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Sample records for deep core-level photoexcitation

  1. Dynamics deep from the core

    PubMed Central

    Carbone, F.

    2015-01-01

    In van der Veen et al., [Struct. Dyn. 2, 024302 (2015)], femtosecond and nanosecond electron energy loss spectroscopy of deep core-levels are demonstrated. These results pave the way to the investigation of materials and molecules with combined energy, time, and spatial resolution in a transmission electron microscope. Furthermore, the authors elucidate the role of the electron phonon coupling in the band-gap renormalization that takes place in graphite upon photo-excitation. PMID:26798787

  2. Trends in adsorbate induced core level shifts

    NASA Astrophysics Data System (ADS)

    Nilsson, Viktor; Van den Bossche, Maxime; Hellman, Anders; Grönbeck, Henrik

    2015-10-01

    Photoelectron core level spectroscopy is commonly used to monitor atomic and molecular adsorption on metal surfaces. As changes in the electron binding energies are convoluted measures with different origins, calculations are often used to facilitate the decoding of experimental signatures. The interpretation could in this sense benefit from knowledge on trends in surface core level shifts for different metals and adsorbates. Here, density functional theory calculations have been used to systematically evaluate core level shifts for (111) and (100) surfaces of 3d, 4d, and 5d transition metals upon CO, H, O and S adsorption. The results reveal trends and several non-intuitive cases. Moreover, the difficulties correlating core level shifts with charging and d-band shifts are underlined.

  3. Photoemission EXAFS on outer core levels

    SciTech Connect

    Choudhary, K.M.; Rothberg, G.M.; denBoer, M.L.; Williams, G.P.; Hecht, M.H.; Lindau, I.

    1984-01-01

    The first definitive measurements of EXAFS by monitoring the direct photoelectron emission as a function of photon energy have been made using the Mn 3p and F 2s core levels in evaporated films of MnF/sub 2/. Good agreement is found with bulk transmission EXAFS obtained with the Mn 1s level. This development is important because: (1) almost all elements have suitable core levels of low binding energy; (2) since photopeaks from adjacent core levels do not cross as the photon energy is varied, the limitation imposed on other EXAFS techniques by this interference is removed. Auger electrons, which have fixed kinetic energies and so can cross photopeaks, will generally have low energies if they originate from the outer core levels and be unlikely to appear in the EXAFS region of kinetic energies, i.e., in excess of about 50 eV; (3) vuv light is used, which greatly extends the useable range of photon energies; and (4) more than one element in a solid may be studied with the same monochromator. In this work all diffraction effects except the backscattering that gives rise to the EXAFS were eliminated by using a polycrystalline evaporated thin film and by making use of the 2..pi.. azimuthal acceptance angle of a cylindrical mirror analyzer. Previously MARGARITONDO and coworkers observed EXAFS-like oscillations in photopeaks as a function of photon energy when a CMA was used; however, their data did not extend over a sufficient photon energy range to prove conclusively that EXAFS was involved.

  4. Core level shifts of intercalated graphene

    NASA Astrophysics Data System (ADS)

    Schröder, Ulrike A.; Petrović, Marin; Gerber, Timm; Martínez-Galera, Antonio J.; Grånäs, Elin; Arman, Mohammad A.; Herbig, Charlotte; Schnadt, Joachim; Kralj, Marko; Knudsen, Jan; Michely, Thomas

    2017-03-01

    Through intercalation of metals and gases the Dirac cone of graphene on Ir(111) can be shifted with respect to the Fermi level without becoming destroyed by strong hybridization. Here, we use x-ray photoelectron spectroscopy to measure the C 1s core level shift (CLS) of graphene in contact with a number of structurally well-defined intercalation layers (O, H, Eu, and Cs). By analysis of our own and additional literature data for decoupled graphene, the C 1s CLS is found to be a non-monotonic function of the doping level. For small doping levels the shifts are well described by a rigid band model. However, at larger doping levels, a second effect comes into play which is proportional to the transferred charge and counteracts the rigid band shift. Moreover, not only the position, but also the C 1s peak shape displays a unique evolution as a function of doping level. Our conclusions are supported by intercalation experiments with Li, with which, due to the absence of phase separation, the doping level of graphene can be continuously tuned.

  5. Ultrafast structural dynamics of photoexcited adenine.

    PubMed

    Mondal, Sayan; Puranik, Mrinalini

    2017-08-02

    We report deep UV initiated excited state dynamics of the canonical nucleobase adenine (Ade) through Resonance Raman (RR) intensity analysis. RR spectra of Ade at excitation wavelengths throughout the Bb absorption band in the 210-230 nm wavelength range are measured and subsequently converted to scattering cross-sections. The time-dependent wave packet (TDWP) formalism has been employed for self-consistent simulations of the resulting wavelength dependent Raman excitation profiles (REP) and absorption spectrum of Ade. These simulations yield instantaneous nuclear dynamics of Ade within tens of femtoseconds (fs) of photoabsorption as structural distortions, linewidth broadening and solvation parameters. The instantaneous geometrical distortions of the purine ring following photoexcitation into the Bb state are analyzed vis-à-vis the low energy La state (∼260 nm) of Ade. We find that while photoabsorption by the La state causes major distortions of the imidazole ring, pyrimidine ring suffers maximal changes following Bb excitation. Seven in-plane stretching vibrations out of fifteen resonantly enhanced modes of Ade are found to contribute 76% of the total internal reorganization energy (981 cm(-1)) in the Bb excited state. In addition, the inertial response of the solvation shell to photoexcitation is found to be of 1190 cm(-1) in magnitude, and with a relaxation time of 26.5 fs. A parallel comparison is drawn between the UV-C initiated photodynamics of Ade (6-aminopurine) with that of two substituted purines, viz., 6-chloroguanine (6-ClG or 2-amino-6-chloropurine) and guanine (2-amino-6-oxo-purie) which were reported earlier.

  6. Disentangling structural information from core-level excitation spectra

    NASA Astrophysics Data System (ADS)

    Niskanen, Johannes; Sahle, Christoph J.; Gilmore, Keith; Uhlig, Frank; Smiatek, Jens; Föhlisch, Alexander

    2017-07-01

    Core-level spectra of liquids can be difficult to interpret due to the presence of a range of local environments. We present computational methods for investigating core-level spectra based on the idea that both local structural parameters and the x-ray spectra behave as functions of the local atomic configuration around the absorbing site. We identify correlations between structural parameters and spectral intensities in defined regions of interest, using the oxygen K-edge excitation spectrum of liquid water as a test case. Our results show that this kind of analysis can find the main structure-spectral relationships of ice, liquid water, and supercritical water.

  7. Core level binding energies of functionalized and defective graphene

    PubMed Central

    Kaukonen, Markus; Havu, Paula; Ljungberg, Mathias P; Ayala, Paola; Kauppinen, Esko I

    2014-01-01

    Summary X-ray photoelectron spectroscopy (XPS) is a widely used tool for studying the chemical composition of materials and it is a standard technique in surface science and technology. XPS is particularly useful for characterizing nanostructures such as carbon nanomaterials due to their reduced dimensionality. In order to assign the measured binding energies to specific bonding environments, reference energy values need to be known. Experimental measurements of the core level signals of the elements present in novel materials such as graphene have often been compared to values measured for molecules, or calculated for finite clusters. Here we have calculated core level binding energies for variously functionalized or defected graphene by delta Kohn–Sham total energy differences in the real-space grid-based projector-augmented wave density functional theory code (GPAW). To accurately model extended systems, we applied periodic boundary conditions in large unit cells to avoid computational artifacts. In select cases, we compared the results to all-electron calculations using an ab initio molecular simulations (FHI-aims) code. We calculated the carbon and oxygen 1s core level binding energies for oxygen and hydrogen functionalities such as graphane-like hydrogenation, and epoxide, hydroxide and carboxylic functional groups. In all cases, we considered binding energy contributions arising from carbon atoms up to the third nearest neighbor from the functional group, and plotted C 1s line shapes by using experimentally realistic broadenings. Furthermore, we simulated the simplest atomic defects, namely single and double vacancies and the Stone–Thrower–Wales defect. Finally, we studied modifications of a reactive single vacancy with O and H functionalities, and compared the calculated values to data found in the literature. PMID:24605278

  8. Collinear scattering of photoexcited carriers in graphene

    NASA Astrophysics Data System (ADS)

    Trushin, Maxim

    2016-11-01

    We propose an explicitly solvable model for collinear scattering of photoexcited carriers in intrinsic graphene irradiated by monochromatic light. We find that the collinear scattering rate is directly proportional to the photocarrier energy and derive an analytic expression for the corresponding relaxation time. The result agrees with the recent numerical prediction [Nat. Commun. 7, 11617 (2016), 10.1038/ncomms11617] and is able to describe the photocarrier evolution at low energies, where scattering on optical phonons is strongly suppressed.

  9. Quantum Mechanics in Biology: Photoexcitations in DNA

    NASA Astrophysics Data System (ADS)

    Bittner, Eric R.; Czader, Arkadiusz

    We consider here the theoretical and quantum chemical description of the photoexcitated states in DNA duplexes. We discuss the motivation and limitations of an exciton model and use this as the starting point for more detailed excited state quantum chemical evaluations. In particular, we focus upon the role of interbase proton transfer between Watson/Crick pairs in localizing an excitation and then quenching it through intersystem crossing and charge transfer.

  10. Efficient terahertz modulator based on photoexcited graphene

    NASA Astrophysics Data System (ADS)

    Fu, Maixia; Wang, Xinke; Wang, Sen; Xie, Zhenwei; Feng, Shengfei; Sun, Wenfeng; Ye, Jiasheng; Han, Peng; Zhang, Yan

    2017-04-01

    An efficient terahertz (THz) modulator consisting of a single-layer graphene on a silicon substrate has been investigated using an external 450 nm continuous-wave laser with a low photoexcitation power. Upon photoexcitation, both transmission and reflection are measured using a THz time-domain spectroscopy. The experimental results show that the modulation depth of the transmission can reach 74% for the proposed modulator under external photoexcitation. The difference between the transmission through the sample and bare silicon substrate can reach a maximal value of 49.3% with a pump power of 420 mW, which indicates that the modulation effect of graphene is dominant with minimal contribution from the silicon substrate. The analyses of the strong attenuation of the transmitted THz waves reveals that an enhanced absorption of the THz wave takes place, which is shown to be rooted in the increase of the doping level in graphene, the accumulation of the photo-induced carrier at the interface of the graphene and silicon substrate, as well as the scattering between carriers, phonons and defects. The results of this study imply promising applications for the development of high-performance THz modulators and absorbers.

  11. Core-level binding-energy shifts for the metallic elements

    NASA Astrophysics Data System (ADS)

    Johansson, Börje; Mårtensson, Nils

    1980-05-01

    chromium relative to the dns2 configuration in vanadium and manganese. When the core-level shift is referred to, the dns2 (or dn+1s) atomic configuration for all the elements in a transition series, a quite regular behavior of the shift is found. However, some structure can still be observed originating from a change of screening within the d band from a bonding to an antibonding type as one proceeds through the series. For elements beyond the coin metals the screening of a core hole is performed by p electrons, which provide a less effective screening mechanism than the d electrons for the transition metals. The coin metals are intermediate cases, partly due to a dominating s-electron screening and partly due to d-electron bonding in the initial state. The effect of the electron-density redistribution between the free atom and the solid on the core-level shift is particularly striking in the case of the rare-earth elements Pr-Sm and Tb-Tm. Here the remarkable situation is that a deep core electron is less bound in the atom than in the solid. Also for the actinides the electronic redistribution upon condensation gives rise to pronounced effects on the core-level shifts. Further, it is shown that the measured 6p32 binding energy in metallic uranium provides a clear demonstration of the occupation of the 5f level in this metal. The present treatment of the core-level shift for bulk metallic atoms can easily be generalized to surface atoms. From an empirical relation for the surface energy a simple expression for the shift of the surface core-level relative to the bulk can be derived. For the earlier transition metals, it is found that the core electrons are more bound at the surface than in the bulk, while for the heavier ones the opposite situation exists. This change of sign of the surface shift depends on the bonding-antibonding division of the d band. To illustrate how the present approach can be applied to alloy systems, a treatment of core-level shifts for rare

  12. Core level photoelectron spectroscopy probed heterogeneous xenon/neon clusters

    NASA Astrophysics Data System (ADS)

    Pokapanich, Wandared; Björneholm, Olle; Öhrwall, Gunnar; Tchaplyguine, Maxim

    2017-06-01

    Binary rare gas clusters; xenon and neon which have a significant contrariety between sizes, produced by a co-expansion set up and have been studied using synchrotron radiation based x-ray photoelectron spectroscopy. Concentration ratios of the heterogeneous clusters; 1%, 3%, 5% and 10% were controlled. The core level spectra were used to determine structure of the mixed cluster and analyzed by considering screening mechanisms. Furthermore, electron binding energy shift calculations demonstrated cluster aggregation models which may occur in such process. The results showed that in the case of low mixing ratios of 3% and 5% of xenon in neon, the geometric structures exhibit xenon in the center and xenon/neon interfaced in the outer shells. However, neon cluster vanished when the concentration of xenon was increased to 10%.

  13. Lattice charge models and core level shifts in disordered alloys.

    PubMed

    Underwood, T L; Cole, R J

    2013-10-30

    Differences in core level binding energies between atoms belonging to the same chemical species can be related to differences in their intra- and extra-atomic charge distributions, and differences in how their core holes are screened. With this in mind, we consider the charge-excess functional model (CEFM) for net atomic charges in alloys (Bruno et al 2003 Phys. Rev. Lett. 91 166401). We begin by deriving the CEFM energy function in order to elucidate the approximations which underpin this model. We thereafter consider the particular case of the CEFM in which the strengths of the 'local interactions' within all atoms are the same. We show that for binary alloys the ground state charges of this model can be expressed in terms of charge transfer between all pairs of unlike atoms analogously to the linear charge model (Magri et al 1990 Phys. Rev. B 42 11388). Hence, the model considered is a generalization of the linear charge model for alloys containing more than two chemical species. We then determine the model's unknown 'geometric factors' over a wide range of parameter space. These quantities are linked to the nature of charge screening in the model, and we illustrate that the screening becomes increasingly universal as the strength of the local interactions is increased. We then use the model to derive analytical expressions for various physical quantities, including the Madelung energy and the disorder broadening in the core level binding energies. These expressions are applied to ternary random alloys, for which it is shown that the Madelung energy and magnitude of disorder broadening are maximized at the composition at which the two species with the largest 'electronegativity difference' are equal, while the remaining species have a vanishing concentration. This result is somewhat counterintuitive with regards to the disorder broadening since it does not correspond to the composition with the highest entropy. Finally, the model is applied to CuPd and Cu

  14. Alkaline Earth Core Level Photoemission Spectroscopy of High-Temperature Superconductors

    NASA Technical Reports Server (NTRS)

    Vasquez, R.

    1993-01-01

    This paper examines photoemission measurements of the alkaline Earth core levels of high-temperature superconductors and related materials, models that seek to explain the large negative shifts observed relative to the corresponding alkaline Earth metals, and the effect of lattice site disorder on the core level spectra and the presence or absence of intrinsic surface peaks.

  15. Alkaline Earth Core Level Photoemission Spectroscopy of High-Temperature Superconductors

    NASA Technical Reports Server (NTRS)

    Vasquez, R.

    1993-01-01

    This paper examines photoemission measurements of the alkaline Earth core levels of high-temperature superconductors and related materials, models that seek to explain the large negative shifts observed relative to the corresponding alkaline Earth metals, and the effect of lattice site disorder on the core level spectra and the presence or absence of intrinsic surface peaks.

  16. Primary Conformation Change in Bacteriorhodopsin on Photoexcitation

    PubMed Central

    Yabushita, Atsushi; Kobayashi, Takayoshi

    2009-01-01

    Ultrafast dynamics of bacteriorhodopsin (bR) has been extensively studied experimentally and theoretically. However, there are several contradictory results reported, indicating that its detailed dynamics and initial process have not yet been fully clarified. In this work, changes in the amplitude and phase of molecular vibration in the isomerization process of bR were real-time probed simultaneously at 128 different wavelengths through intensity modulation of the electronic transition. Systematic information on the transient change in continuous spectrum extending from 505 nm (2.45 eV) to 675 nm (1.84 eV) showed different dynamics in each spectral region reflecting the difference in the excited states and intermediates dominating the dynamics during the photoisomerization. Careful analysis of the transient spectral changes and spectrograms calculated from the vibrational real-time traces elucidated that the primary event just after photoexcitation is the deformation of the retinal configuration, which decays within 30 fs near the C=N bond in the protonated Schiff base. The intensity of C=N stretching mode starts to decrease before the initiation of the frequency modulation of the C=C stretching mode. The C=C stretching mode frequency was modulated by a coupled torsion around the C13=C14 bond, leading to the photoisomerization around the bond. This study clarified the dynamics of the C=N and C=C stretching modes working as key vibration modes in the photoisomerization of bR. Furthermore, we have elucidated the modulation and decay dynamics of the C=C stretching mode in the photoreaction starting from H (Franck-Condon excited state) followed by I (twisted excited), and J (first intermediate) states. PMID:19217861

  17. Dynamics of photoexcited carrier relaxation and recombination in CdTe/CdS thin films

    SciTech Connect

    Levi, D.H.; Fluegel, B.D.; Ahrenkiel, R.K.

