- micron absorption feature attributed to structural hydroxyl (OH) and interlayer and adsorbed water (H2O) in phyllosilicates (clays) (hereafter water of hydration). A weak absorption feature centered near 0.7 microns attributed to an Fe (2+) right arrow Fe (3+) charge transfer transition in oxidized iron in phyllosilicates has been observed in the reflectance spectra and photometry of approximately 50% of the main-belt C-class asteroids. An approximately 85% correlation between this 0.7- micron feature and the 3.0- micron water of hydration absorption feature was found among the low-albedo asteroids. The feature is usually centered near 0.68 microns in asteroid spectra, and ranges in wavelength from approximately 0.57 to 0.83 microns. Serendipitously, three of the Eight Color Asteroid Survey filters the v (0.550 microns), w (0.701 microns), and x (0.853 microns)-bracket this feature well, and can be used to determine the presence of this feature in the reflectance properties of an asteroid, and probe the aqueous alteration history of larger samples of asteroid data. Two efforts to search for evidence of aqueous alteration based on the presence of this 0.7- micron absorption feature are presented here.

STUDENT AWARD FINALIST: Oxygen Pathways in Streamer Discharge for Transient Plasma Ignition

NASA Astrophysics Data System (ADS)

Pendleton, S. J.; Bowman, S.; Singleton, D.; Watrous, J.; Carter, C.; Lempert, W.; Gundersen, M. A.

2011-10-01

The use of streamers for the ignition of fuels, also known as transient plasma ignition (TPI), has been shown in a variety of engines to improve combustion through decreased ignition delay, increased lean burn capability and increased energy release relative to conventional spark ignition. The mechanisms behind these improvements, however, remain poorly understood. Temperature measurements by optical emission spectroscopy demonstrate that ignition by TPI is a nonthermal process, and thus is almost entirely dependent on the production and presence of electron impact-created active species in the discharge afterglow. Of particular interest are active oxygen species due to their relatively long lifetimes at high pressures and the pivotal role they play in combustion reactions. In order to elucidate the oxygen pathways, here we report the investigation of the temporal evolution of the populations of atomic oxygen and ozone by use of two-photon absorption laser induced fluorescence (TALIF) and UV absorption, respectively. Experimental results are presented and compared to kinetic modeling of the streamers. Future experiments are proposed to better understand the physics behind TPI. Supported by NSF, AFOSR, NumerEx-ONR, AFRL-WPAFB.

Apparatus and method for transient thermal infrared spectrometry of flowable enclosed materials

DOEpatents

McClelland, John F.; Jones, Roger W.

1993-03-02

A method and apparatus for enabling analysis of a flowable material enclosed in a transport system having an infrared transparent wall portion. A temperature differential is transiently generated between a thin surface layer portion of the material and a lower or deeper portion of the material sufficient to alter the thermal infrared emission spectrum of the material from the black-body thermal infrared emission spectrum of the material, and the altered thermal infrared emission spectrum is detected through the infrared transparent portion of the transport system while the altered thermal infrared emission spectrum is sufficiently free of self-absorption by the material of emitted infrared radiation. The detection is effected prior to the temperature differential propagating into the lower or deeper portion of the material to an extent such that the altered thermal infrared emission spectrum is no longer sufficiently free of self-absorption by the material of emitted infrared radiation. By such detection, the detected altered thermal infrared emission spectrum is indicative of characteristics relating to molecular composition of the material.

Dynamics of intramolecular electron transfer reaction of FAD studied by magnetic field effects on transient absorption spectra.

PubMed

Murakami, Masaaki; Maeda, Kiminori; Arai, Tatsuo

2005-07-07

The kinetics of intermediates generated from intramolecular electron-transfer reaction by photo irradiation of the flavin adenine dinucleotide (FAD) molecule was studied by a magnetic field effect (MFE) on transient absorption (TA) spectra. Existence time of MFE and MFE action spectra have a strong dependence on the pH of solutions. The MFE action spectra have indicated the existence of interconversion between the radical pair and the cation form of the triplet excited state of flavin part. All rate constants of the triplet and the radical pair were determined by analysis of the MFE action spectra and decay kinetics of TA. The obtained values for the interconversion indicate that the formation of cation radical promotes the back electron-transfer reaction to the triplet excited state. Further, rate constants of spin relaxation and recombination have been studied by the time profiles of MFE at various pH. The drastic change of those two factors has been obtained and can be explained by SOC (spin-orbit coupling) induced back electron-transfer promoted by the formation of a stacking conformation at pH > 2.5.

Complex Resonance Absorption Structure in the X-Ray Spectrum of IRAS 13349+2438

NASA Technical Reports Server (NTRS)

Sako, M.; Kahn, S. M.; Behar, E.; Kaastra, J. S.; Brinkman, A. C.; Boller, Th.; Puchnarewicz, E. M.; Starling, R.; Liedahl, D. A.; Clavel, J.

2000-01-01

The luminous infrared-loud quasar IRAS 13349+2438 was observed with the XMM - Newton Observatory as part of the Performance Verification program. The spectrum obtained by the Reflection Grating Spectrometer (RGS) exhibits broad (FWHM - 1400 km/s) absorption lines from highly ionized elements including hydrogen- and helium-like carbon, nitrogen, oxygen, and neon, and several iron L - shell ions (Fe XVII - XX). Also shown in the spectrum is the first astrophysical detection of a broad absorption feature around lambda = 16 - 17 A identified as an unresolved transition array (UTA) of 2p - 3d inner-shell absorption by iron M-shell ions in a much cooler medium; a feature that might be misidentified as an O VII edge when observed with moderate resolution spectrometers. No absorption edges are clearly detected in the spectrum. We demonstrate that the RGS spectrum of IRAS 13349+2438 exhibits absorption lines from two distinct regions, one of which is tentatively associated with the medium that produces the optical/UV reddening.

Two-Flux and Green's Function Method for Transient Radiative Transfer in a Semi-Transparent Layer

NASA Technical Reports Server (NTRS)

Siegel, Robert

1995-01-01

A method using a Green's function is developed for computing transient temperatures in a semitransparent layer by using the two-flux method coupled with the transient energy equation. Each boundary of the layer is exposed to a hot or cold radiative environment, and is heated or cooled by convection. The layer refractive index is larger than one, and the effect of internal reflections is included with the boundaries assumed diffuse. The analysis accounts for internal emission, absorption, heat conduction, and isotropic scattering. Spectrally dependent radiative properties are included, and transient results are given to illustrate two-band spectral behavior with optically thin and thick bands. Transient results using the present Green's function method are verified for a gray layer by comparison with a finite difference solution of the exact radiative transfer equations; excellent agreement is obtained. The present method requires only moderate computing times and incorporates isotropic scattering without additional complexity. Typical temperature distributions are given to illustrate application of the method by examining the effect of strong radiative heating on one side of a layer with convective cooling on the other side, and the interaction of strong convective heating with radiative cooling from the layer interior.

Chemometric analysis of correlations between electronic absorption characteristics and structural and/or physicochemical parameters for ampholytic substances of biological and pharmaceutical relevance.

PubMed

Judycka-Proma, U; Bober, L; Gajewicz, A; Puzyn, T; Błażejowski, J

2015-03-05

Forty ampholytic compounds of biological and pharmaceutical relevance were subjected to chemometric analysis based on unsupervised and supervised learning algorithms. This enabled relations to be found between empirical spectral characteristics derived from electronic absorption data and structural and physicochemical parameters predicted by quantum chemistry methods or phenomenological relationships based on additivity rules. It was found that the energies of long wavelength absorption bands are correlated through multiparametric linear relationships with parameters reflecting the bulkiness features of the absorbing molecules as well as their nucleophilicity and electrophilicity. These dependences enable the quantitative analysis of spectral features of the compounds, as well as a comparison of their similarities and certain pharmaceutical and biological features. Three QSPR models to predict the energies of long-wavelength absorption in buffers with pH=2.5 and pH=7.0, as well as in methanol, were developed and validated in this study. These models can be further used to predict the long-wavelength absorption energies of untested substances (if they are structurally similar to the training compounds). Copyright © 2014 Elsevier B.V. All rights reserved.

Detection of H I absorption in the dwarf galaxy Haro 11

NASA Astrophysics Data System (ADS)

MacHattie, Jeremy A.; Irwin, Judith A.; Madden, Suzanne C.; Cormier, Diane; Rémy-Ruyer, Aurélie

2014-02-01

We present the results of an analysis of archival 21 cm (H I) data of the blue compact dwarf galaxy Haro 11 (ESO 350-IG038). Observations were obtained at the Very Large Array, and the presence of a compact absorption feature near the optical centre of the galaxy has been detected. The central location of the absorption feature coincides with the centre of the continuum background of the galaxy, as well as with the location of knot B. The absorption feature yields an H I mass in the range of 3-10 × 108 M⊙, corresponding to spin temperatures from 91 K to 200 K, respectively. The absence of H I seen in emission places an upper limit of 1.7 × 109 M⊙ on the mass. To our knowledge this is the first example of a dwarf galaxy that shows H I absorption from its own background continuum. The continuum emission from the galaxy is also used to determine star formation rates, namely 6.85 ± 0.05 M⊙ yr-1 (for a stellar mass range of 5 M⊙ < M < 100 M⊙), or 32.8 ± 0.2 M⊙ yr-1 (for an extended range of 0.1 M⊙ < M < 100 M⊙).

Transient behaviour of EIT and EIA in an optical-radio two-photon coupling configuration

NASA Astrophysics Data System (ADS)

Li, Xiaoli; Yang, Zicai; Shang, Yaxuan

2012-11-01

Both electromagnetically induced absorption (EIA) and transparency (EIT) can be obtained in a modified quasi-lambda four level system consisting of an optical-radio two-photon coupling field and a probing field. A physical account of EIA and EIT is given in terms of a transient state picture in this paper. It can be seen that the optical coupling field in this quasi-lambda four level system has a crucial effect on the forming of EIA and EIT. An EIA is observed under a resonant optical coupling and it evolves into an EIT when there is a detuning.

Influence of carrier density on the electronic cooling channels of bilayer graphene

NASA Astrophysics Data System (ADS)

Limmer, T.; Houtepen, A. J.; Niggebaum, A.; Tautz, R.; Da Como, E.

2011-09-01

We study the electronic cooling dynamics in a single flake of bilayer graphene by femtosecond transient absorption probing the photon-energy range 0.25-1.3 eV. From the transients, we extract the carrier cooling curves for different initial temperatures and densities of the photoexcited electrons and holes. Two regimes of carrier cooling, dominated by optical and acoustic phonons emission, are clearly identified. For increasing carrier density, the crossover between the two regimes occurs at larger carrier temperatures, since cooling via optical phonons experiences a bottleneck. Acoustic phonons, which are less sensitive to saturation, show an increasing contribution at high density.

[Observation of carbon-bear free radicals using far infrared laser magnetic resonance spectroscopy].

PubMed

Huang, Guang-ming; Shi, Li-hua; Cai, Xin; Liu, Yu-yan

2003-06-01

The principle and technical characters of far infrared laser magnetic resonance (FIRLMR) spectrometer built up in China are introduced. A CO2 transversely pumped far infrared laser is adopted. In order to obtain high sensitivity, the sample absorption cell is placed in the FIR laser cavity and separated from laser gain cavity with thin polypropylene film. The spectrometer can be employed to study short lived free radicals. The spectra of many transient free radicals including CCH, CF and CH2 have been detected by the spectrometer. These transients are generated by mixing CH4 with the fluorine atoms produced with microwave discharge.

Spectral characterization of guanine C4-OH adduct: a radiation and quantum chemical study.

PubMed

Phadatare, Suvarna D; Sharma, Kiran Kumar K; Rao, B S M; Naumov, S; Sharma, Geeta K

2011-11-24

The reaction of hydroxyl radical ((•)OH) with guanine was investigated under restricted pH condition (pH 4.6) using pulse radiolysis technique. The time-resolved optical transient absorption spectra showed two peaks centered at 300 and 330 nm at 4 μs after the pulse which exhibited different reactivity toward molecular oxygen (O(2)). The peak at 300 nm was found to be relatively more stable than the peak at 330 nm. The peak corresponding to 330 nm decayed within 20 μs having a first order rate constant 4-7 × 10(4) s(-1) and was pH dependent. On longer time scale, the species decayed by a bimolecular process. The presence of O(2) did not affect its decay rate constant. The (•)OH reacts with guanine at pH 4.6 with a diffusion-controlled second order rate constant of ≥1 × 10(10) mol(-1) dm(3) s(-1). The reaction of Br(2)(•-), O(2)(•-), and 2-hydroxy-2-propyl radical with guanine was also investigated to differentiate among the one-electron oxidized, one-electron reduced species of guanine and the guanine-OH adducts formed in the reaction of (•)OH at pH 4.6. On the basis of the spectral characteristics and reactivity toward O(2), two guanine-OH adduct species were identified (i) the C4-OH adduct species absorbing at 330 nm which has not been reported so far and (ii) the C8-OH adduct species absorbing at 300 nm in agreement with the known literature absorption features. Quantum chemical calculations using BHandHLYP with 6-31+G(d,p) basis set and excited state calculations using TDDFT for all possible transients complement the assignment of the observed spectral peak at 330 nm to the C4-OH adduct of guanine. Furthermore, steady state radiolysis revealed the formation of 8-hydroxy-guanine whose precursor is known to be the C8-OH adduct species. © 2011 American Chemical Society

Bodipy–C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer† †Electronic supplementary information (ESI) available: Syntheses, structure characterization data, and UV/vis absorption and emission spectra. See DOI: 10.1039/c4sc03865g

PubMed Central

Guo, Song; Xu, Liang; Xu, Kejing; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-01-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives (B-1, B-2 and B-3, which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C60 was used as the complementary hydrogen bonding module (C-1), in which the C60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references (B-1-Me, B-2-Me and B-3-Me), which are unable to form strong H-bonds with C-1. Triple H-bonds are formed between each Bodipy antenna (B-1, B-2 and B-3) and the C60 module (C-1). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C60 module (for assembly B-1·C-1), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1). Intra-assembly forward–backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet–triplet annihilation upconversion. PMID:29218142

A frequency quantum interpretation of the surface renewal model of mass transfer

PubMed Central

Mondal, Chanchal

2017-01-01

The surface of a turbulent liquid is visualized as consisting of a large number of chaotic eddies or liquid elements. Assuming that surface elements of a particular age have renewal frequencies that are integral multiples of a fundamental frequency quantum, and further assuming that the renewal frequency distribution is of the Boltzmann type, performing a population balance for these elements leads to the Danckwerts surface age distribution. The basic quantum is what has been traditionally called the rate of surface renewal. The Higbie surface age distribution follows if the renewal frequency distribution of such elements is assumed to be continuous. Four age distributions, which reflect different start-up conditions of the absorption process, are then used to analyse transient physical gas absorption into a large volume of liquid, assuming negligible gas-side mass-transfer resistance. The first two are different versions of the Danckwerts model, the third one is based on the uniform and Higbie distributions, while the fourth one is a mixed distribution. For the four cases, theoretical expressions are derived for the rates of gas absorption and dissolved-gas transfer to the bulk liquid. Under transient conditions, these two rates are not equal and have an inverse relationship. However, with the progress of absorption towards steady state, they approach one another. Assuming steady-state conditions, the conventional one-parameter Danckwerts age distribution is generalized to a two-parameter age distribution. Like the two-parameter logarithmic normal distribution, this distribution can also capture the bell-shaped nature of the distribution of the ages of surface elements observed experimentally in air–sea gas and heat exchange. Estimates of the liquid-side mass-transfer coefficient made using these two distributions for the absorption of hydrogen and oxygen in water are very close to one another and are comparable to experimental values reported in the literature. PMID:28791137

Schumann resonance transients and the search for gravitational waves

NASA Astrophysics Data System (ADS)

Silagadze, Z. K.

2018-02-01

Schumann resonance transients which propagate around the globe can potentially generate a correlated background in widely separated gravitational-wave detectors. We show that due to the distribution of lightning hotspots around the globe, these transients have characteristic time lags, and this feature can be useful to further suppress such a background, especially in searches of the stochastic gravitational-wave background. A brief review of the corresponding literature on Schumann resonances and lightnings is also given.

The widetilde{A}←widetilde{X} ABSORPTION SPECTRUM OF 2-NITROOXYBUTYL PEROXY RADICAL

NASA Astrophysics Data System (ADS)

Eddingsaas, Nathan; Takematsu, Kana; Okumura, Mitchio

2009-06-01

The nitrate radical is an important atmospheric oxidant in the nighttime sky. Nitrate radicals react by addition to alkenes, and in the presence of oxygen form nitrooxyalkyl peroxy radicals. The peroxy radical formed from the reaction of 2-butene, nitrate radical, and oxygen was detected by cavity ringdown spectroscopy (CRDS) via its widetilde{A}←widetilde{X} electronic absorption spectrum. The widetilde{A}←widetilde{X} electronic transition is a bound-bound transition with enough structure to distinguish between different peroxy radicals as well as different conformers of the same peroxy radical. Two conformers of the nitrooxybutyl peroxy radical have been observed; the absorption features are red shifted from the same absorption features of sec-butyl peroxy radical. Calculations on the structure of nitrooxyalkyl peroxy radicals and general trends of the position of the widetilde{A}←widetilde{X} absorption transitions have also been performed and compared to those of unsubstituted peroxy radicals.

Interstellar proteins and the discovery of a new absorption feature at lambda = 2800 A

NASA Astrophysics Data System (ADS)

Karim, L. M.; Hoyle, F.; Wickramasinghe, N. C.

1983-07-01

In order to check the presence of biogenic materials in interstellar grains, the spectra of three early-type, heavily reddened stars recorded by the IUE were examined. These stars showed comparatively weak absorption at 2200 A, minimizing the effect of graphite grains. A broad absorption feature centered on 2800 A is discovered in HD 14250 and interpreted to be due to the amino acid tryptophan. Comparison of the spectrum with that of the calculated extinction behavior of graphite spheres of radii 0.02 microns suggests that the latter are not responsible for the observed spectrum.

Ultrafast Photodissociation Dynamics of Nitromethane.

PubMed

Nelson, Tammie; Bjorgaard, Josiah; Greenfield, Margo; Bolme, Cindy; Brown, Katie; McGrane, Shawn; Scharff, R Jason; Tretiak, Sergei

2016-02-04

Nitromethane (NM), a high explosive (HE) with low sensitivity, is known to undergo photolysis upon ultraviolet (UV) irradiation. The optical transparency, homogeneity, and extensive study of NM make it an ideal system for studying photodissociation mechanisms in conventional HE materials. The photochemical processes involved in the decomposition of NM could be applied to the future design of controllable photoactive HE materials. In this study, the photodecomposition of NM from the nπ* state excited at 266 nm is being investigated on the femtosecond time scale. UV femtosecond transient absorption (TA) spectroscopy and excited state femtosecond stimulated Raman spectroscopy (FSRS) are combined with nonadiabatic excited state molecular dynamics (NA-ESMD) simulations to provide a unified picture of NM photodecomposition. The FSRS spectrum of the photoproduct exhibits peaks in the NO2 region and slightly shifted C-N vibrational peaks pointing to methyl nitrite formation as the dominant photoproduct. A total photolysis quantum yield of 0.27 and an nπ* state lifetime of ∼20 fs were predicted from NA-ESMD simulations. Predicted time scales revealed that NO2 dissociation occurs in 81 ± 4 fs and methyl nitrite formation is much slower having a time scale of 452 ± 9 fs corresponding to the excited state absorption feature with a decay of 480 ± 17 fs observed in the TA spectrum. Although simulations predict C-N bond cleavage as the primary photochemical process, the relative time scales are consistent with isomerization occurring via NO2 dissociation and subsequent rebinding of the methyl radical and nitrogen dioxide.

Mutation-Induced Changes in the Protein Environment and Site Energies in the (M)L214G Mutant of the Rhodobacter sphaeroides Bacterial Reaction Center.

PubMed

Jankowiak, Ryszard; Rancova, Olga; Chen, Jinhai; Kell, Adam; Saer, Rafael G; Beatty, J Thomas; Abramavicius, Darius

2016-08-18

This work focuses on the low-temperature (5 K) photochemical (transient) hole-burned (HB) spectra within the P870 absorption band, and their theoretical analysis, for the (M)L214G mutant of the photosynthetic Rhodobacter sphaeroides bacterial reaction center (bRC). To provide insight into system-bath interactions of the bacteriochlorophyll a (BChl a) special pair, i.e., P870, in the mutated bRC, the optical line shape function for the P870 band is calculated numerically. On the basis of the modeling studies, we demonstrate that (M)L214G mutation leads to a heterogeneous population of bRCs with modified (increased) total electron-phonon coupling strength of the special pair BChl a and larger inhomogeneous broadening. Specifically, we show that after mutation in the (M)L214G bRC a large fraction (∼50%) of the bacteriopheophytin (HA) chromophores shifts red and the 800 nm absorption band broadens, while the remaining fraction of HA cofactors retains nearly the same site energy as HA in the wild-type bRC. Modeling using these two subpopulations allowed for fits of the absorption and nonresonant (transient) HB spectra of the mutant bRC in the charge neutral, oxidized, and charge-separated states using the Frenkel exciton Hamiltonian, providing new insight into the mutant's complex electronic structure. Although the average (M)L214G mutant quantum efficiency of P(+)QA(-) state formation seems to be altered in comparison with the wild-type bRC, the average electron transfer time (measured via resonant transient HB spectra within the P870 band) was not affected. Thus, mutation in the vicinity of the electron acceptor (HA) does not tune the charge separation dynamics. Finally, quenching of the (M)L214G mutant excited states by P(+) is addressed by persistent HB spectra burned within the B band in chemically oxidized samples.

Measurements of gas parameters in plasma-assisted supersonic combustion processes using diode laser spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolshov, Mikhail A; Kuritsyn, Yu A; Liger, V V

2009-09-30

We report a procedure for temperature and water vapour concentration measurements in an unsteady-state combustion zone using diode laser absorption spectroscopy. The procedure involves measurements of the absorption spectrum of water molecules around 1.39 {mu}m. It has been used to determine hydrogen combustion parameters in M = 2 gas flows in the test section of a supersonic wind tunnel. The relatively high intensities of the absorption lines used have enabled direct absorption measurements. We describe a differential technique for measurements of transient absorption spectra, the procedure we used for primary data processing and approaches for determining the gas temperature andmore » H{sub 2}O concentration in the probed zone. The measured absorption spectra are fitted with spectra simulated using parameters from spectroscopic databases. The combustion-time-averaged ({approx}50 ms) gas temperature and water vapour partial pressure in the hot wake region are determined to be 1050 K and 21 Torr, respectively. The large signal-to-noise ratio in our measurements allowed us to assess the temporal behaviour of these parameters. The accuracy in our temperature measurements in the probed zone is {approx}40 K. (laser applications and other topics in quantum electronics)« less

LASER APPLICATIONS AND OTHER TOPICS IN QUANTUM ELECTRONICS: Measurements of gas parameters in plasma-assisted supersonic combustion processes using diode laser spectroscopy

NASA Astrophysics Data System (ADS)

Bolshov, Mikhail A.; Kuritsyn, Yu A.; Liger, V. V.; Mironenko, V. R.; Leonov, S. B.; Yarantsev, D. A.