    1996-05-01

    Efficiency-limiting defects in photovoltaic devices are readily probed by time-resolved spectroscopy. This paper presents the first direct optical measurements of the relaxation and recombination pathways of photoexcited carriers in the CdS window layer of CdTe/CdS polycrystalline thin films. Femtosecond time-resolved pump/probe measurements indicate the possible existence of a two-phase CdS/CdSTe layer, rather than a continuously graded alloy layer at the CdTe/CdS interface. Complementary time-resolved photoluminescence (PL) measurements show that the photoexcited carriers are rapidly captured by deep-level defects. The temporal and density-dependent properties of the photoluminescence prove that the large Stokes shift of the PL relative to the band edge is due to strong phonon coupling to deep-level defects in CdS. The authors suggest that modifications in the CdS processing may enhance carrier collection efficiency in the blue spectral region.

  18. An easy-to-implement filter for separating photo-excited signals from topography in scanning tunneling microscopy.

    PubMed

    Wang, Kangkang; Rosenmann, Daniel; Holt, Martin; Winarski, Robert; Hla, Saw-Wai; Rose, Volker

    2013-06-01

    In order to achieve elemental and chemical sensitivity in scanning tunneling microscopy (STM), synchrotron x-rays have been applied to excite core-level electrons during tunneling. The x-ray photo-excitations result in tip currents that are superimposed onto conventional tunneling currents. While carrying important physical information, the varying x-ray induced currents can destabilize the feedback loop causing it to be unable to maintain a constant tunneling current, sometimes even causing the tip to retract fully or crash. In this paper, we report on an easy-to-implement filter circuit that can separate the x-ray induced currents from conventional tunneling currents, thereby allowing simultaneous measurements of topography and chemical contrasts. The filter and the schematic presented here can also be applied to other variants of light-assisted STM such as laser STM.

  19. An easy-to-implement filter for separating photo-excited signals from topography in scanning tunneling microscopy

    SciTech Connect

    Wang Kangkang; Rosenmann, Daniel; Holt, Martin; Winarski, Robert; Hla, Saw-Wai; Rose, Volker

    2013-06-15

    In order to achieve elemental and chemical sensitivity in scanning tunneling microscopy (STM), synchrotron x-rays have been applied to excite core-level electrons during tunneling. The x-ray photo-excitations result in tip currents that are superimposed onto conventional tunneling currents. While carrying important physical information, the varying x-ray induced currents can destabilize the feedback loop causing it to be unable to maintain a constant tunneling current, sometimes even causing the tip to retract fully or crash. In this paper, we report on an easy-to-implement filter circuit that can separate the x-ray induced currents from conventional tunneling currents, thereby allowing simultaneous measurements of topography and chemical contrasts. The filter and the schematic presented here can also be applied to other variants of light-assisted STM such as laser STM.

  20. Extrinsic photoresponse enhancement under additional intrinsic photoexcitation in organic semiconductors

    SciTech Connect

    Kounavis, P.

    2016-06-28

    Dual light beam photoresponse experiments are employed to explore the photoresponse under simultaneous extrinsic and intrinsic photoexcitation of organic semiconductors. The photoresponse of a red modulated light extrinsic photoexcitation is found that can be significantly enhanced under an additional blue bias-light intrinsic photoexcitation in two terminal pentacene films on glass substrates. From the frequency resolved photoresponse, it is deduced that the phenomenon of photoresponse enhancement can be attributed to an increase in the extrinsic photogeneration rate of the red modulated light and/or an improvement of the drift velocity of carriers under an additional blue light intrinsic photoexcitation. The possible predominant extrinsic photogeneration mechanism, which can be compatible with the observed dependence of the photoresponse enhancement on the frequency and on the light intensities of the red and blue light excitation, is the singlet exciton dissociation through electron transfer to acceptor-like traps. Moreover, an improvement in the drift velocity of carriers traversing grain boundaries with potential energy barriers, which may be reduced by trapping of minority carriers created from the intrinsic photoexcitation, may partly contribute to the photoresponse enhancement.

  1. The surface core level shift for lithium at the surface of lithium borate

    NASA Astrophysics Data System (ADS)

    Wooten, David; Ketsman, I.; Xiao, Jie; Losovyj, Ya. B.; Petrosky, J.; McClory, J.; Burak, Ya. V.; Adamiv, V. T.; Dowben, P. A.

    2010-01-01

    The shallow Li 1s core level exhibits a surface-to-bulk core level shift for the stoichiometric Li 2B 4O 7(1 1 0) surface. Angle-resolved photoemission spectroscopy was used to indentify Li 1s bulk and surface core level components at binding energies -56.5±0.4 and -53.7±0.5 eV, respectively. We find photoemission evidence for surface states of Li 2B 4O 7(1 1 0) that exist in the gap of the projected bulk density of states. The existence of surface states is consistent with the large surface-to-bulk core level shift for the Li 1s core.

  2. A first-principles core-level XPS study on the boron impurities in germanium crystal

    SciTech Connect

    Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

    2013-12-04

    We systematically investigated the x-ray photoelectron spectroscopy (XPS) core-level shifts and formation energies of boron defects in germanium crystals and compared the results to those in silicon crystals. Both for XPS core-level shifts and formation energies, relationship between defects in Si and Ge is roughly linear. From the similarity in the formation energy, it is expected that the exotic clusters like icosahedral B12 exist in Ge as well as in Si.

  3. A first-principles core-level XPS study on the boron impurities in germanium crystal

    NASA Astrophysics Data System (ADS)

    Yamauchi, Jun; Yoshimoto, Yoshihide; Suwa, Yuji

    2013-12-01

    We systematically investigated the x-ray photoelectron spectroscopy (XPS) core-level shifts and formation energies of boron defects in germanium crystals and compared the results to those in silicon crystals. Both for XPS core-level shifts and formation energies, relationship between defects in Si and Ge is roughly linear. From the similarity in the formation energy, it is expected that the exotic clusters like icosahedral B12 exist in Ge as well as in Si.

  4. Phase coherence and pairing amplitude in photo-excited superconductors

    NASA Astrophysics Data System (ADS)

    Perfetti, Luca; Piovera, Christian; Zhang, Zailan

    2016-05-01

    New data on Bi2Sr2CaCu2O8+δ (Bi2212) reveal interesting aspects of photoexcited superconductors. The electrons dynamics show that inelastic scattering by nodal quasiparticles decreases when the temperature is lowered below the critical value of the superconducting phase transition. This drop of electronic dissipation is astonishingly robust and survives to photoexcitation densities much larger than the value sustained by long-range superconductivity. The unconventional behavior of quasiparticle scattering is ascribed to superconducting correlations extending on a length scale comparable to the inelastic mean-free path. Our measurements indicate that strongly driven superconductors enter in a regime without phase coherence but finite pairing amplitude.

  5. Enhancement of Paramagnetic Relaxation by Photoexcited Gold Nanorods

    PubMed Central

    Wen, Tao; Wamer, Wayne G.; Subczynski, Witold K.; Hou, Shuai; Wu, Xiaochun; Yin, Jun-Jie

    2016-01-01

    Electron spin resonance (ESR) spectroscopy was used to investigate the switchable, light-dependent effects of gold nanorods (GNRs) on paramagnetic properties of nitroxide spin probes. The photoexcited GNRs enhanced the spin-spin and spin-lattice relaxations of nitroxide spin probes. It was shown that molecular oxygen plays the key role in this process. Our results demonstrate that ESR is a powerful tool for investigating the events following photoexcitation of GNRs. The novel light-controlled effects observed for GNRs on paramagnetic properties and activities of surrounding molecules have a number of significant applications where oxygen sensing and oxygen activity is important. PMID:27071507

  6. Observation of suppressed terahertz absorption in photoexcited graphene

    NASA Astrophysics Data System (ADS)

    Frenzel, A. J.; Lui, C. H.; Fang, W.; Nair, N. L.; Herring, P. K.; Jarillo-Herrero, P.; Kong, J.; Gedik, N.

    2013-03-01

    When light is absorbed by a semiconductor, photoexcited charge carriers enhance the absorption of far-infrared radiation due to intraband transitions. We observe the opposite behavior in monolayer graphene, a zero-gap semiconductor with linear dispersion. By using time domain terahertz (THz) spectroscopy in conjunction with optical pump excitation, we observe a reduced absorption of THz radiation in photoexcited graphene. The measured spectral shape of the differential optical conductivity exhibits non-Drude behavior. We discuss several possible mechanisms that contribute to the observed low-frequency non-equilibrium optical response of graphene.

  7. Ultrafast X-ray Auger probing of photoexcited molecular dynamics

    DOE PAGES

    McFarland, B. K.; Farrell, J. P.; Miyabe, S.; ...

    2014-06-23

    Here, molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation—X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towardsmore » high kinetic energies, resulting from a particular C–O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.« less

  8. Ultrafast X-ray Auger probing of photoexcited molecular dynamics

    SciTech Connect

    McFarland, B. K.; Farrell, J. P.; Miyabe, S.; Tarantelli, F.; Aguilar, A.; Berrah, N.; Bostedt, C.; Bozek, J. D.; Bucksbaum, P. H.; Castagna, J. C.; Coffee, R. N.; Cryan, J. P.; Fang, L.; Feifel, R.; Gaffney, K. J.; Glownia, J. M.; Martinez, T. J.; Mucke, M.; Murphy, B.; Natan, A.; Osipov, T.; Petrović, V. S.; Schorb, S.; Schultz, Th.; Spector, L. S.; Swiggers, M.; Tenney, I.; Wang, S.; White, J. L.; White, W.; Gühr, M.

    2014-06-23

    Here, molecules can efficiently and selectively convert light energy into other degrees of freedom. Disentangling the underlying ultrafast motion of electrons and nuclei of the photoexcited molecule presents a challenge to current spectroscopic approaches. Here we explore the photoexcited dynamics of molecules by an interaction with an ultrafast X-ray pulse creating a highly localized core hole that decays via Auger emission. We discover that the Auger spectrum as a function of photoexcitation—X-ray-probe delay contains valuable information about the nuclear and electronic degrees of freedom from an element-specific point of view. For the nucleobase thymine, the oxygen Auger spectrum shifts towards high kinetic energies, resulting from a particular C–O bond stretch in the ππ* photoexcited state. A subsequent shift of the Auger spectrum towards lower kinetic energies displays the electronic relaxation of the initial photoexcited state within 200 fs. Ab-initio simulations reinforce our interpretation and indicate an electronic decay to the nπ* state.

  9. The spin signature of charged photoexcitations in carbazolyl substituted polydiacetylene

    NASA Astrophysics Data System (ADS)

    Brabec, C. J.; Johansson, H.; Cravino, A.; Sariciftci, N. S.; Comoretto, D.; Dellepiane, G.; Moggio, I.

    1999-12-01

    In this article, photoinduced infrared absorption (PIA-FTIR) and light induced electron spin resonance (LESR) measurements on an asymmetric carbazolyl substituted polydiacetylene (PDA), the poly{1-(N-carbazolyl) penta-1,3-diyn-5-ol} (polyCPDO) are presented. Results from both experimental techniques imply that contrary to other well-known polydiacetylene derivatives, in polyCPDO there exist only long-living, highly localized charged photoexcitations with spin 1/2 (g value˜2.0026), indicative for polaronic excitations. PolyCPDO also shows a strong dark ESR signal with the same g value as the LESR signal and with a Curie susceptibility of approximately 10-3 spins per CPDO monomer unit. This unusually high number of defects may come from intermediates of the polymerization. Furthermore, the photoexcited states of composites from polyCPDO mixed with a special solubilized methano-fullerene [6,6]-Phenyl C61-butyric acid methyl ester (PCBM) with excellent acceptor properties are investigated and compared with those of the pristine polymer. No enhancement of PIA-FTIR and LESR signals is found for these composites. It is therefore concluded, that even polyCPDO, which shows charged spin 1/2 photoexcitations, does not exhibit a photoexcited charge transfer to fullerenes as observed in other nondegenerate ground state conjugated polymer fullerene composites.

  10. Two-Color Ultrafast Photoexcited Scanning Tunneling Microscopy

    SciTech Connect

    Camillone, N.; Dolocan, A.; Acharya, D.P.; Zahl, P.; Sutter, P.

    2011-05-26

    We report on two-color two-photon photoexcitation of a metal surface driven by ultrafast laser pulses and detected with a scanning tunneling microscope (STM) tip as a proximate anode. Results are presented for two cases: (i) where the tip is retracted from the surface far enough to prohibit tunneling, and (ii) where the tip is within tunneling range of the surface. A delay-modulation technique is implemented to isolate the two-color photoemission from concurrent one-color two-photon photoemission and provide subpicosecond time-resolved detection. When applied with the tip in tunneling range, this approach effectively isolates the two-photon photoexcited current signal from the conventional tunneling current and enables subpicosecond time-resolved detection of the photoexcited surface electrons. The advantage of the two-color approach is highlighted by comparison with the one-color case where optical interference causes thermal modulation of the STM tip length, resulting in tunneling current modulations that are orders of magnitude larger than the current due to photoexcitation of surface electrons. By completely eliminating this interference, and thereby avoiding thermal modulation of the STM tip length, the two-color approach represents an important step toward the ultimate goal of simultaneous subnanometer and subpicosecond measurements of surface electron dynamics by ultrafast-laser-excited STM.

  11. Spin polarization and magnetic dichroism in core-level photoemission from ferromagnets

    SciTech Connect

    Menchero, Jose Gabriel

    1997-05-01

    In this thesis we present a theoretical investigation of angle- and spin-resolved core-level photoemission from ferromagnetic Fe and Ni. We also consider magneto-dichroic effects due to reversal of the photon helicity or reversal of the sample magnetization direction. In chapter 1, we provide a brief outline of the history of photoemission, and show how it has played an important role in the development of modern physics. We then review the basic elements of the theory of core-level photoemission, and discuss the validity of the some of the commonly-used approximations. In chapter 2, we present a one-electron theory to calculate spin- and angle-resolved photoemission spectra for an arbitrary photon polarization. The Hamiltonian includes both spin-orbit and exchange interactions. As test cases for the theory, we calculate the spin polarization and magnetic dichroism for the Fe 2p core level, and find that agreement with experiment is very good.

  12. Femtomagnetism in graphene induced by core level excitation of organic adsorbates

    PubMed Central

    Ravikumar, Abhilash; Baby, Anu; Lin, He; Brivio, Gian Paolo; Fratesi, Guido

    2016-01-01

    We predict the induction or suppression of magnetism in the valence shell of physisorbed and chemisorbed organic molecules on graphene occurring on the femtosecond time scale as a result of core level excitations. For physisorbed molecules, where the interaction with graphene is dominated by van der Waals forces and the system is non-magnetic in the ground state, numerical simulations based on density functional theory show that the valence electrons relax towards a spin polarized configuration upon excitation of a core-level electron. The magnetism depends on efficient electron transfer from graphene on the femtosecond time scale. On the other hand, when graphene is covalently functionalized, the system is magnetic in the ground state showing two spin dependent mid gap states localized around the adsorption site. At variance with the physisorbed case upon core-level excitation, the LUMO of the molecule and the mid gap states of graphene hybridize and the relaxed valence shell is not magnetic anymore. PMID:27089847

  13. Electronic Structure of Heavy Fermion Uranium Compounds Studied by Core-Level Photoelectron Spectroscopy

    NASA Astrophysics Data System (ADS)

    Fujimori, Shin-ichi; Ohkochi, Takuo; Kawasaki, Ikuto; Yasui, Akira; Takeda, Yukiharu; Okane, Tetsuo; Saitoh, Yuji; Fujimori, Atsushi; Yamagami, Hiroshi; Haga, Yoshinori; Yamamoto, Etsuji; Tokiwa, Yoshifumi; Ikeda, Shugo; Sugai, Takashi; Ohkuni, Hitoshi; Kimura, Noriaki; Ōnuki, Yoshichika

    2012-01-01

    High-energy-resolution core-level and valence-band photoelectron spectroscopic studies were performed for the heavy fermion uranium compounds UGe2, UCoGe, URhGe, URu2Si2, UNi2Al3, UPd2Al3, and UPt3 as well as typical localized and itinerant uranium compounds to understand the relationship between the uranium valence state and their core-level spectral line shapes. In addition to the main line and high-binding energy satellite structure recognized in the core-level spectra of uranium compounds, a shoulder structure on the lower binding energy side of the main lines of localized and nearly localized uranium compounds was also found. The spectral line shapes show a systematic variation depending on the U 5f electronic structure. The core-level spectra of UGe2, UCoGe, URhGe, URu2Si2, and UNi2Al3 are rather similar to those of itinerant compounds, suggesting that U 5f electrons in these compounds are well hybridized with ligand states. On the other hand, the core-level spectra of UPd2Al3 and UPt3 show considerably different spectral line shapes from those of the itinerant compounds, suggesting that U 5f electrons in UPd2Al3 and UPt3 are less hybridized with ligand states, leading to the correlated nature of U 5f electrons in these compounds. The dominant final state characters in their core-level spectra suggest that the numbers of 5f electrons in UGe2, UCoGe, URhGe, URu2Si2, UNi2Al3, and UPd2Al3 are close to but less than three, while that of UPt3 is close to two rather than to three.

  14. Origin of the core-level binding energy shifts in Au nanoclusters

    NASA Astrophysics Data System (ADS)

    Tal, Alexey A.; Olovsson, Weine; Abrikosov, Igor A.