2009-09-01

We report a procedure for temperature and water vapour concentration measurements in an unsteady-state combustion zone using diode laser absorption spectroscopy. The procedure involves measurements of the absorption spectrum of water molecules around 1.39 μm. It has been used to determine hydrogen combustion parameters in M = 2 gas flows in the test section of a supersonic wind tunnel. The relatively high intensities of the absorption lines used have enabled direct absorption measurements. We describe a differential technique for measurements of transient absorption spectra, the procedure we used for primary data processing and approaches for determining the gas temperature and H2O concentration in the probed zone. The measured absorption spectra are fitted with spectra simulated using parameters from spectroscopic databases. The combustion-time-averaged (~50 ms) gas temperature and water vapour partial pressure in the hot wake region are determined to be 1050 K and 21 Torr, respectively. The large signal-to-noise ratio in our measurements allowed us to assess the temporal behaviour of these parameters. The accuracy in our temperature measurements in the probed zone is ~40 K.

Bodipy-C60 triple hydrogen bonding assemblies as heavy atom-free triplet photosensitizers: preparation and study of the singlet/triplet energy transfer.

PubMed

Guo, Song; Xu, Liang; Xu, Kejing; Zhao, Jianzhang; Küçüköz, Betül; Karatay, Ahmet; Yaglioglu, Halime Gul; Hayvali, Mustafa; Elmali, Ayhan

2015-07-01

Supramolecular triplet photosensitizers based on hydrogen bonding-mediated molecular assemblies were prepared. Three thymine-containing visible light-harvesting Bodipy derivatives ( B-1 , B-2 and B-3 , which show absorption at 505 nm, 630 nm and 593 nm, respectively) were used as H-bonding modules, and 1,6-diaminopyridine-appended C 60 was used as the complementary hydrogen bonding module ( C-1 ), in which the C 60 part acts as a spin converter for triplet formation. Visible light-harvesting antennae with methylated thymine were prepared as references ( B-1-Me , B-2-Me and B-3-Me ), which are unable to form strong H-bonds with C-1 . Triple H-bonds are formed between each Bodipy antenna ( B-1 , B-2 and B-3 ) and the C 60 module ( C-1 ). The photophysical properties of the H-bonding assemblies and the reference non-hydrogen bond-forming mixtures were studied using steady state UV/vis absorption spectroscopy, fluorescence emission spectroscopy, electrochemical characterization, and nanosecond transient absorption spectroscopy. Singlet energy transfer from the Bodipy antenna to the C 60 module was confirmed by fluorescence quenching studies. The intersystem crossing of the latter produced the triplet excited state. The nanosecond transient absorption spectroscopy showed that the triplet state is either localized on the C 60 module (for assembly B-1·C-1 ), or on the styryl-Bodipy antenna (for assemblies B-2·C-1 and B-3·C-1 ). Intra-assembly forward-backward (ping-pong) singlet/triplet energy transfer was proposed. In contrast to the H-bonding assemblies, slow triplet energy transfer was observed for the non-hydrogen bonding mixtures. As a proof of concept, these supramolecular assemblies were used as triplet photosensitizers for triplet-triplet annihilation upconversion.

Multiepoch Spectropolarimetry of SN 2011fe

DOE Office of Scientific and Technical Information (OSTI.GOV)

Milne, Peter A.; Williams, G. Grant; Smith, Paul S.

2017-01-20

We present multiple spectropolarimetric observations of the nearby Type Ia supernova (SN) 2011fe in M101, obtained before, during, and after the time of maximum apparent visual brightness. The excellent time coverage of our spectropolarimetry has allowed better monitoring of the evolution of polarization features than is typical, which has allowed us new insight into the nature of normal SNe Ia. SN 2011fe exhibits time-dependent polarization in both the continuum and strong absorption lines. At early epochs, red wavelengths exhibit a degree of continuum polarization of up to 0.4%, likely indicative of a mild asymmetry in the electron-scattering photosphere. This behaviormore » is more common in subluminous SNe Ia than in normal events, such as SN 2011fe. The degree of polarization across a collection of absorption lines varies dramatically from epoch to epoch. During the earliest epoch, a λ 4600–5000 Å complex of absorption lines shows enhanced polarization at a different position angle than the continuum. We explore the origin of these features, presenting a few possible interpretations, without arriving at a single favored ion. During two epochs near maximum, the dominant polarization feature is associated with the Si ii λ 6355 Å absorption line. This is common for SNe Ia, but for SN 2011fe the polarization of this feature increases after maximum light, whereas for other SNe Ia, that polarization feature was strongest before maximum light.« less

Risk factors for early death in transient myeloproliferative disorder without phenotypic features of Down syndrome: a case report and literature review.

PubMed

Kawase, Koya; Azuma, Eiichi; Ohshita, Hironori; Tanaka, Tatsushi; Hanada, Yu; Sasaki, Tomoaki; Sugimoto, Mari; Togawa, Takao; Kouwaki, Masanori; Ito, Tsuyoshi; Hirayama, Masahiro; Koyama, Norihisa

2012-08-01

Not only in newborns with Down syndrome, but newborns without phenotypic features of Down syndrome also develop transient myeloproliferative disorder (TMD). In these cases, trisomy 21 and related chromosomal abnormalities are either constitutionally mosaic or limited to blood cells. Risk factors for early death of these patients are unknown so far. We here report a fatal case of TMD without phenotypic features of Down syndrome and review literature to identify risk factors associated with early death. Not only are gestational age and white blood cell count risk factors for early death in TMD with Down syndrome, but they also appear to be risk factors in TMD without Down syndrome.

Ferric iron in primitive asteroids - A 0.43-micron absorption feature

NASA Technical Reports Server (NTRS)

Vilas, Faith; Hatch, Erin C.; Larson, Stephen M.; Sawyer, Scott R.; Gaffey, Michael J.

1993-01-01

A search of reflectance spectra of C- P-, D- and S-class asteroids to hunt for the Soret band near 0.4 micron that is indicative of porphyrins yielded an identification of an 0.43 micron absorption feature in 11 primitive asteroids of the C, P, and G classes and in one S-class asteroid. It is proposed that the feature is an Fe(3+) spin-forbidden transition in aqueously altered material, possibly located near 0.43 micron due to an enhancement effect similar to the mechanism operating in jarosite. The significance of the feature for the aqueous alteration history of these asteroids is addressed.

Preliminary results from an investigation of AIS-1 data over an area of epithermal alteration: Plateau, Northern Queensland, Australia

NASA Technical Reports Server (NTRS)

Mackin, Steve; Munday, Tim; Hook, Simon

1987-01-01

Airborne Imaging Spectrometer-1 (AIS-1) data were flown over undifferentiated sequences of acid to intermediate volcanics and intrusives; meta-sediments; and a series of partially lateritized sedimentary rocks. The area exhibits a considerable spectral variability, after the suppression of striping effects. Log residual, and Internal Average Relative Reflectance (IARR) analytical techniques were used to enhance mineralogically related spectral features. Both methods produce similar results, but did not visually highlight mineral absorption features due to processing artifacts in areas of significant vegetation cover. The enhancement of mineral related absorption features was achieved using a hybrid processing approach based on the relative reflectance differences between vegetated and non-vegetated surfaces at 1.2 and 2.1 micron. The result is an image with little overall contrast, but which enhances the more subtle spectral features believed to be associated with clays and epidote. The AIS data was subject to interactive analysis using SPAM. Clear separation of clay and epidote related absorption features was apparent, and the identification of kaolinite was possible despite detrimental spectral effects.

Line Identifications in the Far Ultraviolet Spectrum of the Eclipsing Binary System 31 Cygni

NASA Astrophysics Data System (ADS)

Hagen Bauer, Wendy; Bennett, P. D.

2011-05-01

The eclipsing binary system 31 Cygni (K4 Ib + B3 V) was observed at several phases with the Far Ultraviolet Spectrosocopic Explorer (FUSE) satellite. During total eclipse, a rich emission spectrum was observed, produced by scattering of hot star photons in the extended wind of the K supergiant. The system was observed during deep chromospheric eclipse, and 2.5 months after total eclipse ended. We present an atlas of line identifications in these spectra. During total eclipse, emission features from C II , C III, N I, N II, N III, O I, Si II, P II, P III, S II, S III, Ar I, Cr III, Fe II, Fe III, and Ni II were detected. The strongest emission features arise from N II. These lines appear strongly in absorption during chromospheric eclipse, and even 2.5 months after total eclipse, the absorption bottoms out on the underlying emission seen during total eclipse. The second strongest features in the emission spectrum arise from Fe III. Any chromospheric Fe III absorption is buried within strong chromospheric absorption from other species, mainly Fe II. The emission profiles of most of the doubly-ionized species are red-shifted relative to the systemic velocity, with asymmetric profiles with a steeper long-wavelength edge. Emission profiles from singly-ionized species tend to be more symmetric and centered near the systemic velocity. In deep chromospheric eclipse, absorption features are seen from neutral and singly-ionized species, arising from lower levels up to 3 eV. Many strong chromospheric features are doubled in the observation obtained during egress from eclipse. The 31 Cygni spectrum taken 2.5 months after total eclipse ended ws compared to single-star B spectra from the FUSE archives. There was still some additional chromospheric absorption from strong low-excitation Fe II, O I and Ar I.

Tuning optical absorption and photoexcited recombination dynamics in La1-xSrxFeO3-δ through A-site substitution and oxygen vacancies

NASA Astrophysics Data System (ADS)

Smolin, Sergey; Scafetta, Mark; Choquette, Amber; Sfeir, Matthew; Baxter, Jason; May, Steven

We study optical absorption and recombination dynamics in La1-xSrxFeO3-δ thin films, uncovering the effects of tuning nominal Fe valence via A-site substitution and oxygen stoichiometry. Variable angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. These results demonstrate that while the static optical absorption is strongly dependent on Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics. Nsf: ECCS-1201957, MRI DMR-0922929, MRI DMR-1040166. This research used resources of the Center for Functional Nanomaterials, which is a U.S. DOE Office of Science Facility, at Brookhaven National Laboratory under Contract No. DE-SC0012704.

Pulse Propagation Effects in Optical 2D Fourier-Transform Spectroscopy: Theory.

PubMed

Spencer, Austin P; Li, Hebin; Cundiff, Steven T; Jonas, David M

2015-04-30

A solution to Maxwell's equations in the three-dimensional frequency domain is used to calculate rephasing two-dimensional Fourier transform (2DFT) spectra of the D2 line of atomic rubidium vapor in argon buffer gas. Experimental distortions from the spatial propagation of pulses through the sample are simulated in 2DFT spectra calculated for the homogeneous Bloch line shape model. Spectral features that appear at optical densities of up to 3 are investigated. As optical density increases, absorptive and dispersive distortions start with peak shape broadening, progress to peak splitting, and ultimately result in a previously unexplored coherent transient twisting of the split peaks. In contrast to the low optical density limit, where the 2D peak shape for the Bloch model depends only on the total dephasing time, these distortions of the 2D peak shape at finite optical density vary with the waiting time and the excited state lifetime through coherent transient effects. Experiment-specific conditions are explored, demonstrating the effects of varying beam overlap within the sample and of pseudo-time domain filtering. For beam overlap starting at the sample entrance, decreasing the length of beam overlap reduces the line width along the ωτ axis but also reduces signal intensity. A pseudo-time domain filter, where signal prior to the center of the last excitation pulse is excluded from the FID-referenced 2D signal, reduces propagation distortions along the ωt axis. It is demonstrated that 2DFT rephasing spectra cannot take advantage of an excitation-detection transformation that can eliminate propagation distortions in 2DFT relaxation spectra. Finally, the high optical density experimental 2DFT spectrum of rubidium vapor in argon buffer gas [J. Phys. Chem. A 2013, 117, 6279-6287] is quantitatively compared, in line width, in depth of peak splitting, and in coherent transient peak twisting, to a simulation with optical density higher than that reported.