    2017-06-01

    We investigate the shifts of the core-level binding energies in small gold nanoclusters by using ab initio density-functional-theory calculations. The shift of the 4 f states is calculated for magic-number nanoclusters in a wide range of sizes and morphologies. We find a nonmonotonous behavior of the core-level shift in nanoclusters depending on the size. We demonstrate that there are three main contributions to the Au 4 f shifts, which depend sensitively on the interatomic distances, coordination, and quantum confinement. They are identified and explained by the change of the on-site electrostatic potential.

  15. Detection of subsurface core-level shifts in Si 2p core-level photoemission from Si(111)-(1x1):As

    SciTech Connect

    Paggel, J.J.; Hasselblatt, M.; Horn, K.

    1997-04-01

    The (7 x 7) reconstruction of the Si(111) surface arises from a lowering energy through the reduction of the number of dangling bonds. This reconstruction can be removed by the adsorption of atoms such as hydrogen which saturate the dangling bonds, or by the incorporation of atoms, such as arsenic which, because of the additional electron it possesses, can form three bonds and a nonreactive lone pair orbital from the remaining two electrons. Core and valence level photoemission and ion scattering data have shown that the As atoms replace the top silicon atoms. Previous core level spectra were interpreted in terms of a bulk and a single surface doublet. The authors present results demonstrate that the core level spectrum contains two more lines. The authors assign these to subsurface silicon layers which also experience changes in the charge distribution when a silicon atom is replaced by an arsenic atom. Subsurface core level shifts are not unexpected since the modifications of the electronic structure and/or of photohole screening are likely to decay into the bulk and not just to affect the top-most substrate atoms. The detection of subsurface components suggests that the adsorption of arsenic leads to charge flow also in the second double layer of the Si(111) surface. In view of the difference in atomic radius between As and Si, it was suggested that the (1 x 1): As surface is strained. The presence of charge rearrangement up to the second double layer implies that the atomic coordinates also exhibit deviations from their ideal Si(111) counterparts, which might be detected through a LEED I/V or photoelectron diffraction analysis.

  16. Identification of underlayer components in the surface core-level spectra of W(111)

    NASA Astrophysics Data System (ADS)

    Purcell, Kevin G.; Jupille, Jacques; Derby, Glyn P.; King, David A.

    1987-07-01

    Core-level photoemission spectra from a W(111) surface using synchrotron radiation are presented. These core-level spectra are shown to be composed of four components with the same peak shape: one from bulk atoms and three from different crystallographic sites in the selvedge. The selvedge peaks comprise a peak from the topmost surface atoms (shifted by -0.45+/-0.01 eV) and two different underlayer sites (shifted by -0.30+/-0.02 eV and -0.11+/-0.02 eV from the bulk peak). This contrasts with a previous model, proposed by Wertheim, Citrin and Van der Veen, which used only two surface components: a broadened surface atom peak and one underlayer peak. The data presented can be fitted with three peaks, yielding good agreement with the peak energies obtained by these authors; however, we show that the four-peak model gives a better fit to the experimental spectra. The use of two underlayer peaks is in good agreement both with intuitive arguments based on the coordination number of atoms in the selvedge and with two previous theoretical calculations of the surface core-level shift. The values determined from the fitting parameters for the core-level line shape are also in good agreement with values calculated by other workers.

  17. Identification of underlayer components in the surface core-level spectra of W(111)

    SciTech Connect

    Purcell, K.G.; Jupille, J.; Derby, G.P.; King, D.A.

    1987-07-15

    Core-level photoemission spectra from a W(111) surface using synchrotron radiation are presented. These core-level spectra are shown to be composed of four components with the same peak shape: one from bulk atoms and three from different crystallographic sites in the selvedge. The selvedge peaks comprise a peak from the topmost surface atoms (shifted by -0.45 +- 0.01 eV) and two different underlayer sites (shifted by -0.30 +- 0.02 eV and -0.11 +- 0.02 eV from the bulk peak). This contrasts with a previous model, proposed by Wertheim, Citrin and Van der Veen, which used only two surface components: a broadened surface atom peak and one underlayer peak. The data presented can be fitted with three peaks, yielding good agreement with the peak energies obtained by these authors; however, we show that the four-peak model gives a better fit to the experimental spectra. The use of two underlayer peaks is in good agreement both with intuitive arguments based on the coordination number of atoms in the selvedge and with two previous theoretical calculations of the surface core-level shift. The values determined from the fitting parameters for the core-level line shape are also in good agreement with values calculated by other workers.

  18. Modeling Shallow Core-Level Transitions in the Reflectance Spectra of Gallium-Containing Semiconductors

    NASA Astrophysics Data System (ADS)

    Stoute, Nicholas; Aspnes, David

    2012-02-01

    The electronic structure of covalent materials is typically approached by band theory. However, shallow core level transitions may be better modeled by an atomic-scale approach. We investigate shallow d-core level reflectance spectra in terms of a local atomic-multiplet theory, a novel application of a theory typically used for higher-energy transitions on more ionic type material systems. We examine specifically structure in reflectance spectra of GaP, GaAs, GaSb, GaSe, and GaAs1-xPx due to transitions that originate from Ga3d core levels and occur in the 20 to 25 eV range. We model these spectra as a Ga^+3 closed-shell ion whose transitions are influenced by perturbations on 3d hole-4p electron final states. These are specifically spin-orbit effects on the hole and electron, and a crystal-field effect on the hole, attributed to surrounding bond charges and positive ligand anions. Empirical radial-strength parameters were obtained by least-squares fitting. General trends with respect to anion electronegativity are consistent with expectations. In addition to the spin-orbit interaction, crystal-field effects play a significant role in breaking the degeneracy of the d levels, and consequently are necessary to understand shallow 3d core level spectra.

  19. Core level shifts in Cu-Pd alloys as a function of bulk composition and structure

    NASA Astrophysics Data System (ADS)

    Boes, Jacob R.; Kondratyuk, Peter; Yin, Chunrong; Miller, James B.; Gellman, Andrew J.; Kitchin, John R.

    2015-10-01

    CuPd alloys are important materials in hydrogen purification, where they are used as dense Pd-based separation membranes. Cu is added to impart sulfur tolerance and improved mechanical properties. At intermediate compositions and T < 873 K, a BCC alloy (B2) phase occurs, which has superior separation characteristics to those of the FCC phases that form at high Cu and high Pd compositions. Identifying the composition and temperature window where the B2 phase forms is a critical need to enable the design of improved alloys. A composition spread alloy film of Cu and Pd was synthesized. The film was characterized by electron back scatter diffraction and X-ray photoelectron spectroscopy, providing the core level shifts as a function of bulk composition and bulk structure. An anomalous deviation in the Cu core level shift was observed in the composition range 0.33 < xPd < 0.55 over which the B2 phase occurs. Density functional theory calculations were used to simulate core level shifts in the FCC and B2 alloy structures. They suggest that the anomalous deviation in core level shift is due to formation of the ordered B2 phase in this composition range.

  20. Separation of distinct photoexcitation species in femtosecond transient absorption microscopy

    SciTech Connect

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

    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 spatial 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.

  1. Quantum tunneling of hydrogen atom in dissociation of photoexcited methylamine.

    PubMed

    Marom, Ran; Levi, Chen; Weiss, Tal; Rosenwaks, Salman; Zeiri, Yehuda; Kosloff, Ronnie; Bar, Ilana

    2010-09-16

    The probability of hydrogen atom release, following photoexcitation of methylamine, CH(3)NH(2), is found to increase extensively as higher vibrational states on the first excited electronic state are accessed. This behavior is consistent with theoretical calculations, based on the probability of H atom tunneling through an energy barrier on the excited potential energy surface, implying that N-H bond breaking is dominated by quantum tunneling.

  2. Microscopic view on the ultrafast photoluminescence from photoexcited graphene.

    PubMed

    Winzer, Torben; Ciesielski, Richard; Handloser, Matthias; Comin, Alberto; Hartschuh, Achim; Malic, Ermin

    2015-02-11

    We present a joint theory-experiment study on ultrafast photoluminescence from photoexcited graphene. On the basis of a microscopic theory, we reveal two distinct mechanisms behind the occurring photoluminescence: besides the well-known incoherent contribution driven by nonequilibrium carrier occupations, we found a coherent part that spectrally shifts with the excitation energy. In our experiments, we demonstrate for the first time the predicted appearance and spectral shift of the coherent photoluminescence.

  3. Skirting terahertz waves in a photo-excited nanoslit structure

    SciTech Connect

    Shalaby, Mostafa E-mail: thomas.feurer@iap.unibe.ch; Fabiańska, Justyna; Feurer, Thomas E-mail: thomas.feurer@iap.unibe.ch; Peccianti, Marco; Ozturk, Yavuz; Vidal, Francois; Morandotti, Roberto; Sigg, Hans

    2014-04-28

    Terahertz fields can be dramatically enhanced as they propagate through nanometer-sized slits. The enhancement is mediated by a significant accumulation of the induced surface charges on the surrounding metal. This enhancement is shown here to be dynamically modulated while the nanoslits are gradually shunted using a copropagating optical beam. The terahertz fields are found to skirt the nanoscale photo-excited region underneath the slits, scattering to the far field and rigorously mapping the near field.

  4. Absolute Binding Energies of Core Levels in Solids from First Principles

    NASA Astrophysics Data System (ADS)

    Ozaki, Taisuke; Lee, Chi-Cheng

    2017-01-01

    A general method is presented to calculate absolute binding energies of core levels in metals and insulators, based on a penalty functional and an exact Coulomb cutoff method in the framework of density functional theory. The spurious interaction of core holes between supercells is avoided by the exact Coulomb cutoff method, while the variational penalty functional enables us to treat multiple splittings due to chemical shift, spin-orbit coupling, and exchange interaction on equal footing, both of which are not accessible by previous methods. It is demonstrated that the absolute binding energies of core levels for both metals and insulators are calculated by the proposed method in a mean absolute (relative) error of 0.4 eV (0.16%) for eight cases compared to experimental values measured with x-ray photoemission spectroscopy within a generalized gradient approximation to the exchange-correlation functional.

  5. Photoexcited riboflavin induces oxidative damage to human serum albumin

    NASA Astrophysics Data System (ADS)

    Hirakawa, Kazutaka; Yoshioka, Takuto

    2015-08-01

    Photoexcited riboflavin induced damage of human serum albumin (HSA), a water soluble protein, resulting in the diminishment of fluorescence from the tryptophan residue. Because riboflavin hardly photosensitized singlet oxygen generation and sodium azide, a singlet oxygen quencher, did not inhibit protein damage, electron transfer-mediated oxidation of HSA was speculated. Fluorescence lifetime of riboflavin was not affected by HSA, suggesting that the excited triplet state of riboflavin is responsible for protein damage through electron transfer. In addition, the preventive effect of xanthone derivatives, triplet quenchers, on photosensitized protein damage could be evaluated using this photosensitized reaction system of riboflavin and HSA.

  6. Photoexcitation dynamics in thin films of insulated molecular wires

    NASA Astrophysics Data System (ADS)

    Chang, M. H.; Frampton, M. J.; Anderson, H. L.; Herz, L. M.

    2006-12-01

    A study is presented on how encapsulation of conjugated polymer chains affects the motion of photoexcitations and the formation of interchain aggregates in solid films. It is shown that threading of a poly(diphenylene vinylene) backbone inside insulating cyclodextrins (rotaxination) and/or complexation of the chains with poly(ethylene oxide) are effective means of preventing the diffusion of excitons to nonradiative defect sites. Ultrafast time-resolved photoluminescence data reveal that excitation transfer between encapsulated chains is still possible and, for the case of rotaxination, is likely to be facilitated through close packing of end groups belonging to adjacent chains.

  7. Modeling photoexcited reactions of simple molecules in solution

    NASA Astrophysics Data System (ADS)

    Zhang, Jing

    Photoexcited iodine in rare gas systems offer a paradigm for understanding excited state condensed phase chemistry. Solvent induced nonadiabaticity plays an important role in the dynamics of these systems and modifies electronic structure by introducing off-diagonal coupling elements to our electronic Hamiltonian matrix. A semi-empirical electronic structure method, diatomics-in-molecules (DIM), together with its extension designed for ionic systems, diatomics-in-ionic-systems (DIIS), is applied to dynamical studies of photoexcited iodine in Ar and Xe rare gas systems. Mixed quantum-classical molecular dynamics implemented using a surface hopping algorithm is employed in a trajectory study which successfully describes the nonadiabatic nature of these systems. First we looked into the photoexcited I2 in its manifold of covalent states in solid Ar, focusing on the cage-bound but otherwise dissociative potential curves. Cage motions disturb the electronic structure and influence the coupling between electronic states to a large extent due to the large-scale intramolecular motion associated with stretching of the I2 bond resulting from double-photon excitation. Dynamical simulation with a surface hopping algorithm describes the cage-bound state photoexcitation dynamics which has only been simulated by other groups using classical methods that do not allow for nonadiabatic electronic transitions. A characteristic recursion time of the cage-bound state motion is found though our simulation which matches the experimental results, and our simulated pump-probe signals successfully reproduce the experimental spectrum. Finally we apply our potential model and surface hopping dynamical calculation method to the charge transfer complex Xe+2I- in xenon clusters. The states of this system are accessed at much higher energy than the covalent states. Charge transfer occurs between atoms and requires a significantly more complex potential energy model for which we use an extension

  8. Photoexcited quantum dots for killing multidrug-resistant bacteria

    NASA Astrophysics Data System (ADS)

    Courtney, Colleen M.; Goodman, Samuel M.; McDaniel, Jessica A.; Madinger, Nancy E.; Chatterjee, Anushree; Nagpal, Prashant

    2016-05-01

    Multidrug-resistant bacterial infections are an ever-growing threat because of the shrinking arsenal of efficacious antibiotics. Metal nanoparticles can induce cell death, yet the toxicity effect is typically nonspecific. Here, we show that photoexcited quantum dots (QDs) can kill a wide range of multidrug-resistant bacterial clinical isolates, including methicillin-resistant Staphylococcus aureus, carbapenem-resistant Escherichia coli, and extended-spectrum β-lactamase-producing Klebsiella pneumoniae and Salmonella typhimurium. The killing effect is independent of material and controlled by the redox potentials of the photogenerated charge carriers, which selectively alter the cellular redox state. We also show that the QDs can be tailored to kill 92% of bacterial cells in a monoculture, and in a co-culture of E. coli and HEK 293T cells, while leaving the mammalian cells intact, or to increase bacterial proliferation. Photoexcited QDs could be used in the study of the effect of redox states on living systems, and lead to clinical phototherapy for the treatment of infections.

  9. Photoexcited quantum dots for killing multidrug-resistant bacteria.

    PubMed

    Courtney, Colleen M; Goodman, Samuel M; McDaniel, Jessica A; Madinger, Nancy E; Chatterjee, Anushree; Nagpal, Prashant

    2016-05-01

    Multidrug-resistant bacterial infections are an ever-growing threat because of the shrinking arsenal of efficacious antibiotics. Metal nanoparticles can induce cell death, yet the toxicity effect is typically nonspecific. Here, we show that photoexcited quantum dots (QDs) can kill a wide range of multidrug-resistant bacterial clinical isolates, including methicillin-resistant Staphylococcus aureus, carbapenem-resistant Escherichia coli, and extended-spectrum β-lactamase-producing Klebsiella pneumoniae and Salmonella typhimurium. The killing effect is independent of material and controlled by the redox potentials of the photogenerated charge carriers, which selectively alter the cellular redox state. We also show that the QDs can be tailored to kill 92% of bacterial cells in a monoculture, and in a co-culture of E. coli and HEK 293T cells, while leaving the mammalian cells intact, or to increase bacterial proliferation. Photoexcited QDs could be used in the study of the effect of redox states on living systems, and lead to clinical phototherapy for the treatment of infections.

  10. 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

  11. Symmetry rules in magnetic core-level photoelectron spectroscopy from epitaxial ferromagnetic ultrathin films

    NASA Astrophysics Data System (ADS)

    Schellenberg, R.; Meinert, H.; Perez, A.; Kisker, E.

    2001-09-01

    For two x-ray incidence directions onto an epitaxial FeNi(001) film, one to the left and a second one to the right side of the symmetry plane spanned by the magnetization direction and the photoelectron wave vector, we have measured distributions of the emission-angle dependence with respect to the crystallographic axes of the Fe 2p3/2 core-level photoelectron intensity asymmetry occurring upon magnetization reversal. The two angular distributions transform into each other when the signs of the magnetization and of the photoelectron emission angle are inverted, in accordance with the conservation of parity.

  12. Communication: Application of state-specific multireference coupled cluster methods to core-level excitations

    NASA Astrophysics Data System (ADS)

    Brabec, Jiří; Bhaskaran-Nair, Kiran; Govind, Niranjan; Pittner, Jiří; Kowalski, Karol

    2012-11-01

    The concept of the model space underlying multireference coupled-cluster (MRCC) formulations is a powerful tool to deal with complex correlation effects for various electronic states. Here, we demonstrate that iterative state-specific MRCC methods (SS-MRCC) based on properly defined model spaces can be used to describe core-level excited states even when Hartree-Fock orbitals are utilized. We show that the SS-MRCC models with single and double excitations are comparable in accuracy to high-level single reference equation-of-motion coupled cluster (EOMCC) formalism.