Aliphatic Hydrocarbon Content of Interstellar Dust

NASA Astrophysics Data System (ADS)

Günay, B.; Schmidt, T. W.; Burton, M. G.; Afşar, M.; Krechkivska, O.; Nauta, K.; Kable, S. H.; Rawal, A.

2018-06-01

There is considerable uncertainty as to the amount of carbon incorporated in interstellar dust. The aliphatic component of the carbonaceous dust is of particular interest because it produces a significant 3.4 μm absorption feature when viewed against a background radiation source. The optical depth of the 3.4 μm absorption feature is related to the number of aliphatic carbon C-H bonds along the line of sight. It is possible to estimate the column density of carbon locked up in the aliphatic hydrocarbon component of interstellar dust from quantitative analysis of the 3.4 μm interstellar absorption feature providing that the absorption coefficient of aliphatic hydrocarbons incorporated in the interstellar dust is known. We report laboratory analogues of interstellar dust by experimentally mimicking interstellar/circumstellar conditions. The resultant spectra of these dust analogues closely match those from astronomical observations. Measurements of the absorption coefficient of aliphatic hydrocarbons incorporated in the analogues were carried out by a procedure combining FTIR and 13C NMR spectroscopies. The absorption coefficients obtained for both interstellar analogues were found to be in close agreement (4.76(8) × 10-18 cm group-1 and 4.69(14) × 10-18 cm group-1), less than half those obtained in studies using small aliphatic molecules. The results thus obtained permit direct calibration of the astronomical observations, providing rigorous estimates of the amount of aliphatic carbon in the interstellar medium.

"CHON" particles: The interstellar component of cometary dust

NASA Technical Reports Server (NTRS)

Lien, David J.

1998-01-01

Interstellar dust is characterized by strong absorption in the ultraviolet and the mid-IR. Current models of interstellar dust are based on three chemically distinct components: a form of carbon (usually graphite), a silicate, and a blend of polycyclic aromatic hydrocarbons or other carbonaceous material. Previous work using effective medium theories to understand the optical properties of cometary dust suggested that an amalgam of materials could reproduce the observed interstellar and cometary dust features. Recently, Lawler and Brownlee (1992) re-analyzed the PIA and PUMA-1 data sets from the Giotto flyby of P/Halley and discovered that the so-called "CHON" particles were actually composed of a blend of carbon-bearing and silicon-bearing materials. Based on effective medium theories, the absorption spectrum of such a material would display the spectral features of each of the components - strong UV absorption from the carbonaceous component and strong absorption in the IR from the silicate component. To test this idea, vapor-deposited samples were created using two different deposition techniques: sputtering with an argon RF magnetron and deposition from an argon plasma torch. Two different compositions were tested: a blend of graphite and silica in a 7:1 ratio and an amalgam of materials whose approximate composition matches the "CHON"-silicate abundances for the uncompressed PIA data set of Lawler and Brownlee: graphite, iron oxide, magnesium oxide, ammonium sulfate, calcium carbonate, and silica in mass ratios of 6:4.3:4:2.2:1:9. The samples were finely ground and pressed into 2" diameter disks using a 40 ton press. In all, four different experiments were performed: one with each of the compositions (C:SiO and "CHON") in both the RF magnetron and the plasma torch chambers. The RF magnetron created a uniform dark thin film on the substrate surface, and the plasma torch created a coating of small (<100 micron) diameter grey particles. The spectra of all four samples show a strong, broad absorption feature at around 220 nm as well as a strong but narrower absorption peak near 10 microns. The RF magnetron sputtered samples showed some sub-structure in the UV, and the peak of the absorption was shifted toward longer wavelengths. The UV absorption in the plasma torch deposited samples have no sub-structure, and the peak absorption is very near 220 nm. Strong absorption near 9 microns is seen in the spectra from both sample preparation techniques, and is consistent with the IR spectra of some terrestrial silicates. Other features, particularly at 6.2 and 8.6 microns, are seen in the interstellar medium. A strong feature near 2 microns is due to absorbed water in the sample. Based on the results of these experiments, there is evidence that a material with a composition similar to that detected in "CHON" particles in the coma of P/Halley have a spectral signature which reproduces the main absorption features of interstellar dust. This suggests that the "CHON" particles could be the interstellar component of cometary dust.

Transient Heat Transfer in a Semitransparent Radiating Layer with Boundary Convection and Surface Reflections

NASA Technical Reports Server (NTRS)

Siegel, Robert

1996-01-01

Surface convection and refractive index are examined during transient radiative heating or cooling of a grey semitransparent layer with internal absorption, emission and conduction. Each side of the layer is exposed to hot or cold radiative surroundings, while each boundary is heated or cooled by convection. Emission within the layer and internal reflections depend on the layer refractive index. The reflected energy and heat conduction distribute energy across the layer and partially equalize the transient temperature distributions. Solutions are given to demonstrate the effect of radiative heating for layers with various optical thicknesses, the behavior of the layer heated by radiation on one side and convectively cooled on the other, and a layer heated by convection while being cooled by radiation. The numerical method is an implicit finite difference procedure with non-uniform space and time increments. The basic method developed in earlier work is expanded to include external convection and incident radiation.

Transient GaAs plasmonic metasurfaces at terahertz frequencies

DOE PAGES

Yang, Yuanmu; Kamaraju, N.; Campione, Salvatore; ...

2016-12-09

Here we demonstrate the ultrafast formation of terahertz (THz) metasurfaces through all-optical creation of spatially modulated carrier density profiles in a deep-subwavelength GaAs film. The switch-on of the transient plasmon mode, governed by the GaAs effective electron mass and electron–phonon interactions, is revealed by structured-optical pump THz probe spectroscopy, on a time scale of 500 fs. By modulating the carrier density using different pump fluences, we observe a wide tuning of the electric dipole resonance of the transient GaAs metasurface from 0.5 THz to 1.7 THz. Furthermore, we numerically demonstrate that the metasurface presented here can be generalized to moremore » complex architectures for realizing functionalities such as perfect absorption, leading to a 30 dB modulation depth. In conclusion, the platform also provides a pathway to achieve ultrafast manipulation of infrared beams in the linear and, potentially, nonlinear regime.« less

Sub-10 fs Time-Resolved Vibronic Optical Microscopy

PubMed Central

2016-01-01

We introduce femtosecond wide-field transient absorption microscopy combining sub-10 fs pump and probe pulses covering the complete visible (500–650 nm) and near-infrared (650–950 nm) spectrum with diffraction-limited optical resolution. We demonstrate the capabilities of our system by reporting the spatially- and spectrally-resolved transient electronic response of MAPbI3–xClx perovskite films and reveal significant quenching of the transient bleach signal at grain boundaries. The unprecedented temporal resolution enables us to directly observe the formation of band-gap renormalization, completed in 25 fs after photoexcitation. In addition, we acquire hyperspectral Raman maps of TIPS pentacene films with sub-400 nm spatial and sub-15 cm–1 spectral resolution covering the 100–2000 cm–1 window. Our approach opens up the possibility of studying ultrafast dynamics on nanometer length and femtosecond time scales in a variety of two-dimensional and nanoscopic systems. PMID:27934055

Ultrafast re-structuring of the electronic landscape of transparent dielectrics: new material states (Die-Met)

NASA Astrophysics Data System (ADS)

Gamaly, E. G.; Rode, A. V.

2018-03-01

Swift excitation of transparent dielectrics by ultrashort and highly intense laser pulse leads to ultra-fast re-structuring of the electronic landscape and generates many transient material states, which are continuously reshaped in accord with the changing pulse intensity. These unconventional transient material states, which exhibit simultaneously both dielectric and metallic properties, we termed here as the `Die-Met' states. The excited material is transparent and conductive at the same time. The real part of permittivity of the excited material changes from positive to negative values with the increase of excitation, which affects strongly the interaction process during the laser pulse. When the incident field has a component along the permittivity gradient, the amplitude of the field increases resonantly near the point of zero permittivity, which dramatically changes the interaction mode and increases absorption in a way that is similar to the resonant absorption in plasma. The complex 3D structure of the permittivity makes a transparent part of the excited dielectric (at ɛ 0 > ɛ re > 0) optically active. The electro-magnetic wave gets a twisted trajectory and accrues the geometric phase while passing through such a medium. Both the phase and the rotation of the polarisation plane depend on the 3D permittivity structure. Measuring the transmission, polarisation and the phase of the probe beam allows one to quantitatively identify these new transient states. We discuss the revelations of this effect in different experimental situations and their possible applications.

Airborne imaging spectrometer data of the Ruby Mountains, Montana: Mineral discrimination using relative absorption band-depth images

USGS Publications Warehouse

Crowley, J.K.; Brickey, D.W.; Rowan, L.C.

1989-01-01

Airborne imaging spectrometer data collected in the near-infrared (1.2-2.4 ??m) wavelength range were used to study the spectral expression of metamorphic minerals and rocks in the Ruby Mountains of southwestern Montana. The data were analyzed by using a new data enhancement procedure-the construction of relative absorption band-depth (RBD) images. RBD images, like bandratio images, are designed to detect diagnostic mineral absorption features, while minimizing reflectance variations related to topographic slope and albedo differences. To produce an RBD image, several data channels near an absorption band shoulder are summed and then divided by the sum of several channels located near the band minimum. RBD images are both highly specific and sensitive to the presence of particular mineral absorption features. Further, the technique does not distort or subdue spectral features as sometimes occurs when using other data normalization methods. By using RBD images, a number of rock and soil units were distinguished in the Ruby Mountains including weathered quartz - feldspar pegmatites, marbles of several compositions, and soils developed over poorly exposed mica schists. The RBD technique is especially well suited for detecting weak near-infrared spectral features produced by soils, which may permit improved mapping of subtle lithologic and structural details in semiarid terrains. The observation of soils rich in talc, an important industrial commodity in the study area, also indicates that RBD images may be useful for mineral exploration. ?? 1989.

Exocomet Orbit Fitting: Accelerating Coma Absorption During Transits of β Pictoris

NASA Astrophysics Data System (ADS)

Kennedy, Grant M.

2018-06-01

Comets are a remarkable feature in our night sky, visible on their passage through the inner Solar system as the Sun's energy sublimates ices and liberates surface material, generating beautiful comae, dust, and ion tails. Comets are also thought to orbit other stars, and are the most promising interpretation of sporadic absorption features (i.e. transits) seen in spectra of stars such as β Pictoris and 49 Ceti. These "exocomets" are thought to form and evolve in the same way as in the Solar system, and as in the Solar system we may gain insight into their origins by deriving their orbits. In the case of β Pictoris, orbits have been estimated indirectly, using the radial velocity of the absorption features coupled with a physical evaporation model to estimate the stellocentric distance at transit dtr. Here, we note that the inferred dtr imply that some absorption signatures should accelerate over several hours, and show that this acceleration is indeed seen in HARPS spectra. This new constraint means that orbital characteristics can be obtained directly, and the pericentre distance and longitude constrained when parabolic orbits are assumed. The results from fitting orbits to 12 accelerating features, and a handful of non-accelerating ones, are in broad agreement with previous estimates based on an evaporation model, thereby providing some validation of the exocomet hypothesis. A prediction of the evaporation model, that coma absorption is deeper for more distant transits, is also seen here.

Brush border membrane vesicle and Caco-2 cell line: Two experimental models for evaluation of absorption enhancing effects of saponins, bile salts, and some synthetic surfactants

PubMed Central

Moghimipour, Eskandar; Tabassi, Sayyed Abolghassem Sajadi; Ramezani, Mohammad; Handali, Somayeh; Löbenberg, Raimar

2016-01-01

The aim of this study was to investigate the influence of absorption enhancers in the uptake of hydrophilic compounds. The permeation of the two hydrophilic drug models gentamicin and 5 (6)-carboxyfluorescein (CF) across the brush border membrane vesicles and Caco-2 cell lines were evaluated using total saponins of Acanthophyllum squarrosum, Quillaja saponaria, sodium lauryl sulfate, sodium glycocholate, sodium taurodeoxycholate, and Tween 20 as absorption enhancers. Transepithelial electrical resistance (TEER) measurement was utilized to assess the paracellular permeability of cell lines. Confocal laser scanning microscopy (CLSM) was performed to obtain images of the distribution of CF in Caco-2 cells. These compounds were able to loosen tight junctions, thus increasing paracellular permeability. CLSM confirmed the effect of these absorption enhancers on CF transport across Caco-2 lines and increased the Caco-2 permeability via transcellular route. It was also confirmed that the decrease in TEER was transient and reversible after removal of permeation enhancers. PMID:27429925

Transient bleaching of small PbS colloids. Influence of surface properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nenadovic, M.T.; Comor, M.I.; Vasic, V.

1990-08-09

Small PbS colloids with a particle diameter of 40 {angstrom} were prepared in aqueous solution, and their absorption spectra exhibit several maxima. Injection of electrons into these particles was achieved by using the pulse radiolysis technique. Excess electrons trapped on the surface lead to a blue shift in the absorption edge of colloids. The appearance of this shift depends critically on the method of colloid preparation. PbS and CdS colloids prepared at pH < 6 have long-lived bleaching, which disappears after several seconds. On the other hand, absorption bleaching does not appear after the addition of hydroxide ions to colloidalmore » solutions (pH > 8). The existence of a hydroxide ion on the particle surface most likely removes surface defects on which electrons are trapped. PbS colloids prepared in the presence of 3-mercapto-1,2-propanediol have an unstructured absorption spectrum, which is due to a wide particle size distribution (10-50 {angstrom}).« less

Calcium Signaling in Intact Dorsal Root Ganglia

PubMed Central

Gemes, Geza; Rigaud, Marcel; Koopmeiners, Andrew S.; Poroli, Mark J.; Zoga, Vasiliki; Hogan, Quinn H.

2013-01-01

Background Ca2+ is the dominant second messenger in primary sensory neurons. In addition, disrupted Ca2+ signaling is a prominent feature in pain models involving peripheral nerve injury. Standard cytoplasmic Ca2+ recording techniques use high K+ or field stimulation and dissociated neurons. To compare findings in intact dorsal root ganglia, we used a method of simultaneous electrophysiologic and microfluorimetric recording. Methods Dissociated neurons were loaded by bath-applied Fura-2-AM and subjected to field stimulation. Alternatively, we adapted a technique in which neuronal somata of intact ganglia were loaded with Fura-2 through an intracellular microelectrode that provided simultaneous membrane potential recording during activation by action potentials (APs) conducted from attached dorsal roots. Results Field stimulation at levels necessary to activate neurons generated bath pH changes through electrolysis and failed to predictably drive neurons with AP trains. In the intact ganglion technique, single APs produced measurable Ca2+ transients that were fourfold larger in presumed nociceptive C-type neurons than in nonnociceptive Aβ-type neurons. Unitary Ca2+ transients summated during AP trains, forming transients with amplitudes that were highly dependent on stimulation frequency. Each neuron was tuned to a preferred frequency at which transient amplitude was maximal. Transients predominantly exhibited monoexponential recovery and had sustained plateaus during recovery only with trains of more than 100 APs. Nerve injury decreased Ca2+ transients in C-type neurons, but increased transients in Aβ-type neurons. Conclusions Refined observation of Ca2+ signaling is possible through natural activation by conducted APs in undissociated sensory neurons and reveals features distinct to neuronal types and injury state. PMID:20526180

Feature-based and statistical methods for analyzing the Deepwater Horizon oil spill with AVIRIS imagery

USGS Publications Warehouse

Rand, R.S.; Clark, R.N.; Livo, K.E.

2011-01-01

The Deepwater Horizon oil spill covered a very large geographical area in the Gulf of Mexico creating potentially serious environmental impacts on both marine life and the coastal shorelines. Knowing the oil's areal extent and thickness as well as denoting different categories of the oil's physical state is important for assessing these impacts. High spectral resolution data in hyperspectral imagery (HSI) sensors such as Airborne Visible and Infrared Imaging Spectrometer (AVIRIS) provide a valuable source of information that can be used for analysis by semi-automatic methods for tracking an oil spill's areal extent, oil thickness, and oil categories. However, the spectral behavior of oil in water is inherently a highly non-linear and variable phenomenon that changes depending on oil thickness and oil/water ratios. For certain oil thicknesses there are well-defined absorption features, whereas for very thin films sometimes there are almost no observable features. Feature-based imaging spectroscopy methods are particularly effective at classifying materials that exhibit specific well-defined spectral absorption features. Statistical methods are effective at classifying materials with spectra that exhibit a considerable amount of variability and that do not necessarily exhibit well-defined spectral absorption features. This study investigates feature-based and statistical methods for analyzing oil spills using hyperspectral imagery. The appropriate use of each approach is investigated and a combined feature-based and statistical method is proposed.

Feature conjunctions and auditory sensory memory.

PubMed

Sussman, E; Gomes, H; Nousak, J M; Ritter, W; Vaughan, H G

1998-05-18

This study sought to obtain additional evidence that transient auditory memory stores information about conjunctions of features on an automatic basis. The mismatch negativity of event-related potentials was employed because its operations are based on information that is stored in transient auditory memory. The mismatch negativity was found to be elicited by a tone that differed from standard tones in a combination of its perceived location and frequency. The result lends further support to the hypothesis that the system upon which the mismatch negativity relies processes stimuli in an holistic manner. Copyright 1998 Elsevier Science B.V.

Evaluating Zeolite-Modified Sensors: towards a faster set of chemical sensors

NASA Astrophysics Data System (ADS)

Berna, A. Z.; Vergara, A.; Trincavelli, M.; Huerta, R.; Afonja, A.; Parkin, I. P.; Binions, R.; Trowell, S.

2011-09-01

The responses of zeolite-modified sensors, prepared by screen printing layers of chromium titanium oxide (CTO), were compared to unmodified tin oxide sensors using amplitude and transient responses. For transient responses we used a family of features, derived from the exponential moving average (EMA), to characterize chemo-resistive responses. All sensors were tested simultaneously against 20 individual volatile compounds from four chemical groups. The responses of the two types of sensors showed some independence. The zeolite-modified CTO sensors discriminated compounds better using either amplitude response or EMA features and CTO-modified sensors also responded three times faster.

Particle Detectors and Data Analysis for Cusp Transient Features Campaign

NASA Technical Reports Server (NTRS)

Sharber, J. R.

1998-01-01

Grant NAG5-5084 was awarded to support the participation of South West Research Institute (SwRI) in building the energy per unit charge particle detectors for the Cusp Transient Features Campaign and analysis of flight data from these instruments. The detectors are part of an instrumented payload (Rocket 36.152, Dr. R. Pfaff, P.I.) launched from Svalbard on December 3, 1997, into the dark cusp. The particle instruments, a Cusp Electron Detector (CED) and a Cusp Ion Detector (CID), built on this project, provided differential energy and angular measurements along the rocket trajectory throughout the flight.

Interplay of Collective Excitations in Quantum Well Intersubband Resonances

NASA Technical Reports Server (NTRS)

Li, Jian-Zhong; Ning, C. Z.

2003-01-01

Intersubband resonances in a semiconductor quantum well (QW) display some of the most fascinating features involving various collective excitations such as Fermi-edge singularity (FES) and intersubband plasmon (ISP). Using a density matrix approach, we treated many-body effects such as depolarization, vertex correction, and self-energy consistently for a two-subband system. We found a systematic change in resonance spectra from FES-dominated to ISP-dominated features, as QW- width or electron density is varied. Such an interplay between FES and ISP significantly changes both line shape and peak position of the absorption spectrum. In particular, we found that a cancellation of FES and ISP undresses the resonant responses and recovers the single-particle features of absorption for semiconductors with a strong nonparabolicity such as InAs, leading to a dramatic broadening of the absorption spectrum.

Ultrafast Energy Transfer Dynamics Between a Polypyridyl Ru(II) Chromophore and a Covalently Attached Acceptor

NASA Astrophysics Data System (ADS)

Styers-Barnett, David; Gannon, Erika; Papanikolas, John; Meyer, Thomas

2003-03-01

The energy transfer dynamics between the ^3MLCT excited state of a polypyridyl Ru(II) chromophore and a ligand-bound anthracene has been studied using femtosecond transient absorption spectroscopy. Photoexcitation of the metal complex at 450 nm promotes an electron from a d-orbital on the metal to a π* orbital on the bipyridine, forming a metal-to-ligand charge-transfer (MLCT) excited state. Energy transfer to the covalently appended anthracene is followed by the growth of the anthracene excited state absorption at 425 nm, and the simultaneous decay of the ^3MLCT absorption at 380 nm. The observed growth is biexponential, with the fast component attributed to energy transfer (19 ps), and the slow component arising from a combination of interligand electron transfer between the polypyridyl ligands and energy transfer (75 ps).

Ultrafast time-resolved X-ray absorption spectroscopy of ferrioxalate photolysis with a laser plasma X-ray source and microcalorimeter array

DOE PAGES

O’Neil, Galen C.; Miaja-Avila, Luis; Joe, Young Il; ...

2017-02-17

The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. We provide quantitative limits on the Fe–O bond length change. Lastly, we review potential improvements to our measurementmore » technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.« less

Ultrafast time-resolved X-ray absorption spectroscopy of ferrioxalate photolysis with a laser plasma X-ray source and microcalorimeter array

DOE Office of Scientific and Technical Information (OSTI.GOV)

O’Neil, Galen C.; Miaja-Avila, Luis; Joe, Young Il

The detailed pathways of photoactivity on ultrafast time scales are a topic of contemporary interest. Using a tabletop apparatus based on a laser plasma X-ray source and an array of cryogenic microcalorimeter X-ray detectors, we measured a transient X-ray absorption spectrum during the ferrioxalate photoreduction reaction. With these high-efficiency detectors, we observe the Fe K edge move to lower energies and the amplitude of the extended X-ray absorption fine structure reduce, consistent with a photoreduction mechanism in which electron transfer precedes disassociation. We provide quantitative limits on the Fe–O bond length change. Lastly, we review potential improvements to our measurementmore » technique, highlighting the future potential of tabletop X-ray science using microcalorimeter sensors.« less

Spectroscopic Classification of DLT18w/AT2018bko with SOAR

NASA Astrophysics Data System (ADS)

Pan, Y.-C.; Foley, R. J.

2018-05-01

< p > We report the classification of DLT18w/AT2018bko (ATel #11638) from spectroscopic observation performed on 2018 May 13 UT with the Goodman spectrograph on the Southern Astrophysical Research (SOAR) telescope. The spectrum appears to be blue and shows Balmer absorption lines at z=0, indicating that the transient is Galactic.