  13. Photoemission core-level shifts reveal the thiolate-Au(111) interface

    SciTech Connect

    Groenbeck, Henrik; Odelius, Michael

    2010-08-15

    The nature of the thiolate/Au(111) interface is a long-standing puzzle. It has been suggested that thiolates drive surface reconstruction, however, a consensus regarding the adsorption configuration is missing. Herein, the density-functional theory is used to evaluate surface core-level shifts (SCLSs) for methyl thiolates on Au(111) assuming a representative set of different surface reconstructions. The SCLSs are found to provide sensitive fingerprints of the anchoring configuration, and it is only thiolate adsorption in the form of MeS-Au-SMe complexes that can be reconciled with experimental data.

  14. Direct Measurement of Core-Level Relaxation Dynamics on a Surface-Adsorbate System

    NASA Astrophysics Data System (ADS)

    Miaja-Avila, L.; Saathoff, G.; Mathias, S.; Yin, J.; La-O-Vorakiat, C.; Bauer, M.; Aeschlimann, M.; Murnane, M. M.; Kapteyn, H. C.

    2008-07-01

    The coupling between electronic states in a surface-adsorbate system is fundamental to the understanding of many surface interactions. In this Letter, we present the first direct time-resolved observations of the lifetime of core-excited states of an atom adsorbed onto a surface. By comparing laser-assisted photoemission from a substrate with a delayed Auger decay process from an adsorbate, we measure the lifetime of the 4d-1 core level of xenon on Pt(111) to be 7.1±1.1fs. This result opens up time-domain measurements of surface dynamics where energy-resolved measurements may provide incomplete information.

  15. Control of lasing from a highly photoexcited semiconductor microcavity

    NASA Astrophysics Data System (ADS)

    Hsu, Feng-Kuo

    Technological advances in the fabrication of optical cavities and crystal growth have enabled the studies on macroscopic quantum states and emergent nonequilibrium phenomena of light-matter hybrids in condensed matter. Optical excitations in a semiconductor microcavity can result in a coupled electron-hole-photon (e-h-gamma) system, in which various many-body physics can be studied by varying particle densities and particle-particle interactions. Recently there have been reports of phenomena analogous to Bose-Einstein condensates or superfluids for exciton-polaritons in a microcavity. An exciton-polariton is a quasiparticle resulting from strong coupling between the cavity light field and the exciton (e-h pair) transition, and typically is only stable at a low density ( 10 11 to 1012 cm-2 or less). At a higher density, it has been theoretically predicted that pairing of electrons and holes can result in a BCS-like state at cryogenic temperatures, which can produce cooperative radiation known as superradiance. In this work, we explore cooperative phenomena caused by e-h correlation and many-body effect in a highly photoexcited microcavity at room temperature. High-density e-h plasmas in a photoexcited microcavity are studied under the following conditions: (1) the sample is photoexcited GaAs-based microcavity with large detuning between the band gap Eg of quantum well and cavity resonance to prevent carriers from radiative loss, (2) the density of e-h pairs is high enough to build long-range correlation with the assistance of cavity light field. The Fermi level of electron-hole pairs is about 80 meV above Eg, and (3) the e-h correlation is stabilized through thermal management, which includes modulating the excitation pulse laser temporally and spatially to reduce the heating and carrier diffusion effect. We have observed ultrafast (sub-10 picoseconds) spin-polarized lasing with sizable energy shifts and linewidth broadenings as pump flux is increased. With

  16. Photoexcited ZnO nanoparticles with controlled defects as a highly sensitive oxygen sensor

    SciTech Connect

    Goto, Taku; Ito, Tsuyohito; Shimizu, Yoshiki; Yasuda, Hidehiro

    2016-07-11

    Conductance of photoexcited ZnO nanoparticles with various defects has been investigated in oxygen. ZnO nanoparticles, which show strong photoluminescence peaks originating from interstitial zinc atom (Zn{sub i}) and singly charged oxygen vacancy (V{sub O}{sup +}), show oxygen-pressure-dependent conductance changes caused by photoexcitation. Herein, a model is proposed to simulate the conductance changes.

  17. Core level excitations—A fingerprint of structural and electronic properties of epitaxial silicene

    SciTech Connect

    Friedlein, R. Fleurence, A.; Aoyagi, K.; Yamada-Takamura, Y.; Jong, M. P. de; Van Bui, H.; Wiggers, F. B.; Yoshimoto, S.; Koitaya, T.; Shimizu, S.; Noritake, H.; Mukai, K.; Yoshinobu, J.

    2014-05-14

    From the analysis of high-resolution Si 2p photoelectron and near-edge x-ray absorption fine structure (NEXAFS) spectra, we show that core level excitations of epitaxial silicene on ZrB{sub 2}(0001) thin films are characteristically different from those of sp{sup 3}-hybridized silicon. In particular, it is revealed that the lower Si 2p binding energies and the low onset in the NEXAFS spectra as well as the occurrence of satellite features in the core level spectra are attributed to the screening by low-energy valence electrons and interband transitions between π bands, respectively. The analysis of observed Si 2p intensities related to chemically distinct Si atoms indicates the presence of at least one previously unidentified component. The presence of this component suggests that the observation of stress-related stripe domains in scanning tunnelling microscopy images is intrinsically linked to the relaxation of Si atoms away from energetically unfavourable positions.

  18. Quanty for core level spectroscopy - excitons, resonances and band excitations in time and frequency domain

    NASA Astrophysics Data System (ADS)

    Haverkort, Maurits W.

    2016-05-01

    Depending on the material and edge under consideration, core level spectra manifest themselves as local excitons with multiplets, edge singularities, resonances, or the local projected density of states. Both extremes, i.e., local excitons and non-interacting delocalized excitations are theoretically well under control. Describing the intermediate regime, where local many body interactions and band-formation are equally important is a challenge. Here we discuss how Quanty, a versatile quantum many body script language, can be used to calculate a variety of different core level spectroscopy types on solids and molecules, both in the frequency as well as the time domain. The flexible nature of Quanty allows one to choose different approximations for different edges and materials. For example, using a newly developed method merging ideas from density renormalization group and quantum chemistry [1-3], Quanty can calculate excitons, resonances and band-excitations in x-ray absorption, photoemission, x-ray emission, fluorescence yield, non-resonant inelastic x-ray scattering, resonant inelastic x-ray scattering and many more spectroscopy types. Quanty can be obtained from: http://www.quanty.org.

  19. Core-level photoemission from nanocluster-matrix composites: Au clusters in amorphous carbon

    NASA Astrophysics Data System (ADS)

    Calliari, L.; Minati, L.; Speranza, G.; Paris, A.; Baranov, A.; Fanchenko, S.

    2014-09-01

    We investigate a system consisting of Au nano-clusters and amorphous carbon (a-C) via core-level photoemission. While the ability of photoemission to characterize nano-sized metal clusters is well-known, still some issues deserve investigation. For example, the well-established dominance of final-state relaxation effects in core-level spectra from nano-clusters necessarily involves a crucial role of the cluster dielectric-environment. To the best of our knowledge however, a thorough discussion on this point is lacking. We thus intend to investigate dielectric-environment effects by considering several configurations for Au clusters, i.e. supported and embedded, with the latter obtained either by depositing a-C on top of supported clusters or by co-depositing a-C and Au. We analyze the Au4 f spectrum from clusters accounting for both cluster size and cluster location with respect to the a-C matrix. We show that spectral changes caused by a-C deposition are entirely explained in terms of changes in the cluster dielectric environment. Moreover, we prove that supported clusters are in a well-characterized dielectric environment, while embedded clusters are not. This is because embedded clusters, whatever the method of production, are spatially distributed over the matrix surface-region which is characterized by rapid fluctuations in the dielectric constant.

  20. Photoexcited Carrier Dynamics of Cu2S Thin Films.

    PubMed

    Riha, Shannon C; Schaller, Richard D; Gosztola, David J; Wiederrecht, Gary P; Martinson, Alex B F

    2014-11-20

    Copper sulfide is a simple binary material with promising attributes for low-cost thin film photovoltaics. However, stable Cu2S-based device efficiencies approaching 10% free from cadmium have yet to be realized. In this Letter, transient absorption spectroscopy is used to investigate the dynamics of the photoexcited state of isolated Cu2S thin films prepared by atomic layer deposition or vapor-based cation exchange of ZnS. While a number of variables including film thickness, carrier concentration, surface oxidation, and grain boundary passivation were examined, grain structure alone was found to correlate with longer lifetimes. A map of excited state dynamics is deduced from the spectral evolution from 300 fs to 300 μs. Revealing the effects of grain morphology on the photophysical properties of Cu2S is a crucial step toward reaching high efficiencies in operationally stable Cu2S thin film photovoltaics.

  1. Spectral Weight Transfer and the Role of Photoexcitation in PCMO

    NASA Astrophysics Data System (ADS)

    McGill, S. A.; Miller, R. I.; Torrens, O. N.; Kikkawa, J. M.; Mamchik, A.; Chen, I.-Wei

    2004-03-01

    We have performed static white light reflectivity measurements on Pr_0.67Ca_0.33MnO3 from T = 35 K to room temperature and magnetic fields up to 7 Tesla to measure spectral weight transfer in the optical and mid-IR ranges. Here we compare our results with pump-probe transient reflectivity obtained for similar conditions of temperature, magnetic field, and photoexcitation. We use these data to assess the contribution of lattice heating to the transient signals. Finally, we have observed long-lived changes in the DC reflectivity spectrum after controlled exposures to pulsed excitation. We discuss these effects in terms of the destruction and creation of the B = 0 T, low-temperature, charge-ordered insulating state and the subsequent implications for the material's magnetic order.

  2. Defect-induced supercollision cooling of photoexcited carriers in graphene.

    PubMed

    Alencar, Thonimar V; Silva, Mychel G; Malard, Leandro M; de Paula, Ana M

    2014-10-08

    Defects play a fundamental role in the energy relaxation of hot photoexcited carriers in graphene, thus a complete understanding of these processes are vital for improving the development of graphene devices. Recently, it has been theoretically predicted and experimentally demonstrated that defect-assisted acoustic phonon supercollision, the collision between a carrier and both an acoustic phonon and a defect, is an important energy relaxation process for carriers with excess energy below the optical phonon emission. Here, we studied samples with defects optically generated in a controlled manner to experimentally probe the supercollision model as a function of the defect density. We present pump and probe transient absorption measurements showing that the decay time decreases as the density of defect increases as predicted by the supercollision model.

  3. Theory of Primary Photoexcitations in Donor-Acceptor Copolymers.

    PubMed

    Aryanpour, Karan; Dutta, Tirthankar; Huynh, Uyen N V; Vardeny, Zeev Valy; Mazumdar, Sumit

    2015-12-31

    We present a generic theory of primary photoexcitations in low band gap donor-acceptor conjugated copolymers. Because of the combined effects of strong electron correlations and broken symmetry, there is considerable mixing between a charge-transfer exciton and an energetically proximate triplet-triplet state with an overall spin singlet. The triplet-triplet state, optically forbidden in homopolymers, is allowed in donor-acceptor copolymers. For an intermediate difference in electron affinities of the donor and the acceptor, the triplet-triplet state can have a stronger oscillator strength than the charge-transfer exciton. We discuss the possibility of intramolecular singlet fission from the triplet-triplet state, and how such fission can be detected experimentally.

  4. Carrier confinement and bond softening in photoexcited bismuth films

    NASA Astrophysics Data System (ADS)

    Shin, Taeho; Wolfson, Johanna W.; Teitelbaum, Samuel W.; Kandyla, Maria; Nelson, Keith A.

    2015-11-01

    Femtosecond pump-probe spectroscopy of bismuth thin films has revealed strong dependencies of reflectivity and phonon frequency on film thickness in the range of 25 -40 nm . The reflectivity variations are ascribed to distinct electronic structures originating from strongly varying electronic temperatures and proximity of the film thickness to the optical penetration depth of visible light. The phonon frequency is redshifted by an amount that increases with decreasing film thickness under the same excitation fluence, indicating carrier density-dependent bond softening that increases due to suppressed diffusion of carriers away from the photoexcited region in thin films. The results have significant implications for nonthermal melting of bismuth as well as lattice heating due to inelastic electron-phonon scattering.

  5. Plasmon-driven acceleration in a photo-excited nanotube

    DOE PAGES

    Shin, Young -Min

    2017-02-21

    A plasmon-assisted channeling acceleration can be realized with a large channel, possibly at the nanometer scale. Carbon nanotubes (CNTs) are the most typical example of nano-channels that can confine a large number of channeled particles in a photon-plasmon coupling condition. This paper presents a theoretical and numerical study on the concept of high-field charge acceleration driven by photo-excited Luttinger-liquid plasmons in a nanotube. An analytic description of the plasmon-assisted laser acceleration is detailed with practical acceleration parameters, in particular, with the specifications of a typical tabletop femtosecond laser system. Lastly, the maximally achievable acceleration gradients and energy gains within dephasingmore » lengths and CNT lengths are discussed with respect to laser-incident angles and CNT-filling ratios.« less

  6. Photoexcited Carrier Dynamics of Cu2S Thin Films

    DOE PAGES

    Riha, Shannon C.; Schaller, Richard D.; Gosztola, David J.; ...

    2014-11-11

    Copper sulfide is a simple binary material with promising attributes for low-cost thin film photovoltaics. However, stable Cu2S-based device efficiencies approaching 10% free from cadmium have yet to be realized. In this paper, transient absorption spectroscopy is used to investigate the dynamics of the photoexcited state of isolated Cu2S thin films prepared by atomic layer deposition or vapor-based cation exchange of ZnS. While a number of variables including film thickness, carrier concentration, surface oxidation, and grain boundary passivation were examined, grain structure alone was found to correlate with longer lifetimes. A map of excited state dynamics is deduced from themore » spectral evolution from 300 fs to 300 μs. Finally, revealing the effects of grain morphology on the photophysical properties of Cu2S is a crucial step toward reaching high efficiencies in operationally stable Cu2S thin film photovoltaics.« less

  7. Near-field spectroscopy of graphene during ultrafast photoexcitation

    NASA Astrophysics Data System (ADS)

    Wagner, Martin; Fei, Zhe; McLeod, Alexander; Rodin, Aleksandr; Bao, Wenzhong; Zhang, Lingfeng; Zhao, Zeng; Iwinski, Eric; Thiemens, Mark; Fogler, Michael; Castro-Neto, Antonio; Lau, Chunning; Keilmann, Fritz; Basov, Dimitri

    2013-03-01

    Recently, impressive progress in nanoplasmonics of graphene using near-field spectroscopy and imaging has been reported [Z. Fei et al., Nano Lett. 11, 4701 (2011); Z. Fei et al., Nature 487, 82 (2012)]. However, these studies of the interaction of the graphene plasmon with the SiO2 substrate surface phonon were time-independent. Here we combine imaging and material characterization on the nano scale with ultrafast sub-picosecond time resolution and present optical pump broadband mid-infrared probe spectroscopy of graphene. We discuss the optical pump induced changes of the coupled plasmon-phonon modes with respect to carrier density and time-dependence. The difference between ultrafast photoexcitation and conventional electrostatic doping via the field effect is analyzed and compared with modeling.

  8. Low-temperature galvanomagnetic studies of nominally undoped germanium subjected to intrinsic photoexcitation

    SciTech Connect

    Bannaya, V. F.

    2015-09-15

    The results of studying the heating of charge carriers by an electric field in nominally undoped Ge (with impurity concentrations of (N{sub a} + N{sub g}) ≤ 5 × 10{sup 13} cm{sup –3}) subjected to interband illumination are reported. It is necessary in this situation to take into account two types of free charge carriers. In the case of such generation, the relation between the concentrations of electrons and holes depends to a large extent on the value of the electric field since this field differently affects the recombination coefficients of charge carriers and gives rise to new effects. The results of experimental studies of the conductivity σ and the Hall constant R{sub H} in n-Ge and p-Ge at T = 4.2 K and at different intensities of intrinsic photoexcitation are reported. A model of interband recombination, which takes into account deep-level impurity centers, is suggested for explanation of the results.

  9. Er/Si (111) interface intermixing investigation using core level photoemission

    SciTech Connect

    Haderbache, L.; Wetzel, P.; Pirri, C.; Peruchetti, J.C.; Bolmont, D.; Gewinner, G. )

    1990-07-23

    We present in this letter Si 2{ital p} core level photoemission measurements on the Er/Si (111) interface formed at room temperature. These spectroscopic data are compared with those measured on amorphous silicide films for various Er concentrations grown by coevaporation of Er and Si species at room temperature under ultrahigh vacuum conditions. This study reveals a strong interaction between Er and the Si (111) substrate even at very low coverage. A mixed interface is observed with silicide formation up to 6 monolayers of deposited metal which corresponds to the onset of erbium metal overgrowth. The Er concentration in the interfacial silicide is found to increase as a function of the deposited Er thickness. A model for the interface is proposed and discussed.

  10. Exciton and core-level electron confinement effects in transparent ZnO thin films

    PubMed Central

    Mosquera, Adolfo A.; Horwat, David; Rashkovskiy, Alexandr; Kovalev, Anatoly; Miska, Patrice; Wainstein, Dmitry; Albella, Jose M.; Endrino, Jose L.

    2013-01-01

    The excitonic light emission of ZnO films have been investigated by means of photoluminescence measurements in ultraviolet-visible region. Exciton confinement effects have been observed in thin ZnO coatings with thickness below 20 nm. This is enhanced by a rise of the intensity and a blue shift of the photoluminescence peak after extraction of the adsorbed species upon annealing in air. It is found experimentally that the free exciton energy (determined by the photoluminescence peak) is inversely proportional to the square of the thickness while core-level binding energy is inversely proportional to the thickness. These findings correlate very well with the theory of kinetic and potential confinements.