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

ERIC Educational Resources Information Center

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

2018-01-01

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

Multi-Electron Effects in Attosecond Transient Absorption of CO Molecules

NASA Astrophysics Data System (ADS)

Zhang, Bin; Zhao, Jian; Zhao, Zeng-Xiu

2018-04-01

Not Available Supported by the National Basic Research Program of China under Grant No 2013CB922203, the National Natural Science Foundation of China under Grant No 11374366, the Innovation Foundation of National University of Defense Technology under Grant No B110204, and the Hunan Provincial Innovation Foundation for Postgraduate under Grant No CX2011B010.

Hypomagnesaemia associated with long-term use of proton pump inhibitors

PubMed Central

Toh, James Wei Tatt; Ong, Evonne; Wilson, Robert

2015-01-01

Hypomagnesaemia and associated hypocalcaemia and hypoparathyroidism have been increasingly recognised as rare long-term side-effects of proton pump inhibitors (PPIs). The PPIs may inhibit active magnesium (Mg) absorption by interfering with transcellular transient receptor potential melastatin-6 and -7 (TRPM 6 and 7) channels. More recent cell culture studies have suggested concomitant inhibition of passive Mg absorption by omeprazole. After being treated with a range of PPIs, the four patients in our case series developed hypomagnesaemia, which responded to withdrawal of therapy and initiation of Mg replacement. Their clinical course and management demonstrate key aspects of hypomagnesaemia associated with long-term use of PPIs. PMID:25138239

Coherent virtual absorption for discretized light

NASA Astrophysics Data System (ADS)

Longhi, S.

2018-05-01

Coherent virtual absorption (CVA) is a recently-introduced phenomenon for which exponentially growing waves incident onto a conservative optical medium are neither reflected nor transmitted, at least transiently. CVA has been associated to complex zeros of the scattering matrix and can be regarded as the time reversal of the decay process of a quasi-mode sustained by the optical medium. Here we consider CVA for discretized light transport in coupled resonator optical waveguides or waveguide arrays and show that a distinct kind of CVA, which is not related to complex zero excitation of quasi-modes, can be observed. This result suggests that scattering matrix analysis can not fully capture CVA phenomena.

Thermal infrared spectroscopy and modeling of experimentally shocked plagioclase feldspars

USGS Publications Warehouse

Johnson, J. R.; Horz, F.; Staid, M.I.

2003-01-01

Thermal infrared emission and reflectance spectra (250-1400 cm-1; ???7???40 ??m) of experimentally shocked albite- and anorthite-rich rocks (17-56 GPa) demonstrate that plagioclase feldspars exhibit characteristic degradations in spectral features with increasing pressure. New measurements of albite (Ab98) presented here display major spectral absorptions between 1000-1250 cm-1 (8-10 ??m) (due to Si-O antisymmetric stretch motions of the silica tetrahedra) and weaker absorptions between 350-700 cm-1 (14-29 ??m) (due to Si-O-Si octahedral bending vibrations). Many of these features persist to higher pressures compared to similar features in measurements of shocked anorthite, consistent with previous thermal infrared absorption studies of shocked feldspars. A transparency feature at 855 cm-1 (11.7 ??m) observed in powdered albite spectra also degrades with increasing pressure, similar to the 830 cm-1 (12.0 ??m) transparency feature in spectra of powders of shocked anorthite. Linear deconvolution models demonstrate that combinations of common mineral and glass spectra can replicate the spectra of shocked anorthite relatively well until shock pressures of 20-25 GPa, above which model errors increase substantially, coincident with the onset of diaplectic glass formation. Albite deconvolutions exhibit higher errors overall but do not change significantly with pressure, likely because certain clay minerals selected by the model exhibit absorption features similar to those in highly shocked albite. The implication for deconvolution of thermal infrared spectra of planetary surfaces (or laboratory spectra of samples) is that the use of highly shocked anorthite spectra in end-member libraries could be helpful in identifying highly shocked calcic plagioclase feldspars.

New insights into the operative network of FaEO, an enone oxidoreductase from Fragaria x ananassa Duch.

PubMed

Collu, Gabriella; Farci, Domenica; Esposito, Francesca; Pintus, Francesca; Kirkpatrick, Joanna; Piano, Dario

2017-05-01

The 2-methylene-furan-3-one reductase or Fragaria x ananassa Enone Oxidoreductase (FaEO) catalyses the last reductive step in the biosynthesis of 4-hydroxy-2,5-dimethyl-3(2H)-furanone, a major component in the characteristic flavour of strawberries. In the present work, we describe the association between FaEO and the vacuolar membrane of strawberry fruits. Even if FaEO lacks epitopes for stable or transient membrane-interactions, it contains a calmodulin-binding region, suggesting that in vivo FaEO may be associated with the membrane via a peripheral protein complex with calmodulin. Moreover, we also found that FaEO occurs in dimeric form in vivo and, as frequently observed for calmodulin-regulated proteins, it may be expressed in different isoforms by alternative gene splicing. Further mass spectrometry analysis confirmed that the isolated FaEO consists in the already known isoform and that it is the most characteristic during ripening. Finally, a characterization by absorption spectroscopy showed that FaEO has specific flavoprotein features. The relevance of these findings and their possible physiological implications are discussed.

Functional single-wall carbon nanotube nanohybrids--associating SWNTs with water-soluble enzyme model systems.

PubMed

Guldi, Dirk M; Rahman, G M Aminur; Jux, Norbert; Balbinot, Domenico; Hartnagel, Uwe; Tagmatarchis, Nikos; Prato, Maurizio

2005-07-13

We succeeded in integrating single-wall carbon nanotubes (SWNTs), several water-soluble pyrene derivatives (pyrene(-)), which bear negatively charged ionic headgroups, and a series of water-soluble metalloporphyrins (MP(8+)) into functional nanohybrids through a combination of associative van der Waals and electrostatic interactions. The resulting SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8+) were characterized by spectroscopic and microscopic means and were found to form stable nanohybrid structures in aqueous media. A crucial feature of our SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8)(+) is that an efficient exfoliation of the initial bundles brings about isolated nanohybrid structures. When the nanohybrid systems are photoexcited with visible light, a rapid intrahybrid charge separation causes the reduction of the electron-accepting SWNT and, simultaneously, the oxidation of the electron-donating MP(8)(+). Transient absorption measurements confirm that the radical ion pairs are long-lived, with lifetimes in the microsecond range. Particularly beneficial are charge recombination dynamics that are located deep in the Marcus-inverted region. We include, for the first time, work devoted to exploring and testing FeP(8)(+) and CoP(8)(+) in donor-acceptor nanohybrids.

Features of the impact of the solar wind diamagnetic structure on Earth's magnetosphere

NASA Astrophysics Data System (ADS)

Parhomov, Vladimir; Borodkova, Natalia; Eselevich, Viktor; Eselevich, Maxim; Dmitriev, Aleksey; Chilikin, Vitaliy

2017-12-01

At Earth's orbit on June 28, 1999, there was a diamagnetic structure (DS) representing a filament with a uniquely high speed (about 900 km/s). We show that the filament is a part of the specific sporadic solar wind (SW) stream, which is characterized as a small interplanetary transient. We report the results of studies on the interaction between such a fast filament (DS) and Earth's magnetosphere. Around noon hours at daytime cusp latitudes, we recorded a powerful aurora in the UV band (shock aurora), which rapidly spread to the west and east. Ground-based observations of geo-magnetic field variations, auroral absorption, and auroras on the midnight meridian have shown the development of a powerful substorm-like disturbance (SLD) (AE∼1000 nT), whose origin is associated with the impact of the SW diamagnetic structure on the magnetosphere. The geostationary satellite GOES-8, which was in the midnight sector of the outer quasi capture region during SLD, recorded variations of the Bz and Bx geomagnetic components corresponding to the dipolization process.

Iron alteration minerals in the visible and near-infrared spectra of low-albedo asteroids

NASA Technical Reports Server (NTRS)

Vilas, Faith; Jarvis, Kandy S.; Gaffey, Michael J.

1994-01-01

Absorption features centered near 0.60-0.65 and 0.80-0.90 micrometers have been identified in the spectra of five low-albedo main-belt and outer-belt asteroids. These absorption features are attributed respectively to the (6)A(sub 1) goes to (4)T(sub 2)(G) and (6)A(sub 1) goes to (4)T(sub 1)(G) charge transfer transitions in minerals such as goethite, hematite, and jarosite that are products of the aqueous alteration of anhydrous silicates. A shoulder near 0.63 micrometers has also been identified in the absorption feature centered near 0.7 micrometers attributed to oxidized iron in phyllosilicates found predominantly in C- and G-class asteroids reflectance spectra. The coexistence of iron oxides with phyllosilicates in asteroids believed to have undergone aqueous alteration would be expected based upon analogy with terrestrial aqueous alteration and the observed mineralogy of carbonaceous chondrites. The number of low-albedo asteroids having only iron alteration absorption features compared to the number of low-albedo asteroids having spectral characteristics indicative of phyllosilicates is small. Either the conditions under which these asteroids formed are rare, or the iron alteration minerals could be formed in the interiors of objects where phyllosilicates dominate the surface mineralogy.

Discrimination Enhancement with Transient Feature Analysis of a Graphene Chemical Sensor.

PubMed

Nallon, Eric C; Schnee, Vincent P; Bright, Collin J; Polcha, Michael P; Li, Qiliang

2016-01-19

A graphene chemical sensor is subjected to a set of structurally and chemically similar hydrocarbon compounds consisting of toluene, o-xylene, p-xylene, and mesitylene. The fractional change in resistance of the sensor upon exposure to these compounds exhibits a similar response magnitude among compounds, whereas large variation is observed within repetitions for each compound, causing a response overlap. Therefore, traditional features depending on maximum response change will cause confusion during further discrimination and classification analysis. More robust features that are less sensitive to concentration, sampling, and drift variability would provide higher quality information. In this work, we have explored the advantage of using transient-based exponential fitting coefficients to enhance the discrimination of similar compounds. The advantages of such feature analysis to discriminate each compound is evaluated using principle component analysis (PCA). In addition, machine learning-based classification algorithms were used to compare the prediction accuracies when using fitting coefficients as features. The additional features greatly enhanced the discrimination between compounds while performing PCA and also improved the prediction accuracy by 34% when using linear discrimination analysis.

Measurements of reflectance spectra of ion-bombarded ice and application to surfaces in the outer solar system

NASA Technical Reports Server (NTRS)

O'Shaughnessy, D. J.; Boring, J. W.; Johnson, R. E.

1988-01-01

The first results of laboratory measurements of the wavelength dependence of the alternation of the visible reflectance of H2O ice irradiated by keV ions are presented. When the implanted species is chemically neutral, absorption is slightly enhanced below 0.55 micron. For an incident species containing sulfur, a strong absorption feature is produced at 0.4 micron, probably corresponding to S3. This occurs at too large a wavelength to account for the absorption feature observed at Europa by Voyager and therefore casts doubt on the recent interpretation of the reflectance data of Europa.

Voyager 1 imaging and IRIS observations of Jovian methane absorption and thermal emission: Implications for cloud structure

NASA Technical Reports Server (NTRS)

West, R. A.; Kupferman, P. N.; Hart, H.

1984-01-01

Images from three filters of the Voyager 1 wide angle camera are used to measure the continuum reflectivity and spectral gradient near 6000 A and the 6190 A band methane/continuum ratio for a variety of cloud features in Jupiter's atmosphere. The dark barge features in the North Equatorial Belt have anomalously strong positive continuum spectral gradients suggesting unique composition. Methane absorption is shown at unprecedented spatial scales for the Great Red Spot and its immediate environment, for a dark barge feature in the North Equatorial Belt, and for two hot spot and plume regions in the North Equatorial Belt. Methane absorption and five micrometer emission are correlated in the vicinity of the Great Red Spot but are anticorrelated in one of the plume hot spot regions. Methane absorption and simultaneous maps of five micrometer brightness temperature is quantitatively compared to realistic cloud structure models which include multiple scattering at five micrometer as well as in the visible. Variability in H2 quadrupole lines are also investigated.

Voyager 1 imaging and IRIS observations of Jovian methane absorption and thermal emission - Implications for cloud structure

NASA Technical Reports Server (NTRS)

West, R. A.; Kupferman, P. N.; Hart, H.

1985-01-01

Images from three filters of the Voyager 1 wide angle camera are used to measure the continuum reflectivity and spectral gradient near 6000 A and the 6190 A band methane/continuum ratio for a variety of cloud features in Jupiter's atmosphere. The dark barge features in the North Equatorial Belt have anomalously strong positive continuum spectral gradients suggesting unique composition. Methane absorption is shown at unprecedented spatial scales for the Great Red Spot and its immediate environment, for a dark barge feature in the North Equatorial Belt, and for two hot spot and plume regions in the North Equatorial Belt. Methane absorption and five micrometer emission are correlated in the vicinity of the Great Red Spot but are anticorrelated in one of the plume hot spot regions. Methane absorption and simultaneous maps of five micrometer brightness temperature are quantitatively compared to realistic cloud structure models which include multiple scattering at five micrometer as well as in the visible. Variability in H2 quadrupole lines are also investigated.

Vibrational Excitation of Both Products of the Reaction of CN Radicals with Acetone in Solution

PubMed Central

2015-01-01

Transient electronic and vibrational absorption spectroscopy unravel the mechanisms and dynamics of bimolecular reactions of CN radicals with acetone in deuterated chloroform solutions. The CN radicals are produced by ultrafast ultraviolet photolysis of dissolved ICN. Two reactive forms of CN radicals are distinguished by their electronic absorption bands: “free” (uncomplexed) CN radicals, and “solvated” CN radicals that are complexed with solvent molecules. The lifetimes of the free CN radicals are limited to a few picoseconds following their photolytic production because of geminate recombination to ICN and INC, complexation with CDCl3 molecules, and reaction with acetone. The acetone reaction occurs with a rate coefficient of (8.0 ± 0.5) × 1010 M–1 s–1 and transient vibrational spectra in the C=N and C=O stretching regions reveal that both the nascent HCN and 2-oxopropyl (CH3C(O)CH2) radical products are vibrationally excited. The rate coefficient for the reaction of solvated CN with acetone is 40 times slower than for free CN, with a rate coefficient of (2.0 ± 0.9) × 109 M–1 s–1 obtained from the rise in the HCN product v1(C=N stretch) IR absorption band. Evidence is also presented for CN complexes with acetone that are more strongly bound than the CN–CDCl3 complexes because of CN interactions with the carbonyl group. The rates of reactions of these more strongly associated radicals are slower still. PMID:26192334

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

DOE PAGES

Hayes, Dugan; Kohler, Lars; Hadt, Ryan G.; ...

2017-11-28

Here, the kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(I) bis(phenanthroline)/ruthenium(II) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(I)–Ru(II) analogs of the homodinuclear Cu(I)–Cu(I) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These resultsmore » suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.« less

Excited state electron and energy relays in supramolecular dinuclear complexes revealed by ultrafast optical and X-ray transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, Dugan; Kohler, Lars; Hadt, Ryan G.

Here, the kinetics of photoinduced electron and energy transfer in a family of tetrapyridophenazine-bridged heteroleptic homo- and heterodinuclear copper(I) bis(phenanthroline)/ruthenium(II) polypyridyl complexes were studied using ultrafast optical and multi-edge X-ray transient absorption spectroscopies. This work combines the synthesis of heterodinuclear Cu(I)–Ru(II) analogs of the homodinuclear Cu(I)–Cu(I) targets with spectroscopic analysis and electronic structure calculations to first disentangle the dynamics at individual metal sites by taking advantage of the element and site specificity of X-ray absorption and theoretical methods. The excited state dynamical models developed for the heterodinuclear complexes are then applied to model the more challenging homodinuclear complexes. These resultsmore » suggest that both intermetallic charge and energy transfer can be observed in an asymmetric dinuclear copper complex in which the ground state redox potentials of the copper sites are offset by only 310 meV. We also demonstrate the ability of several of these complexes to effectively and unidirectionally shuttle energy between different metal centers, a property that could be of great use in the design of broadly absorbing and multifunctional multimetallic photocatalysts. This work provides an important step toward developing both a fundamental conceptual picture and a practical experimental handle with which synthetic chemists, spectroscopists, and theoreticians may collaborate to engineer cheap and efficient photocatalytic materials capable of performing coulombically demanding chemical transformations.« less

Using principal component analysis to understand the variability of PDS 456

NASA Astrophysics Data System (ADS)

Parker, M. L.; Reeves, J. N.; Matzeu, G. A.; Buisson, D. J. K.; Fabian, A. C.

2018-02-01

We present a spectral-variability analysis of the low-redshift quasar PDS 456 using principal component analysis. In the XMM-Newton data, we find a strong peak in the first principal component at the energy of the Fe absorption line from the highly blueshifted outflow. This indicates that the absorption feature is more variable than the continuum, and that it is responding to the continuum. We find qualitatively different behaviour in the Suzaku data, which is dominated by changes in the column density of neutral absorption. In this case, we find no evidence of the absorption produced by the highly ionized gas being correlated with this variability. Additionally, we perform simulations of the source variability, and demonstrate that PCA can trivially distinguish between outflow variability correlated, anticorrelated and un-correlated with the continuum flux. Here, the observed anticorrelation between the absorption line equivalent width and the continuum flux may be due to the ionization of the wind responding to the continuum. Finally, we compare our results with those found in the narrow-line Seyfert 1 IRAS 13224-3809. We find that the Fe K UFO feature is sharper and more prominent in PDS 456, but that it lacks the lower energy features from lighter elements found in IRAS 13224-3809, presumably due to differences in ionization.

Ionized absorbers, ionized emitters, and the X-ray spectrum of active galactic nuclei

NASA Technical Reports Server (NTRS)

Netzer, Hagai

1993-01-01

Broad absorption features are common in the X-ray spectrum of low-luminosity AGNs. The features have been modeled by leaky neutral absorbers or by highly ionized gas that completely occult the continuum source. Such models are incomplete since they do not take into account all the physical processes in the gas. In particular, no previous model included the X-ray emission by the ionized absorbing gas and the reflection of the continuum source radiation. The present work discusses the emission, absorption, and reflection properties of photoionized gases with emphasis on conditions thought to prevail in AGNs. It shows that such gas is likely to produce intense X-ray line and continuum radiation and to reflect a sizable fraction of the nonstellar continuum at all energies. If such gas is indeed responsible for the observed X-ray absorption, then absorption edges are much weaker than commonly assumed, and some residual X-ray continuum is likely to be observed even if the line of sight is completely blocked. Moreover, X-ray emission features may show up in sources not showing X-ray absorption. This has immense consequences for medium-resolution X-ray missions, such as BBXRT and Astro-D, and for the planned high-resolution experiments on board XMM and AXAF.

A decision tree-based on-line preventive control strategy for power system transient instability prevention

NASA Astrophysics Data System (ADS)

Xu, Yan; Dong, Zhao Yang; Zhang, Rui; Wong, Kit Po

2014-02-01

Maintaining transient stability is a basic requirement for secure power system operations. Preventive control deals with modifying the system operating point to withstand probable contingencies. In this article, a decision tree (DT)-based on-line preventive control strategy is proposed for transient instability prevention of power systems. Given a stability database, a distance-based feature estimation algorithm is first applied to identify the critical generators, which are then used as features to develop a DT. By interpreting the splitting rules of DT, preventive control is realised by formulating the rules in a standard optimal power flow model and solving it. The proposed method is transparent in control mechanism, on-line computation compatible and convenient to deal with multi-contingency. The effectiveness and efficiency of the method has been verified on New England 10-machine 39-bus test system.

Generalization of Wilemski-Fixman-Weiss decoupling approximation to the case involving multiple sinks of different sizes, shapes, and reactivities.

PubMed

Uhm, Jesik; Lee, Jinuk; Eun, Changsun; Lee, Sangyoub

2006-08-07

We generalize the Wilemski-Fixman-Weiss decoupling approximation to calculate the transient rate of absorption of point particles into multiple sinks of different sizes, shapes, and reactivities. As an application we consider the case involving two spherical sinks. We obtain a Laplace-transform expression for the transient rate that is in excellent agreement with computer simulations. The long-time steady-state rate has a relatively simple expression, which clearly shows the dependence on the diffusion constant of the particles and on the sizes and reactivities of sinks, and its numerical result is in good agreement with the known exact result that is given in terms of recursion relations.

Real-Time Time-Frequency Two-Dimensional Imaging of Ultrafast Transient Signals in Solid-State Organic Materials

PubMed Central

Takeda, Jun; Ishida, Akihiro; Makishima, Yoshinori; Katayama, Ikufumi

2010-01-01

In this review, we demonstrate a real-time time-frequency two-dimensional (2D) pump-probe imaging spectroscopy implemented on a single shot basis applicable to excited-state dynamics in solid-state organic and biological materials. Using this technique, we could successfully map ultrafast time-frequency 2D transient absorption signals of β-carotene in solid films with wide temporal and spectral ranges having very short accumulation time of 20 ms per unit frame. The results obtained indicate the high potential of this technique as a powerful and unique spectroscopic tool to observe ultrafast excited-state dynamics of organic and biological materials in solid-state, which undergo rapid photodegradation. PMID:22399879

OBSERVATIONS OF THE OPTICAL TRANSIENT IN NGC 300 WITH AKARI/IRC: POSSIBILITIES OF ASYMMETRIC DUST FORMATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ohsawa, R.; Sakon, I.; Onaka, T.

2010-08-01

We present the results of near-infrared (NIR) multi-epoch observations of the optical transient in the nearby galaxy NGC 300 (NGC 300-OT) at 398 and 582 days after the discovery with the Infrared Camera (IRC) on board AKARI. NIR spectra (2-5 {mu}m) of NGC 300-OT were obtained for the first time. They show no prominent emission nor absorption features, but are dominated by continuum thermal emission from the dust around NGC 300-OT. NIR images were taken in the 2.4, 3.2, and 4.1 {mu}m bands. The spectral energy distributions (SEDs) of NGC 300-OT indicate the dust temperature of 810 {+-} 14 Kmore » at 398 days and 670 {+-} 12 K at 582 days. We attribute the observed NIR emission to the thermal emission from dust grains formed in the ejecta of NGC 300-OT. The multi-epoch observations enable us to estimate the dust optical depth as {approx}>12 at 398 days and {approx}>6 at 582 days at 2.4 {mu}m by assuming an isothermal dust cloud. The observed NIR emission must be optically thick, unless the amount of dust grains increases with time. Little extinction at visible wavelengths reported in earlier observations suggests that the dust cloud around NGC 300-OT should be distributed inhomogeneously so as to not screen the radiation from the ejecta gas and the central star. The present results suggest the dust grains are not formed in a spherically symmetric geometry, but rather in a torus, a bipolar outflow, or clumpy cloudlets.« less

Multi-Wavelength Spectroscopy of Tidal Disruption Flares: A Legacy Sample for the LSST Era

NASA Astrophysics Data System (ADS)

Cenko, Stephen

2017-08-01

When a star passes within the sphere of disruption of a massive black hole, tidal forces will overcome self-gravity and unbind the star. While approximately half of the stellar debris is ejected at high velocities, the remaining material stays bound to the black hole and accretes, resulting in a luminous, long-lived transient known as a tidal disruption flare (TDF). In addition to serving as unique laboratories for accretion physics, TDFs offer the hope of measuring black hole masses in galaxies much too distant for resolved kinematic studies.In order to realize this potential, we must better understand the detailed processes by which the bound debris circularizes and forms an accretion disk. Spectroscopy is critical to this effort, as emission and absorption line diagnostics provide insight into the location and physical state (velocity, density, composition) of the emitting gas (in analogy with quasars). UV spectra are particularly critical, as most strong atomic features fall in this bandpass, and high-redshift TDF discoveries from LSST will sample rest-frame UV wavelengths.Here we propose to obtain a sequence of UV (HST) and optical (Gemini/GMOS) spectra for a sample of 5 TDFs discovered by the Zwicky Transient Facility, doubling the number of TDFs with UV spectra. Our observations will directly test models for the generation of the UV/optical emission (circularization vs reprocessing) by searching for outflows and measuring densities, temperatures, and composition as a function of time. This effort is critical to developing the framework by which we can infer black hole properties (e.g., mass) from LSST TDF discoveries.