  11. LDA+DMFT approach to core-level spectroscopy: Application to 3 d transition metal compounds

    NASA Astrophysics Data System (ADS)

    Hariki, Atsushi; Uozumi, Takayuki; Kuneš, Jan

    2017-07-01

    We present a computational study of 2 p core-level x-ray photoemission spectra of transition metal monoxides M O (M =Ni ,Co,Mn) and sesquioxides M2O3 (M =V ,Cr,Fe) using a theoretical framework based on the local-density approximation + dynamical mean-field theory. We find a very good description of the fine spectral features, which is a considerable improvement over the conventional cluster model. We analyze the role of nonlocal screening and its relationship to long-range magnetic order and lattice geometry. Our results reveal the potential of the present method for the analysis and interpretation of modern high-energy-resolution experiments.

  12. Physics of the Be(10{bar 1} 0) Surface Core Level Spectrum

    SciTech Connect

    Lizzit, S.; Pohl, K. |; Baraldi, A.; Comelli, G.; Fritzsche, V.; Plummer, E.W. |; Stumpf, R.; Hofmann, P. ||

    1998-10-01

    Photoelectron diffraction has been utilized to confirm the theoretical prediction that the surface core level shifts observed for Be(10{bar 1}0) have been improperly assigned. The original assignment based upon the relative intensity of the shifted components was intuitively obvious: the peak with the largest shift of {minus}0.7 eV with respect to the bulk was associated with the surface plane, the next peak shifted by {minus}0.5 eV stems from the second layer, and the third peak at {minus}0.22 eV from the third and fourth layers. First-principles theory and our experimental data show that the largest shift is associated with the second plane, not the first plane. {copyright} {ital 1998} {ital The American Physical Society }

  13. Direct measurement of core-level relaxation dynamics on a surface- adsorbate system

    NASA Astrophysics Data System (ADS)

    Yin, Jing; Miaja-Avila, Luis; Saathoff, Guido; La-O-Vorakiat, Chan; Murnane, Margaret; Kapteyn, Henry; Mathias, Stefan; Aeschlimann, Martin; Bauer, Michael

    2008-03-01

    Electronic coupling between an adsorbate and the surface on which it resides is fundamental to the understanding of many surface interactions. However, the interaction of highly-excited adsorbate states is an area that has been explored only indirectly to-date. In this work, we present the first direct time-resolved observations of the lifetime of core-excited states of an atom adsorbed onto a surface. By implementing laser-assisted Auger decay on an adsorbate/surface system, we directly measure the lifetime of the 4d-1 core level of Xenon on Pt(111) to be 7.1 ± 1.1 fs. This result opens up time domain measurements of highly-excited state dynamics in materials systems where, because of complex interactions, energy-resolved measurements provide incomplete information.

  14. Direct measurement of core-level relaxation dynamics on a surface- adsorbate system

    NASA Astrophysics Data System (ADS)

    Yin, Jing; Miaja-Avila, Luis; Saathoff, Guido; La-O-Vorakiat, Chan; Murnane, Margaret; Kapteyn, Henry; Mathias, Stefan; Aeschlimann, Martin; Bauer, Michael

    2008-05-01

    Electronic coupling between an adsorbate and the surface on which it resides is fundamental to the understanding of many surface interactions. However, the interaction of highly-excited adsorbate states is an area that has been explored only indirectly to-date. In this work, we present the first direct time-resolved observations of the lifetime of core-excited states of an atom adsorbed onto a surface. By implementing laser-assisted Auger decay on an adsorbate/surface system, we directly measure the lifetime of the 4d-1 core level of Xenon on Pt(111) to be 7.1 ± 1.1 fs. This result opens up time domain measurements of highly-excited state dynamics in materials systems where, because of complex interactions, energy-resolved measurements provide incomplete information.

  15. Reversible and irreversible structural transformations of nanocomponents of molecular layers by resonance photoexcitation or heating

    NASA Astrophysics Data System (ADS)

    Kaliteevskaya, Elena N.; Krutyakova, Valentina P.; Razumova, Tatyana K.; Starovoytov, Anton A.

    2010-09-01

    The reversible and irreversible structural transformations of monomolecular and associated nanocomponents of a polymethine dye layer by photoexcitation or heating are studied experimentally. The photo- and thermodestruction yields of the layers are investigated.

  16. Core level electron binding energies of realgar (As{sub 4}S{sub 4})

    SciTech Connect

    Pratt, A.R.; Nesbitt, H.W.

    2000-04-01

    XPS broad scans and high-resolution narrow-region spectra were collected from fresh realgar (As{sub 4}S{sub 4}) surfaces to measure core level S and As binding energies. Reasonably accurate As and S concentrations were determined from XPS broad scans using peak areas and manufacturer supplied sensitivity factors. High resolution S(2p) and As(3d) narrow region spectra were comprised of photoelectron emissions indicative of As and S in intermediate oxidation states akin to binding energies of As and S polymeric species. S(2p) spectra were interpreted using only S contributions expected from the bulk mineral matrix and showed that S was not greatly affected by surface state phenomena. This was attributed to breakage of intermolecular van der Waals bonds rather than covalent interatomic bonds. As(3d) spectra were found to contain two contributions one from As atoms in As{sub 4}S{sub 4} molecules in the bulk mineral matrix and another possibly from As atoms in molecules situated at the surface.

  17. Large-scale Bethe-Salpeter equation calculations of core-level x-ray spectra

    NASA Astrophysics Data System (ADS)

    Rehr, J. J.; Vinson, J.; Gilmore, K.

    2013-03-01

    Recently an approach has been developed for Bethe-Salpeter equation (BSE) calculations of core-level x-ray spectra, which is implemented in the OCEAN package [3] which combines plane-wave, pseudopotential DFT electronic structure, PAW transition elements, GW self-energy corrections, and the NIST BSE solver. The method yields both dipole limited and finite momentum transfer spectra. Here we discuss several recent advances which yield a unified treatment of both extended states and atomic multiplet effects. In particular our approach now includes spin-dependent potentials and hole-dependent lifetimes, and gives an improved treatment of L2,3 edges, where contributions to spectral weight come from a mix of two distinct core holes. We have also extended the code interface to include pseudopotential wave functions from ABINIT, QUANTUMESPRESSO, or an interpolation based scheme, thus enabling large-scale calculations with unit cells in excess of 2000 Å3. Applications to water and ice structures are briefly discussed. Supported by DOE BES Grant DE-FG03-97ER45623 and facilitated by the DOE CMCSN

  18. Atomic signatures of local environment from core-level spectroscopy in β -Ga2O3

    NASA Astrophysics Data System (ADS)

    Cocchi, Caterina; Zschiesche, Hannes; Nabok, Dmitrii; Mogilatenko, Anna; Albrecht, Martin; Galazka, Zbigniew; Kirmse, Holm; Draxl, Claudia; Koch, Christoph T.

    2016-08-01

    We present a joint theoretical and experimental study on core-level excitations from the oxygen K edge of β -Ga2O3 . A detailed analysis of the electronic structure reveals the importance of O-Ga hybridization effects in the conduction region. The spectrum from O 1 s core electrons is dominated by excitonic effects, which overall redshift the absorption onset by 0.5 eV, and significantly redistribute the intensity to lower energies. Analysis of the spectra obtained within many-body perturbation theory reveals atomic fingerprints of the inequivalent O atoms. From the comparison of energy-loss near-edge fine-structure (ELNES) spectra computed with respect to different crystal planes, with measurements recorded under the corresponding diffraction conditions, we show how the spectral contributions of specific O atoms can be enhanced while quenching others. These results suggest ELNES, combined with ab initio many-body theory, as a very powerful technique to characterize complex systems, with sensitivity to individual atomic species and to their local environment.

  19. Calculation of core-level excitation in some MAX-phase compounds

    NASA Astrophysics Data System (ADS)

    Wang, Liaoyuan; Rulis, Paul; Ching, W. Y.

    2013-07-01

    We report first-principles spectroscopic calculation of core level excitations in five MAX-phase compounds. The spectra of Ti-K edges in Ti2AlC and Ti2AlN, C-K edge in Ti2AlC, N-K edge in Ti2AlN, and Nb-K edge in Nb2AlC are calculated and found to be in good agreement with reported experimental measurements. Based on this agreement, the Al-K and Al-L3 edges in the same five phases plus the Cr-K and C-K edges in Cr2AlC and the C-K edge in Nb2AlC are calculated as theoretical predictions. We further analyze the anisotropy in the calculated spectra to gain additional insights on the structure-properties relationships in these MAX-phase compounds. These results are further discussed in the context of the local atomic environments of the M, A, and X elements in MAX-phase compounds and in relation to their fundamental electronic structures.

  20. Pressure-induced crossing of the core levels in 5 d metals

    NASA Astrophysics Data System (ADS)

    Tal, Alexey A.; Katsnelson, Mikhail I.; Ekholm, Marcus; Jönsson, H. Johan M.; Dubrovinsky, Leonid; Dubrovinskaia, Natalia; Abrikosov, Igor A.

    2016-05-01

    A pressure-induced interaction between core electrons, the core-level crossing (CLC) transition, has been observed in hcp Os at P ≈400 GPa [L. Dubrovinsky et al., Nature (London) 525, 226 (2015)], 10.1038/nature14681. By carrying out a systematic theoretical study for all metals of the 5 d series (Hf, Ta, W, Re, Os, Ir, Pt, Au) we have found that the CLC transition is a general effect for this series of metals. While in Pt it occurs at ≈1500 GPa , at a pressure substantially higher than in Os, in Ir it occurs already at 80 GPa. Moreover, we predict that in Re the CLC transition may take place already at ambient pressure. We explain the effect of the CLC and analyze the shift of the transition pressure across the series within the Thomas-Fermi model. In particular, we show that the effect has many common features with the atomic collapse in rare-earth elements.

  1. Photoexcited energy transfer in a weakly coupled dimer

    DOE PAGES

    Hernandez, Laura Alfonso; Nelson, Tammie; Tretiak, Sergei; ...

    2015-01-08

    Nonadiabatic excited-state molecular dynamics (NA-ESMD) simulations have been performed in order to study the time-dependent exciton localization during energy transfer between two chromophore units of the weakly coupled anthracene dimer dithia-anthracenophane (DTA). Simulations are done at both low temperature (10 K) and room temperature (300 K). The initial photoexcitation creates an exciton which is primarily localized on a single monomer unit. Subsequently, the exciton experiences an ultrafast energy transfer becoming localized on either one monomer unit or the other, whereas delocalization between both monomers never occurs. In half of the trajectories, the electronic transition density becomes completely localized on themore » same monomer as the initial excitation, while in the other half, it becomes completely localized on the opposite monomer. In this article, we present an analysis of the energy transfer dynamics and the effect of thermally induced geometry distortions on the exciton localization. Finally, simulated fluorescence anisotropy decay curves for both DTA and the monomer unit dimethyl anthracene (DMA) are compared. As a result, our analysis reveals that changes in the transition density localization caused by energy transfer between two monomers in DTA is not the only source of depolarization and exciton relaxation within a single DTA monomer unit can also cause reorientation of the transition dipole.« less

  2. Photoexcited energy transfer in a weakly coupled dimer

    SciTech Connect

    Hernandez, Laura Alfonso; Nelson, Tammie; Tretiak, Sergei; Fernandez-Alberti, Sebastian

    2015-01-08

    Nonadiabatic excited-state molecular dynamics (NA-ESMD) simulations have been performed in order to study the time-dependent exciton localization during energy transfer between two chromophore units of the weakly coupled anthracene dimer dithia-anthracenophane (DTA). Simulations are done at both low temperature (10 K) and room temperature (300 K). The initial photoexcitation creates an exciton which is primarily localized on a single monomer unit. Subsequently, the exciton experiences an ultrafast energy transfer becoming localized on either one monomer unit or the other, whereas delocalization between both monomers never occurs. In half of the trajectories, the electronic transition density becomes completely localized on the same monomer as the initial excitation, while in the other half, it becomes completely localized on the opposite monomer. In this article, we present an analysis of the energy transfer dynamics and the effect of thermally induced geometry distortions on the exciton localization. Finally, simulated fluorescence anisotropy decay curves for both DTA and the monomer unit dimethyl anthracene (DMA) are compared. As a result, our analysis reveals that changes in the transition density localization caused by energy transfer between two monomers in DTA is not the only source of depolarization and exciton relaxation within a single DTA monomer unit can also cause reorientation of the transition dipole.

  3. Ultrafast electron injection into photo-excited organic molecules.

    PubMed

    Cvetko, Dean; Fratesi, Guido; Kladnik, Gregor; Cossaro, Albano; Brivio, Gian Paolo; Venkataraman, Latha; Morgante, Alberto

    2016-08-10

    Charge transfer rates at metal/organic interfaces affect the efficiencies of devices for organic based electronics and photovoltaics. A quantitative study of electron transfer rates, which take place on the femtosecond timescale, is often difficult, especially since in most systems the molecular adsorption geometry is unknown. Here, we use X-ray resonant photoemission spectroscopy to measure ultrafast charge transfer rates across pyridine/Au(111) interfaces while also controlling the molecular orientation on the metal. We demonstrate that a bi-directional charge transfer across the molecule/metal interface is enabled upon creation of a core-exciton on the molecule with a rate that has a strong dependence on the molecular adsorption angle. Through density functional theory calculations, we show that the alignment of molecular levels relative to the metal Fermi level is dramatically altered when a core-hole is created on the molecule, allowing the lowest unoccupied molecular orbital to fall partially below the metal Fermi level. We also calculate charge transfer rates as a function of molecular adsorption geometry and find a trend that agrees with the experiment. These findings thus give insight into the charge transfer dynamics of a photo-excited molecule on a metal surface.

  4. Competing ultrafast energy relaxation pathways in photoexcited graphene.

    PubMed

    Jensen, S A; Mics, Z; Ivanov, I; Varol, H S; Turchinovich, D; Koppens, F H L; Bonn, M; Tielrooij, K J

    2014-10-08

    For most optoelectronic applications of graphene, a thorough understanding of the processes that govern energy relaxation of photoexcited carriers is essential. The ultrafast energy relaxation in graphene occurs through two competing pathways: carrier-carrier scattering, creating an elevated carrier temperature, and optical phonon emission. At present, it is not clear what determines the dominating relaxation pathway. Here we reach a unifying picture of the ultrafast energy relaxation by investigating the terahertz photoconductivity, while varying the Fermi energy, photon energy and fluence over a wide range. We find that sufficiently low fluence (≲4 μJ/cm(2)) in conjunction with sufficiently high Fermi energy (≳0.1 eV) gives rise to energy relaxation that is dominated by carrier-carrier scattering, which leads to efficient carrier heating. Upon increasing the fluence or decreasing the Fermi energy, the carrier heating efficiency decreases, presumably due to energy relaxation that becomes increasingly dominated by phonon emission. Carrier heating through carrier-carrier scattering accounts for the negative photoconductivity for doped graphene observed at terahertz frequencies. We present a simple model that reproduces the data for a wide range of Fermi levels and excitation energies and allows us to qualitatively assess how the branching ratio between the two distinct relaxation pathways depends on excitation fluence and Fermi energy.

  5. Two-Step Photoexcitation Mechanism in Amorphous Se

    NASA Astrophysics Data System (ADS)

    Berashevich, J.; Mishchenko, A.; Reznik, A.

    2014-04-01

    The first-principles simulations are applied to study a photoinduced metastability in amorphous selenium and contribution of the valence-alteration pair (VAP) defects in this process. The VAP defect is confirmed to be the equilibrium defect; it minimizes the destabilizing interaction induced by disorientation of the lone-pair (LP) electrons along the Se chains, and, thus, relieves tension in a system. The photoexcitation involves the LP electrons, and it is proposed to be described by two coexisting processes, namely, single- and double-electron excitations. Both processes are found to induce the defect states in the band gap and cause experimentally observed photodarkening; however, only double-electron excitation is capable of triggering bond rearrangement and structural transformation. Lattice relaxation, which follows bond rearrangement, occurs with characteristic energy of -0.9±0.3 eV. It is found to promote formation of energetically favorable VAP defects and to trigger the ringlike to helixlike transformations, thus, ultimately stimulating the photoinduced crystallization. The photoinduced crystallization is directly simulated in a system characterized by increased crystalline order.

  6. Kinetics of photoconductivity in ZnSe crystals upon photoexcitation of deep centers

    SciTech Connect

    Bruk, L.I.; Gorya, O.S.; Korotkov, V.A.

    1995-10-01

    It has long been known that investigation of the spectral characteristics of photoconductivity (PC) in wide-band-gap semiconductors does not provide full information on the position of photosensitive centers in the forbidden band. The broad spectrum of intrinsic and impurity PC consists of several overlapping bands. In the long-wavelength region, impurity photoeffect is superimposed over the falling-off spectrum of intrinsic PC. In addition, measurements of steady-state PC are incapable of revealing photoinsensitive recombination and trapping centers. Those levels that were not excited prior to illumination of the semiconductor may provide no contribution to PC and may appear either photoinsensitive or indistinguishable from dominant channels of recombination and trapping on other centers. Preliminary excitation may alter the state of these levels to such a degree that they will show up as a spike in the PC relaxation curve. In this paper, we report kinetic studies of the PC and the effective cross section for photon capture (CSPC) in the photosensitivity range of zinc selenide single crystals containing trace impurities.

  7. Gamma Spectra Resulting From the Annihilation of Positrons with Electrons in Single, Selected Core Levels of Cu, Ag and Au

    SciTech Connect

    Kim, S; Eshed, A; Goktepeli, S; Sterne, P A; Koymen, A R; Chen, W C; Weiss, A H

    2005-07-25

    The {gamma}-ray energy spectra due to positron annihilation with the 3p core-level of Cu, the 4p core-level of Ag, and 5p core level of Au were obtained separately from the total annihilation spectrum by measuring the energies of {gamma}-rays time coincident with Auger electrons emitted as a result of filling the core-hole left by annihilation. The results of these measurements are compared to the total annihilation spectra and with LDA based theoretical calculations. A comparison of area normalized momentum distributions with the individual cores extracted from the Doppler measurements shows good qualitative agreement, however, in all three spectra, the calculated values of the momentum density appears to fall below the measured values as the momentum increases. The discrepancies between theory and experiment are well outside the statistical uncertainties of the experiment and become more pronounced with increasing Z going down the column from Cu to Ag to Au. The comparison with the experimental results clearly indicates that the calculations are not predicting the correct ratio of high momentum to low momentum spectral weight and suggest the need to improve the treatment of many body electron-positron correlation effects in annihilation as they pertain to core levels.

  8. Pronounced Surface Band Bending of Thin-Film Silicon Revealed by Modeling Core Levels Probed with Hard X-rays.

    PubMed

    Wippler, David; Wilks, Regan G; Pieters, Bart E; van Albada, Sacha J; Gerlach, Dominic; Hüpkes, Jürgen; Bär, Marcus; Rau, Uwe

    2016-07-13

    Enhancing the probing depth of photoemission studies by using hard X-rays allows the investigation of buried interfaces of real-world device structures. However, it also requires the consideration of photoelectron-signal attenuation when evaluating surface effects. Here, we employ a computational model incorporating surface band bending and exponential photoelectron-signal attenuation to model depth-dependent spectral changes of Si 1s and Si 2s core level lines. The data were acquired from hydrogenated boron-doped microcrystalline thin-film silicon, which is applied in silicon-based solar cells. The core level spectra, measured by hard X-ray photoelectron spectroscopy using different excitation energies, reveal the presence of a 0.29 nm thick surface oxide layer. In the silicon film a downward surface band bending of eVbb = -0.65 eV over ∼6 nm obtained via inverse modeling explains the observed core level shifts and line broadening. Moreover, the computational model allows the extraction of the "real" Si 1s and Si 2s bulk core level binding energies as 1839.13 and 150.39 eV, and their natural Lorentzian line widths as 496 and 859 meV, respectively. These values significantly differ from those directly extracted from the measured spectra. Because band bending usually occurs at material surfaces we highly recommend the detailed consideration of signal integration over depth for quantitative statements from depth-dependent measurements.

  9. Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production

    SciTech Connect

    Yoshii, Hiroshi; Yoshii, Yukie; Asai, Tatsuya; Furukawa, Takako; Takaichi, Shinichi; Fujibayashi, Yasuhisa

    2012-01-06

    Highlights: Black-Right-Pointing-Pointer Some photo-excited carotenoids have photosensitizing ability. Black-Right-Pointing-Pointer They are able to produce ROS. Black-Right-Pointing-Pointer Photo-excited fucoxanthin can produce singlet oxygen through energy transfer. -- Abstract: Carotenoids, natural pigments widely distributed in algae and plants, have a conjugated double bond system. Their excitation energies are correlated with conjugation length. We hypothesized that carotenoids whose energy states are above the singlet excited state of oxygen (singlet oxygen) would possess photosensitizing properties. Here, we demonstrated that human skin melanoma (A375) cells are damaged through the photo-excitation of several carotenoids (neoxanthin, fucoxanthin and siphonaxanthin). In contrast, photo-excitation of carotenoids that possess energy states below that of singlet oxygen, such as {beta}-carotene, lutein, loroxanthin and violaxanthin, did not enhance cell death. Production of reactive oxygen species (ROS) by photo-excited fucoxanthin or neoxanthin was confirmed using a reporter assay for ROS production with HeLa Hyper cells, which express a fluorescent indicator protein for intracellular ROS. Fucoxanthin and neoxanthin also showed high cellular penetration and retention. Electron spin resonance spectra using 2,2,6,6-tetramethil-4-piperidone as a singlet oxygen trapping agent demonstrated that singlet oxygen was produced via energy transfer from photo-excited fucoxanthin to oxygen molecules. These results suggest that carotenoids such as fucoxanthin, which are capable of singlet oxygen production through photo-excitation and show good penetration and retention in target cells, are useful as photosensitizers in photodynamic therapy for skin disease.

  10. Photo-excitation of carotenoids causes cytotoxicity via singlet oxygen production.

    PubMed

    Yoshii, Hiroshi; Yoshii, Yukie; Asai, Tatsuya; Furukawa, Takako; Takaichi, Shinichi; Fujibayashi, Yasuhisa

    2012-01-06

    Carotenoids, natural pigments widely distributed in algae and plants, have a conjugated double bond system. Their excitation energies are correlated with conjugation length. We hypothesized that carotenoids whose energy states are above the singlet excited state of oxygen (singlet oxygen) would possess photosensitizing properties. Here, we demonstrated that human skin melanoma (A375) cells are damaged through the photo-excitation of several carotenoids (neoxanthin, fucoxanthin and siphonaxanthin). In contrast, photo-excitation of carotenoids that possess energy states below that of singlet oxygen, such as β-carotene, lutein, loroxanthin and violaxanthin, did not enhance cell death. Production of reactive oxygen species (ROS) by photo-excited fucoxanthin or neoxanthin was confirmed using a reporter assay for ROS production with HeLa Hyper cells, which express a fluorescent indicator protein for intracellular ROS. Fucoxanthin and neoxanthin also showed high cellular penetration and retention. Electron spin resonance spectra using 2,2,6,6-tetramethil-4-piperidone as a singlet oxygen trapping agent demonstrated that singlet oxygen was produced via energy transfer from photo-excited fucoxanthin to oxygen molecules. These results suggest that carotenoids such as fucoxanthin, which are capable of singlet oxygen production through photo-excitation and show good penetration and retention in target cells, are useful as photosensitizers in photodynamic therapy for skin disease. Copyright © 2011 Elsevier Inc. All rights reserved.

  11. Slow deactivation channels in UV-photoexcited adenine DNA.

    PubMed

    Chen, Xuebo; Fang, Weihai; Wang, Haobin

    2014-03-07

    The molecular mechanism for removing the excess energy in DNA bases is responsible for the high photostability of DNA and is thus the subject of intense theoretical/computational investigation. To understand why the excited state decay of the stacked bases is significantly longer than that of the monomers, we carried out electronic structure calculations on an adenine monomer and an aqueous (dA)5 oligonucleotide employing the CASPT2//CASSCF and CASPT2//CASSCF/AMBER levels of theory. The newly-found bright excited state pair Sstack1((1)ππ*) and Sstack2((1)ππ*) of d(A)5, originated from base stacking, is of intra-base charge transfer nature and occurs in different stacked bases with charge transfer along opposite directions. Two slow deactivation channels of d(A)5 were proposed as a result of the sizable barriers along the relaxation paths starting from the FC point of the Sstack1((1)ππ*) state. The SN1P((1)nπ*) state of d(A)5 serves as an intermediate state in one relaxation channel, to which a nonadiabatic decay from the Sstack1((1)ππ*) state occurs in an energy degeneracy region. A relatively high barrier in this state is found and attributed to the steric hindrance of the DNA environment due to the large NH2 group twisting, which gives a weak and red-shifted fluorescence. Another direct relaxation channel, induced by the C2-H2 bond twisting motion, is found to go through a conical intersection between the Sstack1((1)ππ*) and the ground state. The barrier found here enables fluorescence from the Sstack1((1)ππ*) state and may explain the bright state emission observed in the fluorescence upconversion measurements. The inter-molecular SCT((1)ππ*) state may be involved in the slow relaxation process of the photoexcited adenine oligomers through efficient internal conversion to the intra-base Sstack1((1)ππ*) state.

  12. A Model for Nonlinear Photoexcitation of Molecular Hydrogen in Space

    NASA Astrophysics Data System (ADS)

    Glownia, J. H.; Sorokin, P. P.

    2000-05-01

    A model for nonlinear photoexcitation of H2 molecules in tenuous clouds near bright stars (e.g. PDRs or PNe) is presented. In the model, H atoms and H2 molecules coexist in a cold neutral cloud surrounding an H II region represented by a conventional Strömgren sphere. An intense band of Ly-α radiation is produced by H++ e- recombination and frequency redistribution occuring in the H II region. Due to elastic scattering by H atoms, the Ly-α radiation slowly diffuses outward through the neutral cloud, its photon density becoming enormously enhanced in the process. This provides the basic pumping field required for the nonlinear effects to be described. Via resonant inverse Raman scattering (IRS), the intense Ly-α radiation field induces strong nonlinear absorption of VUV continuum starlight by orthohydrogen molecules in X0, J''=1 around three ''primary'' frequencies (B9-0P1, B6-0P1, and B3-0R1), the primary IRS terminal levels (X5, J''=1), (X4, J''=1), and (X3, J''=1) simultaneously becoming strongly populated. (Parahydrogen absorbs via IRS on B3-0R0.) Via either Ly-α -pumped, spontaneous resonant Raman scattering, or secondary IRS processes, molecules in the primary IRS terminal levels are selectively redistributed into higher-lying X-state levels such as (X10, J''=5), (X13, J''=5), and (X14, J''=1). A thin shell (thickness ~ 10,000 km) of H2 molecules populating select vibrationally excited X-state levels thus surrounds the Strömgren sphere. >From a handful of the populated high-lying X-state levels, there occur strong resonances with Ly-α . Intense Ly-α radiation can thus induce broadband stimulated Raman scattering (SRS) to occur on these transitions, generating broadband IR Stokes-wave light on strong transitions to EF-state levels. An SRS process would occur as part of a 2n-wave parametric oscillation (SRS-PO) process, with light at additional frequencies being generated on strong transitions ultimately returning molecules to the X-state level from

  13. Investigating photoexcitation-induced mitochondrial damage by chemotherapeutic corroles using multimode optical imaging

    NASA Astrophysics Data System (ADS)

    Hwang, Jae Youn; Lubow, David J.; Sims, Jessica D.; Gray, Harry B.; Mahammed, Atif; Gross, Zeev; Medina-Kauwe, Lali K.; Farkas, Daniel L.

    2012-01-01

    We recently reported that a targeted, brightly fluorescent gallium corrole (HerGa) is highly effective for breast tumor detection and treatment. Unlike structurally similar porphryins, HerGa exhibits tumor-targeted toxicity without the need for photoexcitation. We have now examined whether photoexcitation further modulates HerGa toxicity, using multimode optical imaging of live cells, including two-photon excited fluorescence, differential interference contrast (DIC), spectral, and lifetime imaging. Using two-photon excited fluorescence imaging, we observed that light at specific wavelengths augments the HerGa-mediated mitochondrial membrane potential disruption of breast cancer cells in situ. In addition, DIC, spectral, and fluorescence lifetime imaging enabled us to both validate cell damage by HerGa photoexcitation and investigate HerGa internalization, thus allowing optimization of light dose and timing. Our demonstration of HerGa phototoxicity opens the way for development of new methods of cancer intervention using tumor-targeted corroles.

  14. Photoexcited terahertz conductivity dynamics of graphene tuned by oxygen-adsorption

    NASA Astrophysics Data System (ADS)

    Zhang, Zeyu; Lin, Tie; Xing, Xiao; Lin, Xian; Meng, Xiangjian; Cheng, Zhenxiang; Jin, Zuanming; Ma, Guohong

    2017-03-01

    By using optical pump-terahertz (THz) probe spectroscopy, the photoexcited terahertz conductivity dynamics of chemical vapor deposition grown graphene is investigated in different atmospheric environments. It is shown that the Fermi energy of doped graphene is engineered by oxygen adsorption and desorption, which is probed by transient THz conductivity measurement. We show that the ultrafast energy relaxation processes depend on Fermi energy (changed by environmental gas) and the density of excited carriers (changed by photo-excitation fluence). The rise process of the negative conductivity dynamics becomes less efficient upon decreasing the Fermi energy and/or increasing the pump fluence. All findings show that the Fermi energy of graphene engineered by environmental gas allows us to tune the ultrafast energy relaxation pathways in photoexcited graphene.

  15. Influence of photoexcitation on hopping conduction in neutron-transmutation-doped GaAs

    SciTech Connect

    Satoh, M.; Kawahara, H.; Kuriyama, K.; Kawakubo, T.; Yoneda, K.; Kimura, I.

    1988-02-15

    The nature of the tunneling-assisted hopping conduction in neutron-transmutation-doped GaAs has been studied under photoexcitation with a photon energy of 1.32 eV. It is found that the dopants activated by annealing around 400 /sup 0/C provide the electrons to the defect levels originating the hopping conduction even when under photoexcitation. The hopping conduction under photoexcitation is affected by quenching in photoconductance below 120 K concerned with the main electron trap (EL2) and/or the As antisite defect (As/sub Ga/) induced by the neutron irradiation. The photoconductance of the samples with a lower radiation damage, As/sub Ga/less than or equal to1 x 10/sup 18/ cm/sup -3/, consists of the coexistence of the hopping and band conductions.

  16. Observation of perturbed 3snp double photoexcited Ryberg series of beryllium atoms

    SciTech Connect

    Yoshida, Fumiko; Matsuoka, Leo; Osaki, Hiroyuki; Kikkawa, Satoshi; Fukushima, Yu; Hasegawa, Shuichi; Nagata, Tetsuo; Azuma, Yoshiro; Obara, Satoshi

    2006-04-15

    We observed the 3snp autoionizing Rydberg series of the Be atom in order to investigate the double-photoexcitation processes in two-s-electron systems. We employed synchrotron radiation to photoexcite the Be atoms and measured the generated Be{sup +} photoions by the time-of-flight method. The 3snp (n=3-9) photoexcitation resonance peaks with interloper state of 3p4s that converges to Be{sup +}(3p) threshold were observed. We derived the resonance parameters of 3snp series from a fitting procedure and obtained the Fano parameter q, energy position E{sub 0}, and resonance width {gamma}. These parameters are in good agreement with theoretical values. In the vicinity of the 3s5p state these experimental results clearly revealed the influence of the interloper 3p4s state, and the comparison with the numerical calculations indicates that more detailed calculations might be required to fully explain this phenomenon.

  17. Measurement of excited layer thickness in highly photo-excited GaAs

    NASA Astrophysics Data System (ADS)

    Liang, Lingliang; Tian, Jinshou; Wang, Tao; Wu, Shengli; Li, Fuli; Gao, Guilong

    2016-10-01

    Highly photo-excited layer thickness in GaAs is measured using a pump probe arrangement. A normally incident pump illumination spatially modulated by a mask will induce a corresponding refractive index change distribution in the depth direction due to edge scattering and attenuation absorption effect, which can deflect the probe beam passing through this excited region. Maximum deflection of the probe beam will be limited by the thickness of excited layer, and thus can also be employed to measure the thickness of the photo-excited layer of the material. Theoretical calculation confirms the experimental results. This method can find its application in measurements of photo-excited layer thickness of many kinds of materials and be significant to study the characteristics of materials in laser machining, grating and waveguide fabricating.

  18. The S(2p) Core Level Binding Energies for Alternative Adsorption Sites and the Example of Thiol Self Assembly

    NASA Astrophysics Data System (ADS)

    Jia, Juanjuan; Esaulov, Vladimir; Kara, Abdelkader

    2015-03-01

    Results of an investigation of the characteristics of thiol SAMs obtained by vacuum evaporative adsorption, useful for reactive substrates, are presented along with core level binding energy (BE) calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) are obtained by evaporation on Au. They display an unconventional BE structure at about 161 eV, which is close to a known BE of an S atom on Au. S(2p) core level BE calculations for molecules chemisorbed on hollow, bridge and atop sites are reported and suggest that the 161 eV peak is indeed due to an alternative adsorption site, which can be associated to an atop configuration. This must therefore not be confused with atomic sulfur and dissociation processes with S-C bond scission. Work partially supported by the U.S. Department of Energy Basic Energy Science under Contract No DE-FG02-11ER16243.

  19. Effects of non-local exchange on core level shifts for gas-phase and adsorbed molecules

    NASA Astrophysics Data System (ADS)

    Van den Bossche, M.; Martin, N. M.; Gustafson, J.; Hakanoglu, C.; Weaver, J. F.; Lundgren, E.; Grönbeck, H.

    2014-07-01

    Density functional theory calculations are often used to interpret experimental shifts in core level binding energies. Calculations based on gradient-corrected (GC) exchange-correlation functionals are known to reproduce measured core level shifts (CLS) of isolated molecules and metal surfaces with reasonable accuracy. In the present study, we discuss a series of examples where the shifts calculated within a GC-functional significantly deviate from the experimental values, namely the CLS of C 1s in ethyl trifluoroacetate, Pd 3d in PdO and the O 1s shift for CO adsorbed on PdO(101). The deviations are traced to effects of the electronic self-interaction error with GC-functionals and substantially better agreements between calculated and measured CLS are obtained when a fraction of exact exchange is used in the exchange-correlation functional.

  20. Photoemission studies of core level shifts in HgCdTe, CdMnTe, and HgZnTe

    NASA Technical Reports Server (NTRS)

    Shih, C. K.; Spicer, W. E.; Furdyna, J. K.; Sher, A.