Rapidly Rising Optical Transients from the Birth of Binary Neutron Stars

NASA Astrophysics Data System (ADS)

Hotokezaka, Kenta; Kashiyama, Kazumi; Murase, Kohta

2017-11-01

We study optical counterparts of a new-born pulsar in a double neutron star system like PSR J0737-3039A/B. This system is believed to have ejected a small amount of mass of { O }(0.1 {M}⊙ ) at the second core-collapse supernova. We argue that the initial spin of the new-born pulsar can be determined by the orbital period at the time when the second supernova occurs. The spin angular momentum of the progenitor is expected to be similar to that of the He-burning core, which is tidally synchronized with the orbital motion, and then the second remnant may be born as a millisecond pulsar. If the dipole magnetic field strength of the nascent pulsar is comparable with that inferred from the current spin-down rate of PSR J0737-3039B, the initial spin-down luminosity is comparable to the luminosity of super-luminous supernovae. We consider thermal emission arising from the supernova ejecta driven by the relativistic wind from such a new-born pulsar. The resulting optical light curves have a rise time of ˜10 days and a peak luminosity of ˜1044 erg s-1. The optical emission may last for a month to several months, due to the reprocessing of X-rays and UV photons via photoelectric absorption. These features are broadly consistent with those of the rapidly rising optical transients. The high spin-down luminosity and small ejecta mass are favorable for the progenitor of the repeating fast radio burst, FRB 121102. We discuss a possible connection between new-born double pulsars and fast radio bursts.

Airborne spectroradiometry: The application of AIS data to detecting subtle mineral absorption features

NASA Technical Reports Server (NTRS)

Cocks, T. D.; Green, A. A.

1986-01-01

Analysis of Airborne Imaging Spectrometer (AIS) data acquired in Australia has revealed a number of operational problems. Horizontal striping in AIS imagery and spectral distortions due to order overlap were investigated. Horizontal striping, caused by grating position errors can be removed with little or no effect on spectral details. Order overlap remains a problem that seriously compromises identification of subtle mineral absorption features within AIS spectra. A spectrometric model of the AIS was developed to assist in identifying spurious spectral features, and will be used in efforts to restore the spectral integrity of the data.

Iron K Features in the Quasar E 1821+643: Evidence for Gravitationally Redshifted Absorption?

NASA Technical Reports Server (NTRS)

Yaqoob, Tahir; Serlemitsos, Peter

2005-01-01

We report a Chandra high-energy grating detection of a narrow, redshifted absorption line superimposed on the red wing of a broad Fe K line in the z = 0.297 quasar E 1821+643. The absorption line is detected at a confidence level, estimated by two different methods, in the range approx. 2 - 3 sigma. Although the detection significance is not high enough to exclude a non-astrophysical origin, accounting for the absorption feature when modeling the X-ray spectrum implies that the Fe-K emission line is broad, and consistent with an origin in a relativistic accretion disk. Ignoring the apparent absorption feature leads to the conclusion that the Fe-K emission line is narrower, and also affects the inferred peak energy of the line (and hence the inferred ionization state of Fe). If the absorption line (at approx. 6.2 keV in the quasar frame) is real, we argue that it could be due to gravitationally redshifted Fe XXV or Fe XXVI resonance absorption within approx. 10 - 20 gravitational radii of the putative central black hole. The absorption line is not detected in earlier ASCA and Chandra low-energy grating observations, but the absorption line is not unequivocally ruled out by these data. The Chandra high-energy grating Fe-K emission line is consistent with an origin predominantly in Fe I-XVII or so. In an ASCA observation eight years earlier, the Fe-K line peaked at approx. 6.6 keV, closer to the energies of He-like Fe triplet lines. Further, in a Chandra low-energy grating observation the Fe-K line profile was double-peaked, one peak corresponding to Fe I-XVII or so, the other peak to Fe XXVI Ly alpha. Such a wide range in ionization state of Fe is not ruled out by the HEG and ASCA data either, and is suggestive of a complex structure for the line-emitter.

Features of postfailure fuel behavior in transient overpower and transient undercooled/overpower tests in the transient reactor test facility

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doerner, R.C.; Bauer, T.H.; Morman, J.A.

Prototypic oxide fuel was subjected to simulated, fast reactor severe accident conditions in a series of in-pile tests in the Transient Reactor Test Facility reactor. Seven experiments were performed on fresh and previously irradiated oxide fuel pins under transient overpower and transient undercooled. overpower accident conditions. For each of the tests, fuel motions were observed by the hodoscope. Hodoscope data are correlated with coolant flow, pressure, and temperature data recorded by the loop instrumentation. Data were analyzed from the onset of initial failure to a final mass distribution at the end of the test. In this paper results of thesemore » analyses are compared to pre- and posttest accident calculations and to posttest metallographic accident calculations and to posttest metallographic examinations and computed tomographic reconstructions from neutron radiographs.« less

CosmoQuest Transient Tracker: Opensource Photometry & Astrometry software

NASA Astrophysics Data System (ADS)

Myers, Joseph L.; Lehan, Cory; Gay, Pamela; Richardson, Matthew; CosmoQuest Team

2018-01-01

CosmoQuest is moving from online citizen science, to observational astronomy with the creation of Transient Trackers. This open source software is designed to identify asteroids and other transient/variable objects in image sets. Transient Tracker’s features in final form will include: astrometric and photometric solutions, identification of moving/transient objects, identification of variable objects, and lightcurve analysis. In this poster we present our initial, v0.1 release and seek community input.This software builds on the existing NIH funded ImageJ libraries. Creation of this suite of opensource image manipulation routines is lead by Wayne Rasband and is released primarily under the MIT license. In this release, we are building on these libraries to add source identification for point / point-like sources, and to do astrometry. Our materials released under the Apache 2.0 license on github (http://github.com/CosmoQuestTeam) and documentation can be found at http://cosmoquest.org/TransientTracker.

Evaluation of wavelet spectral features in pathological detection and discrimination of yellow rust and powdery mildew in winter wheat with hyperspectral reflectance data

NASA Astrophysics Data System (ADS)

Shi, Yue; Huang, Wenjiang; Zhou, Xianfeng

2017-04-01

Hyperspectral absorption features are important indicators of characterizing plant biophysical variables for the automatic diagnosis of crop diseases. Continuous wavelet analysis has proven to be an advanced hyperspectral analysis technique for extracting absorption features; however, specific wavelet features (WFs) and their relationship with pathological characteristics induced by different infestations have rarely been summarized. The aim of this research is to determine the most sensitive WFs for identifying specific pathological lesions from yellow rust and powdery mildew in winter wheat, based on 314 hyperspectral samples measured in field experiments in China in 2002, 2003, 2005, and 2012. The resultant WFs could be used as proxies to capture the major spectral absorption features caused by infestation of yellow rust or powdery mildew. Multivariate regression analysis based on these WFs outperformed conventional spectral features in disease detection; meanwhile, a Fisher discrimination model exhibited considerable potential for generating separable clusters for each infestation. Optimal classification returned an overall accuracy of 91.9% with a Kappa of 0.89. This paper also emphasizes the WFs and their relationship with pathological characteristics in order to provide a foundation for the further application of this approach in monitoring winter wheat diseases at the regional scale.

Io: Near-Infrared Absorptions Not Attributable to SO2

NASA Astrophysics Data System (ADS)

Shirley, J. H.; Clark, R. N.; Soderblom, L. A.; Carlson, R. W.; Kamp, L. W.; Galileo NIMS Team

2001-11-01

The Near-Infrared Mapping Spectrometer (NIMS) onboard the Galileo spacecraft imaged the leading side of Jupiter's satellite Io at full spectral resolution and with triple Nyquist spatial sampling during the fifteenth orbital encounter (E15). New despiking and "dejittering" algorithms have been applied to this high S/N observation (15INHRSPEC01A). Spectral absorption features not attributable to SO2 are found between 3.0-3.4 microns and near 4.65 microns. The patterns of the spatial distributions of both absorbers differ from that of the omnipresent SO2. The broad 3.0-3.4 micron absorption is most pronounced in polar regions. Preliminary work suggests that the 4.65 micron feature may be associated with an unidentified sulfate mineral, while the 3.0-3.4 micron feature may result from the presence of more than one absorbing material. Hydrogen-bearing species are likely candidates. For example, H2O ice provides a good match for the absorption near 3.2 microns, but the absorption is shifted to wavelengths longer than that in pure H2O ice. If only one absorber is present, then hydrogen bonding of small numbers of H2O molecules could perhaps account for the shift. The absorption is weak; if H20 related, optical path lengths of a fraction of a micron are indicated. Portions of this research were carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

Ca II and Na I absorption in the QSO S4 0248 + 430 due to an intervening galaxy

NASA Technical Reports Server (NTRS)

Womble, Donna S.; Junkkarinen, Vesa T.; Cohen, Ross D.; Burbidge, E. Margaret

1990-01-01

Observations of the QSO S4 0248 + 430 and a nearby anonymous galaxy are presented. Two absorption components are found in both Ca II H and K and Na I D1 and D2 at z(a) = 0.0515, 0.0523. Column densities of log N(Ca II) = 13.29, 13.50, and log N(Na I) = 13.79, 14.18 are found for z(a) = 0.0515, 0.0523 absorption systems, respectively. The column density ratios imply considerable calcium depletion and disk-type absorbing gas. At least one and possibly both absorption components are produced by high-velocity gas. A broadband image of the field shows an asymmetrical armlike feature or possible tidal tail covering and extending past the position of the QSO. The presence of this extended feature and the apparent difference between the absorption velocities and galaxy rotation velocity suggest that the absorbing gas is not ordinary disk gas, but rather is a result of tidal disruption.

Excited state absorption spectra of dissolved and aggregated distyrylbenzene: A TD-DFT state and vibronic analysis

NASA Astrophysics Data System (ADS)

Oliveira, Eliezer Fernando; Shi, Junqing; Lavarda, Francisco Carlos; Lüer, Larry; Milián-Medina, Begoña; Gierschner, Johannes

2017-07-01

A time-dependent density functional theory study is performed to reveal the excited state absorption (ESA) features of distyrylbenzene (DSB), a prototype π-conjugated organic oligomer. Starting with a didactic insight to ESA based on simple molecular orbital and configuration considerations, the performance of various density functional theory functionals is tested to reveal the full vibronic ESA features of DSB at short and long probe delay times.