    1987-01-01

    The results of photoemission studies of core level shifts in the Hg(1-x)Cd(x)Te, Cd(1-x)Mn(x)Te, and Hg(1-x)Zn(x)Te alloys are discussed. In Hg(0.7)Cd(0.3)Te, the Hg 5d level is found to shift to lower binding energy by 0.1 eV, and the Cd 4d level to shift to higher binding energy by 0.25 eV upon alloying (relative to their binaries). The Born-Haber cycle is used to determine core level binding energies relative to the valence-band maximum in the context of tight-binding theory, and calculated core level shifts upon alloying in HgCdTe are shown to be too small to account for the observed values. A natural valence-band offset between HgTe and CdTe of 0.35 eV is found.

  1. Predicting core level binding energies shifts: Suitability of the projector augmented wave approach as implemented in VASP.

    PubMed

    Pueyo Bellafont, Noèlia; Viñes, Francesc; Hieringer, Wolfgang; Illas, Francesc

    2017-03-30

    Here, we assess the accuracy of various approaches implemented in Vienna ab initio simulation package code to estimate core-level binding energy shifts (ΔBEs) using a projector augmented wave method to treat core electrons. The performance of the Perdew-Burke-Ernzerhof (PBE) and the Tao-Perdew-Staroverov-Scuseria (TPSS) exchange-correlation density functionals is examined on a dataset of 68 molecules containing B→F atoms in diverse chemical environments, accounting for 185 different 1s core level binding energy shifts, for which both experimental gas-phase X-ray photoemission (XPS) data and accurate all electron ΔBEs are available. Four procedures to calculate core-level shifts are investigated. Janak-Slater transition state approach yields mean absolute errors of 0.37 (0.21) eV at PBE (TPSS) level, similar to highly accurate all electron ΔSCF approaches using same functionals, and close to XPS experimental accuracy of 0.1 eV. The study supports the use of these procedures to assign ΔBEs of molecular moieties on material surfaces of interest in surface science, nanotechnology, and heterogeneous catalysis. © 2017 Wiley Periodicals, Inc.

  2. Theoretical and experimental study of kinetics of photoexcited carriers in wide band gap semiconductors

    NASA Astrophysics Data System (ADS)

    Shishehchi, Sara; Rudin, Sergey; Garrett, Gregory; Wraback, Michael; Bellotti, Enrico

    2013-03-01

    We present a theoretical and experimental study of the subpicosecond kinetics of photo-excited carriers in the wide band gap semiconductors GaN and ZnO. In the theoretical model, interaction with a photo-excitation laser pulse is treated coherently and a generalized Monte Carlo simulation is used to account for scattering and dephasing. The scattering mechanisms included are carrier interactions with polar optical phonons and acoustic phonons, and carrier-carrier Coulomb interactions. For comparison, experimental time-resolved photoluminescence studies on GaN and ZnO samples are performed over a range of temperatures and excitation powers.

  3. Resonance tunneling of charge carriers in photoexcited type-II ZnSe/BeTe heterostructures

    SciTech Connect

    Zaitsev, S. V. Maksimov, A. A.; Tartakovskii, I. I.; Yakovlev, D. R.; Waag, A.

    2008-05-15

    In is shown that, at high densities of spatially separated electrons and holes in type-II ZnSe/BeTe heterostructures, the conditions for resonance tunneling of photoexcited holes from the ZnSe layer to the BeTe layer are attainable. Nonlinear behavior of the intensity of the photoluminescence band corresponding to spatially direct optical transitions with photoexcitation intensity is observed. Numerical calculations are carried out, and the results are in good agreement with the experimental data in a wide region of variation of the optical pumping intensity.

  4. Instantaneous band gap collapse in photoexcited monoclinic VO2 due to photocarrier doping.

    PubMed

    Wegkamp, Daniel; Herzog, Marc; Xian, Lede; Gatti, Matteo; Cudazzo, Pierluigi; McGahan, Christina L; Marvel, Robert E; Haglund, Richard F; Rubio, Angel; Wolf, Martin; Stähler, Julia

    2014-11-21

    Using femtosecond time-resolved photoelectron spectroscopy we demonstrate that photoexcitation transforms monoclinic VO2 quasi-instantaneously into a metal. Thereby, we exclude an 80 fs structural bottleneck for the photoinduced electronic phase transition of VO2. First-principles many-body perturbation theory calculations reveal a high sensitivity of the VO2 band gap to variations of the dynamically screened Coulomb interaction, supporting a fully electronically driven isostructural insulator-to-metal transition. We thus conclude that the ultrafast band structure renormalization is caused by photoexcitation of carriers from localized V 3d valence states, strongly changing the screening before significant hot-carrier relaxation or ionic motion has occurred.

  5. Trap density probing on top-gate MoS₂ nanosheet field-effect transistors by photo-excited charge collection spectroscopy.

    PubMed

    Choi, Kyunghee; Raza, Syed Raza Ali; Lee, Hee Sung; Jeon, Pyo Jin; Pezeshki, Atiye; Min, Sung-Wook; Kim, Jin Sung; Yoon, Woojin; Ju, Sang-Yong; Lee, Kimoon; Im, Seongil

    2015-03-19

    Two-dimensional (2D) molybdenum disulfide (MoS₂) field-effect transistors (FETs) have been extensively studied, but most of the FETs with gate insulators have displayed negative threshold voltage values, which indicates the presence of interfacial traps both shallow and deep in energy level. Despite such interface trap issues, reports on trap densities in MoS₂ are quite limited. Here, we probed top-gate MoS₂ FETs with two- (2L), three- (3L), and four-layer (4L) MoS₂/dielectric interfaces to quantify deep-level interface trap densities by photo-excited charge collection spectroscopy (PECCS), and reported the result that deep-level trap densities over 10(12) cm(-2) may exist in the interface and bulk MoS₂ near the interface. Transfer curve hysteresis and PECCS measurements show that shallow traps and deep traps are not that different in density order from each other. We conclude that our PECCS analysis distinguishably provides valuable information on deep level interface/bulk trap densities in 2D-based FETs.

  6. Photoexcited breathers in conjugated polyenes: an excited-state molecular dynamics study.

    PubMed

    Tretiak, S; Saxena, A; Martin, R L; Bishop, A R

    2003-03-04

    pi-conjugated polymers have become an important class of materials for electronic devices. Design of these devices requires understanding such processes as photochemical reactions, spatial dynamics of photoexcitations, and energy and charge transport, which in turn involve complex coupled electron-vibrational dynamics. Here we study nonlinear photoexcitation dynamics in the polyene oligomers by using a quantum-chemical method suitable for the simulation of excited-state molecular dynamics in extended molecular systems with sizes up to hundreds of atoms. The method is based on the adiabatic propagation of the ground-state and transition single-electron density matrices along the trajectory. The simulations reveal formation of a self-localized vibronic excitation ("breather" or multiquanta bound state) with a typical period of 34 fs and allows us to identify specific slow and fast nuclear motions strongly coupled to the electronic degrees of freedom. The effect of chain imperfections and chemical defects on the dynamics is also investigated. A complementary two-dimensional analysis of corresponding transition density matrices provides an efficient way to monitor time-dependent real-space localization of the photoexcitation by identifying the underlying changes in charge densities and bond orders. Possible correlated electronic and vibrational spectroscopic signatures of photoexcited breathers are predicted, and generalizations to energy localization in complex macromolecules are discussed.

  7. Molecular dynamics study of the weakly solvent dependent relaxation dynamics following chlorine dioxide photoexcitation

    NASA Astrophysics Data System (ADS)

    Brooksby, Craig; Prezhdo, Oleg V.; Reid, Philip J.

    2003-11-01

    The solvation dynamics following photoexcitation of chlorine dioxide (OClO) in different solvents are investigated by classical molecular dynamics. Following previous work on the aqueous response to OClO photoexcitation [J. Chem. Phys. 118, 4563 (2003)], the present study considers the response of chloroform and cyclohexane; these three liquids present unique solvent environments that differ significantly in both polarity and structure. The study is designed to ascertain the origin of the solvent-invariant homogeneous linewidth associated with OClO photoexcitation and to confirm, at the molecular level, whether the relaxation dynamics are similar across dissimilar solvents due to chance or a common relaxation origin. The results obtained here are used to predict the time scale of solvent-induced optical dephasing, and excellent agreement with experiment is observed for all solvents. Analysis demonstrates that the solvation dynamics of OClO are dominated by short-ranged mechanical solute-solvent interactions regardless of the identity and electrostatic properties of the solvent. Low-frequency translational motions dominate the coupling spectrum, and virtually no contribution to energy gap relaxation is achieved through intramolecular solvent motions. The invariant homogeneous linewidth is attributed to the similarity in the primary response of all solvents to OClO photoexcitation.

  8. Chemical and reconstruction-induced surface core-level shifts: H on low-index W surfaces

    SciTech Connect

    Riffe, D.M.; Wertheim, G.K.; Citrin, P.H. )

    1990-07-09

    The H-induced shift of the surface-atom core-level binding energy in W(110) is shown to arise from two distinct effects, one chemical in nature and the other structural. The structural shift supports a recently proposed (1{ital p}{times}1) reconstruction that turns on at {similar to}0.5 monolayer coverage. These new findings are used to provide a self-consistent interpretation of previously reported shifts from H-covered W(111) and W(100) surfaces.

  9. Adsorption of lithium on the Si(111)7 × 7 surface studied with high resolution core-level spectroscopy

    NASA Astrophysics Data System (ADS)

    Grehk, T. M.; Larsson, C. U. S.; Prince, N. P.; Flodström, S. A.

    1993-03-01

    Li-adsorption on the Si(111)7 × 7 surface at room temperature has been studied for different metal coverages with core-level spectroscopy. Four Li-induced components are observed in the Si 2p level at high Li-coverages indicating the formation of four thermodynamically stable phases. It is shown that the reaction between the Li atoms and the Si(111)7 × 7 surface takes place in two steps. In the first the surface reconstructs towards a "7 × 1" reconstruction and in the second Li react with the Si-substrate, forming Li suicides, with the Si atom coordinating up to four Li neighbors.

  10. Probing core-electron orbitals by scanning transmission electron microscopy and measuring the delocalization of core-level excitations

    NASA Astrophysics Data System (ADS)

    Jeong, Jong Seok; Odlyzko, Michael L.; Xu, Peng; Jalan, Bharat; Mkhoyan, K. Andre

    2016-04-01

    By recording low-noise energy-dispersive x-ray spectroscopy maps from crystalline specimens using aberration-corrected scanning transmission electron microscopy, it is possible to probe core-level electron orbitals in real space. Both the 1 s and 2 p orbitals of Sr and Ti atoms in SrTi O3 are probed, and their projected excitation potentials are determined. This paper also demonstrates experimental measurement of the electronic excitation impact parameter and the delocalization of an excitation due to Coulombic beam-orbital interaction.

  11. Studies of photo-excited and trapped electrons in cubic Bi[sub 12]SiO[sub 20

    SciTech Connect

    Nouchi, P.

    1992-01-01

    This thesis presents experimental and theoretical studies of charge transport processes in cubic n-type Bi[sub 12]SiO[sub 20] (n-BSO). First, the room-temperature photocurrent response to short-pulse illumination is studied in two n-BSO samples called CT1 and SU1 in previous publications. These experiments suggest that drifting electrons spend much time in shallow traps. They allow the estimation of the corresponding trap-limited mobility and to measure the electron lifetime in the conduction band and the dwell time in shallow traps. In sample CT1, the transient photocurrent behavior below room temperatureis studied. In sample SU1, the trap-limited mobility is measured. The author describes the first measurement of the pure conduction band mobility in n-BSO. A novel holographic [open quotes]time-of-flight[close quotes] technique the author developed for this measurement is described in which the average time for a photoexcited charge carrier to drift in the dark over the period of a grating of charged traps created in the crystal by two interfering short laser pulses. This technique is also used to study the temperature dependence of the mobility. These results suggest the existence of shallow traps of energy depth equal to 320 [+-] 40 meV. The author also derives an analytical solution to the standard material equations which describes the build-up of the photorefractive grating in the dark after an initial low-energy, spatially-sinusoidal, short-pulse excitation. It is the first short-pulse solution to be developed in a band transport model containing both deep photoexcitable traps and shallow thermally excitable traps. The build-up of the space-charge field includes two components which approach their stationary values with complex time constants. Not only does the oscillatory part of this solution fit well the mobility data, the predicted damping of these oscillations fits well the damping seen in all experiments.

  12. Interaction of phosphine with Si(100) from core-level photoemission and real-time scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Lin, Deng-Sung; Ku, Tsai-Shuan; Chen, Ru-Ping

    2000-01-01

    In this paper, we investigate the interaction of phosphine (PH3) on the Si(100)-2×1 surface at temperatures between 635 and 900 K. The hydrogen desorption, growth mode, surface morphology, and chemical composition and ordering of the surface layer are examined by synchrotron radiation core-level photoemission and real-time high-temperature scanning tunneling microscopy. The P 2p core-level spectra indicate that decomposition of PHn is complete above ~550 K and the maximum P coverage is strongly influenced by the growth temperature, which governs the coverage of H-terminated sites. The scanning tunneling microscopy (STM) images taken at real time during PH3 exposure indicate that a surface phosphorus atom readily and randomly displaces one Si atom from the substrate. The ejected Si diffuses, nucleates, and incorporates itself into islands or step edges, leading to similar growth behavior as that found in Si chemical vapor deposition. Line defects both perpendicular and parallel to the dimer rows are observed on the nearly P-saturated surface. Perpendicular line defects act as a strain relief mechanism. Parallel line defects result from growth kinetics. STM images also indicate that incorporating a small amount of phosphorus eliminates the line defects in the Si(100)-2×n surface.

  13. Photoexcited Carrier Dynamics of In2S3 Thin Films.

    PubMed

    McCarthy, Robert F; Schaller, Richard D; Gosztola, David J; Wiederrecht, Gary P; Martinson, Alex B F

    2015-07-02

    Indium sulfide (In2S3) is a promising absorber base for substitutionally doped intermediate band photovoltaics (IBPV); however, the dynamics of charge carriers traversing the electronic density of states that determine the optical and electronic response of thin films under stimuli have yet to be explored. The kinetics of photophysical processes in In2S3 grown by oxygen-free atomic layer deposition are deduced from photoconductivity, photoluminescence (PL), and transient absorption spectroscopy. We develop a map of excited-state dynamics for polycrystalline thin films including a secondary conduction band ∼2.1 eV above the first, plus sulfur vacancy and indium interstitial defect levels resulting in long-lived (∼100 ns) transients. Band-edge recombination produces PL and stimulated emission, which both intensify and red-shift as deposition temperature and grain size increase. The effect of rapid conduction band electron relaxation (<30 ps) and deep defect levels on IBPV employing In2S3-based absorbers is finally considered.

  14. Core-level spectroscopy investigation of the Mo{sub 0.75}Re{sub 0.25}(100) surface

    SciTech Connect

    Lyman, P.F.; Zehner, D.M.

    1993-10-01

    Preferential surface segregation in the Mo{sub 0.75}(100) surface region was investigated using high-resolution core-level spectroscopy with synchrotron radiation. The magnitude and direction of the surface core-level shifts observed in this study can be qualitatively understood by comparison to W and Mo core-level shifts. Measured core-level intensities are found to be consistent with the segregation of Mo to the surface of the alloy, with an enrichment of Re in the second layer (as found in previous investigations). It is inferred that both Tc and Os will segregate to the Mo{sub 0.75}Re{sub 0.25}(100) surface.

  15. An experimental setup to study delayed electron emission upon photoexcitation of trapped polyatomic anions.

    PubMed

    Saha, K; Prabhakaran, A; Chandrasekaran, V; Rappaport, M L; Heber, O; Zajfman, D

    2017-05-01

    A Velocity Map Imaging (VMI) spectrometer has been designed and integrated with an electrostatic ion beam trap to study delayed electron emission from trapped polyatomic anions upon photodetachment. The VMI spectrometer is small in size and can record a wide range of photoelectron energies, with variable magnification. Delayed electron emission can be recorded in our experimental setup for any time duration after the photoexcitation of the polyatomic anions. Experiments were carried out with trapped O(-) and C5(-) ions to demonstrate the capability of the spectrometer. Delayed electron emissions from C5(-) as well as prompt photoelectrons from O(-) were detected by the VMI spectrometer upon photoexcitation. The design and performance of the spectrometer are presented in detail.

  16. An experimental setup to study delayed electron emission upon photoexcitation of trapped polyatomic anions

    NASA Astrophysics Data System (ADS)

    Saha, K.; Prabhakaran, A.; Chandrasekaran, V.; Rappaport, M. L.; Heber, O.; Zajfman, D.

    2017-05-01

    A Velocity Map Imaging (VMI) spectrometer has been designed and integrated with an electrostatic ion beam trap to study delayed electron emission from trapped polyatomic anions upon photodetachment. The VMI spectrometer is small in size and can record a wide range of photoelectron energies, with variable magnification. Delayed electron emission can be recorded in our experimental setup for any time duration after the photoexcitation of the polyatomic anions. Experiments were carried out with trapped O- and C5-ions to demonstrate the capability of the spectrometer. Delayed electron emissions from C5 - as well as prompt photoelectrons from O- were detected by the VMI spectrometer upon photoexcitation. The design and performance of the spectrometer are presented in detail.

  17. Dynamical Evolution of Anisotropic Response in Black Phosphorus under Ultrafast Photoexcitation.

    PubMed

    Ge, Shaofeng; Li, Chaokai; Zhang, Zhiming; Zhang, Chenglong; Zhang, Yudao; Qiu, Jun; Wang, Qinsheng; Liu, Junku; Jia, Shuang; Feng, Ji; Sun, Dong

    2015-07-08

    Black phosphorus has recently emerged as a promising material for high-performance electronic and optoelectronic device for its high mobility, tunable mid-infrared bandgap, and anisotropic electronic properties. Dynamical evolution of photoexcited carriers and the induced transient change of electronic properties are critical for materials' high-field performance but remain to be explored for black phosphorus. In this work, we perform angle-resolved transient reflection spectroscopy to study the dynamical evolution of anisotropic properties of black phosphorus under photoexcitation. We find that the anisotropy of reflectivity is enhanced in the pump-induced quasi-equilibrium state, suggesting an extraordinary enhancement of the anisotropy in dynamical conductivity in hot carrier dominated regime. These results raise attractive possibilities of creating high-field, angle-sensitive electronic, optoelectronic, and remote sensing devices exploiting the dynamical electronic anisotropy with black phosphorus.

  18. Suppression of transient enhanced diffusion following {ital in} {ital situ} photoexcitation during boron ion implantation

    SciTech Connect

    Ravi, J.; Erokhin, Y.; Rozgonyi, G.A.; White, C.W.

    1995-10-09

    The effect of {ital in} {ital situ} photoexcitation during boron ion implantation on subsequent transient enhanced B diffusion in Si has been investigated. Photoexcitation using a mercury arc lamp was performed during B{sup +} implantation at 35 keV for a dose of 5{times}10{sup 14} cm{sup {minus}2} at 177 K. A reduction in the electrical activation dip, i.e., reverse annealing effect, in the temperature range 550--700 {degree}C was observed. Also, the transient enhanced diffusion of B, measured using SIMS following 800 {degree}C, 30 min annealing, was suppressed. Both effects demonstrate that the creation of self-interstitials during the implantation process is significantly reduced. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  19. Hot carrier and hot phonon coupling during ultrafast relaxation of photoexcited electrons in graphene

    SciTech Connect

    Iglesias, J. M.; Martín, M. J.; Pascual, E.; Rengel, R.

    2016-01-25

    We study, by means of a Monte Carlo simulator, the hot phonon effect on the relaxation dynamics in photoexcited graphene and its quantitative impact as compared with considering an equilibrium phonon distribution. Our multi-particle approach indicates that neglecting the hot phonon effect significantly underestimates the relaxation times in photoexcited graphene. The hot phonon effect is more important for a higher energy of the excitation pulse and photocarrier densities between 1 and 3 × 10{sup 12 }cm{sup −2}. Acoustic intervalley phonons play a non-negligible role, and emitted phonons with wavelengths limited up by a maximum (determined by the carrier concentration) induce a slower carrier cooling rate. Intrinsic phonon heating is damped in graphene on a substrate due to the additional cooling pathways, with the hot phonon effect showing a strong inverse dependence with the carrier density.

  20. The new high field photoexcitation muon spectrometer at the ISIS pulsed neutron and muon source.

    PubMed

    Yokoyama, K; Lord, J S; Murahari, P; Wang, K; Dunstan, D J; Waller, S P; McPhail, D J; Hillier, A D; Henson, J; Harper, M R; Heathcote, P; Drew, A J

    2016-12-01

    A high power pulsed laser system has been installed on the high magnetic field muon spectrometer (HiFi) at the International Science Information Service pulsed neutron and muon source, situated at the STFC Rutherford Appleton Laboratory in the UK. The upgrade enables one to perform light-pump muon-probe experiments under a high magnetic field, which opens new applications of muon spin spectroscopy. In this report we give an overview of the principle of the HiFi laser system and describe the newly developed techniques and devices that enable precisely controlled photoexcitation of samples in the muon instrument. A demonstration experiment illustrates the potential of this unique combination of the photoexcited system and avoided level crossing technique.

  1. UV photoexcitation of a dissolved metalloid Ge9 cluster compound and its extensive ultrafast response.

    PubMed

    Klinger, M; Schenk, C; Henke, F; Clayborne, A; Schnepf, A; Unterreiner, A-N

    2015-08-07

    Femtosecond pump-probe absorption spectroscopy in tetrahydrofuran solution has been used to investigate the dynamics of a metalloid cluster compound {Ge9[Si(SiMe3)3]3}(-). Upon UV photoexcitation, the transients in the near-infrared spectral region showed signatures reminiscent of excess electrons in THF (bound or quasi-free) whereas in the visible part excited state dynamics of the cluster complex dominates.

  2. Nanosecond time-scale semiconductor photoexcitations probed by a scanning tunneling microscope

    NASA Astrophysics Data System (ADS)

    Gallagher, Mark J.; Ruskell, Todd G.; Chen, Dong; Sarid, Dror; Jenkinson, Howard

    1994-01-01

    The high-frequency response of scanning tunneling microscopy of a semiconductor is demonstrated by using the beat frequencies of the longitudinal modes of a HeNe laser at the tunneling junction. We present a comparison of the slow and fast optical response of photoexcited charge carriers in the layered structure semiconductors n-type MoS2 and p-type WSe2 using this method.

  3. Ultrafast Scanning Tunneling Microscopy Using a Photoexcited Low-Temperature-Grown GaAs Tip

    SciTech Connect

    Donati, G.P.; Rodriguez, G.; Taylor, A.J.

    1999-05-21

    The authors report ultrafast scanning tunneling microscopy using a low-temperature-grown GaAs tip photoexcited by 100-fs, 800-nm pulses. They use this tip to detect picosecond transients on a coplanar stripline and demonstrate a temporal resolution of 1.7 ps. A dependence of the transient signal upon spatial position of the tip is revealed, indicating that the signal arises from areas on the sample smaller than {approximately}20nm.

  4. Plasma mechanism of terahertz photomixing in high-electron mobility transistor under interband photoexcitation

    NASA Astrophysics Data System (ADS)

    Ryzhii, V.; Khmyrova, I.; Satou, A.; Vaccaro, P. O.; Aida, T.; Shur, M.

    2002-11-01

    We show that modulated near-infrared radiation can generate terahertz plasma oscillations in the channel of a high-electron mobility transistor. This effect is associated with a temporarily periodic injection of the electrons photoexcited by modulated near-infrared radiation into the transistor channel. The excitation of the plasma oscillations has the resonant character. It results in the pertinent excitation of the electric current in the external circuit that can be used for generation of terahertz electromagnetic radiation.

  5. Evidence of the nature of core-level photoemission satellites using angle-resolved photoemission extended fine structure

    SciTech Connect

    Moler, E.J.; Kellar, S.A.; Huff, W.R.A.

    1997-04-01

    The authors present a unique method of experimentally determining the angular momentum and intrinsic/extrinsic origin of core-level photoemission satellites by examining the satellite diffraction pattern in the Angle Resolved Photoemission Extended Fine Structure (ARPEFS) mode. They show for the first time that satellite peaks not associated with chemically differentiated atomic species display an ARPEFS intensity oscillation. They present ARPEFS data for the carbon 1s from ({radical}3x{radical}3)R30 CO/Cu(111) and p2mg(2xl)CO/Ni(110), nitrogen 1s from c(2x2) N{sub 2}/Ni(100), cobalt 1s from p(1x1)Co/Cu(100), and nickel 3p from clean nickel (111). The satellite peaks and tails of the Doniach-Sunjic line shapes in all cases exhibit ARPEFS curves which indicate an angular momentum identical to the main peak and are of an intrinsic nature.

  6. Electrochemical immobilization of Fluorescent labelled probe molecules on a FTO surface for affinity detection based on photo-excited current

    NASA Astrophysics Data System (ADS)

    Haruyama, Tetsuya; Wakabayashi, Ryo; Cho, Takeshi; Matsuyama, Sho-taro

    2011-10-01

    Photo-excited current can be generated at a molecular interface between a photo-excited molecules and a semi-conductive material in appropriate condition. The system has been recognized for promoting photo-energy devices such as an organic dye sensitized solar-cell. The photo-current generated reactions are totally dependent on the interfacial energy reactions, which are in a highly fluctuated interfacial environment. The authors investigated the photo-excited current reaction to develop a smart affinity detection method. However, in order to perform both an affinity reaction and a photo-excited current reaction at a molecular interface, ordered fabrications of the functional (affinity, photo-excitation, etc.) molecules layer on a semi-conductive surface is required. In the present research, we would like to present the fabrication and functional performance of photo-excited current-based affinity assay device and its application for detection of endocrine disrupting chemicals. On the FTO surface, fluorescent pigment labelled affinity peptide was immobilized through the EC tag (electrochemical-tag) method. The modified FTO produced a current when it was irradiated with diode laser light. However, the photo current decreased drastically when estrogen (ES) coexisted in the reaction solution. In this case, immobilized affinity probe molecules formed a complex with ES and estrogen receptor (ER). The result strongly suggests that the photo-excited current transduction between probe molecule-labelled cyanine pigment and the FTO surface was partly inhibited by a complex that formed at the affinity oligo-peptide region in a probe molecule on the FTO electrode. The bound bulky complex may act as an impediment to perform smooth transduction of photo-excited current in the molecular interface. The present system is new type of photo-reaction-based analysis. This system can be used to perform simple high-sensitive homogeneous assays.

  7. Photo-excited hot carrier dynamics in hydrogenated amorphous silicon imaged by 4D electron microscopy.

    PubMed

    Liao, Bolin; Najafi, Ebrahim; Li, Heng; Minnich, Austin J; Zewail, Ahmed H

    2017-09-01

    Charge carrier dynamics in amorphous semiconductors has been a topic of intense research that has been propelled by modern applications in thin-film solar cells, transistors and optical sensors. Charge transport in these materials differs fundamentally from that in crystalline semiconductors owing to the lack of long-range order and high defect density. Despite the existence of well-established experimental techniques such as photoconductivity time-of-flight and ultrafast optical measurements, many aspects of the dynamics of photo-excited charge carriers in amorphous semiconductors remain poorly understood. Here, we demonstrate direct imaging of carrier dynamics in space and time after photo-excitation in hydrogenated amorphous silicon (a-Si:H) by scanning ultrafast electron microscopy (SUEM). We observe an unexpected regime of fast diffusion immediately after photoexcitation, together with spontaneous electron-hole separation and charge trapping induced by the atomic disorder. Our findings demonstrate the rich dynamics of hot carrier transport in amorphous semiconductors that can be revealed by direct imaging based on SUEM.

  8. Photoexcitation of adsorbates on metal surfaces: One-step or three-step

    NASA Astrophysics Data System (ADS)

    Petek, Hrvoje

    2012-09-01

    In this essay we discuss the light-matter interactions at molecule-covered metal surfaces that initiate surface photochemistry. The hot-electron mechanism for surface photochemistry, whereby the absorption of light by a metal surface creates an electron-hole pair, and the hot electron scatters through an unoccupied resonance of adsorbate to initiate nuclear dynamics leading to photochemistry, has become widely accepted. Yet, ultrafast spectroscopic measurements of molecule-surface electronic structure and photoexcitation dynamics provide scant support for the hot electron mechanism. Instead, in most cases the adsorbate resonances are excited through photoinduced substrate-to-adsorbate charge transfer. Based on recent studies of the role of coherence in adsorbate photoexcitation, as measured by the optical phase and momentum resolved two-photon photoemission measurements, we examine critically the hot electron mechanism, and propose an alternative description based on direct charge transfer of electrons from the substrate to adsorbate. The advantage of this more quantum mechanically rigorous description is that it informs how material properties of the substrate and adsorbate, as well as their interaction, influence the frequency dependent probability of photoexcitation and ultimately how light can be used to probe and control surface femtochemistry.

  9. Photo-excited hot carrier dynamics in hydrogenated amorphous silicon imaged by 4D electron microscopy

    NASA Astrophysics Data System (ADS)

    Liao, Bolin; Najafi, Ebrahim; Li, Heng; Minnich, Austin J.; Zewail, Ahmed H.

    2017-09-01

    Charge carrier dynamics in amorphous semiconductors has been a topic of intense research that has been propelled by modern applications in thin-film solar cells, transistors and optical sensors. Charge transport in these materials differs fundamentally from that in crystalline semiconductors owing to the lack of long-range order and high defect density. Despite the existence of well-established experimental techniques such as photoconductivity time-of-flight and ultrafast optical measurements, many aspects of the dynamics of photo-excited charge carriers in amorphous semiconductors remain poorly understood. Here, we demonstrate direct imaging of carrier dynamics in space and time after photo-excitation in hydrogenated amorphous silicon (a-Si:H) by scanning ultrafast electron microscopy (SUEM). We observe an unexpected regime of fast diffusion immediately after photoexcitation, together with spontaneous electron-hole separation and charge trapping induced by the atomic disorder. Our findings demonstrate the rich dynamics of hot carrier transport in amorphous semiconductors that can be revealed by direct imaging based on SUEM.

  10. Photoexcitation of K-shell and L-shell Hollow Beryllium

    SciTech Connect

    Hasegawa, Shuichi; Yoshida, Fumiko; Matsuoka, Leo; Koike, Fumihiro; Fritzsche, Stephan; Obara, Satoshi; Azuma, Yoshiro; Nagata, Tetsuo

    2006-07-14

    We have observed K-shell and L-shell hollow beryllium atoms (2s{sup 2}2p3s and 1s3s{sup 2}3p) created by photoexcitation using synchrotron radiation. Resonance shapes were fitted to the Fano profile and the parameters were deduced. A Dirac-Fock calculation was performed to identify the configuration of the peaks and to predict other hollow atomic peaks. The results of the calculation were in good agreement with the experimental data. The comparison of the transition strength has revealed that the three-electron photoexcitation to the 1s3s{sup 2}3p configuration is stronger than the two-electron photoexcitation to the 2s{sup 2}2p3s configuration. This is attributed to the large overlap between the 2s orbital of the ground state (1s{sup 2}2s{sup 2}) with the 3s orbital of the L-shell hollow state (1s3s{sup 2}3p)

  11. Photoexcitation of adsorbates on metal surfaces: One-step or three-step

    SciTech Connect

    Petek, Hrvoje

    2012-09-07

    In this essay we discuss the light-matter interactions at molecule-covered metal surfaces that initiate surface photochemistry. The hot-electron mechanism for surface photochemistry, whereby the absorption of light by a metal surface creates an electron-hole pair, and the hot electron scatters through an unoccupied resonance of adsorbate to initiate nuclear dynamics leading to photochemistry, has become widely accepted. Yet, ultrafast spectroscopic measurements of molecule-surface electronic structure and photoexcitation dynamics provide scant support for the hot electron mechanism. Instead, in most cases the adsorbate resonances are excited through photoinduced substrate-to-adsorbate charge transfer. Based on recent studies of the role of coherence in adsorbate photoexcitation, as measured by the optical phase and momentum resolved two-photon photoemission measurements, we examine critically the hot electron mechanism, and propose an alternative description based on direct charge transfer of electrons from the substrate to adsorbate. The advantage of this more quantum mechanically rigorous description is that it informs how material properties of the substrate and adsorbate, as well as their interaction, influence the frequency dependent probability of photoexcitation and ultimately how light can be used to probe and control surface femtochemistry.

  12. Low-lying Photoexcited States of a One-Dimensional Ionic Extended Hubbard Model

    NASA Astrophysics Data System (ADS)

    Yokoi, Kota; Maeshima, Nobuya; Hino, Ken-ichi

    2017-10-01

    We investigate the properties of low-lying photoexcited states of a one-dimensional (1D) ionic extended Hubbard model at half-filling. Numerical analysis by using the full and Lanczos diagonalization methods shows that, in the ionic phase, there exist low-lying photoexcited states below the charge transfer gap. As a result of comparison with numerical data for the 1D antiferromagnetic (AF) Heisenberg model, it was found that, for a small alternating potential Δ, these low-lying photoexcited states are spin excitations, which is consistent with a previous analytical study [Katsura et al., Phys. Rev. Lett. 103, 177402 (2009)]. As Δ increases, the spectral intensity of the 1D ionic extended Hubbard model rapidly deviates from that of the 1D AF Heisenberg model and it is clarified that this deviation is due to the neutral-ionic domain wall, an elementary excitation near the neutral-ionic transition point.

  13. Correlating quasiparticle excitations with quantum femtosecond magnetism in photoexcited nonequilibrium states of insulating antiferromagnetic manganites

    NASA Astrophysics Data System (ADS)

    Lingos, P. C.; Patz, A.; Li, T.; Barmparis, G. D.; Keliri, A.; Kapetanakis, M. D.; Li, L.; Yan, J.; Wang, J.; Perakis, I. E.

    2017-06-01

    We describe a mechanism for insulator-to-metal transition triggered by spin canting following femtosecond laser excitation of insulating antiferromagnetic (AFM) states of colossal magnetoresistive (CMR) manganites. We show that photoexcitation of composite fermion quasiparticles dressed by spin fluctuations results in the population of a broad metallic conduction band due to canting of the AFM background spins via strong electron-spin local correlation. By inducing spin canting, photoexcitation can increase the quasiparticle energy dispersion and quench the charge excitation energy gap. This increases the critical Jahn-Teller (JT) lattice displacement required to maintain an insulating state. We present femtosecond-resolved pump-probe measurements showing biexponential relaxation of the differential reflectivity below the AFM transition temperature. We observe a nonlinear dependence of the ratio of the femtosecond and picosecond relaxation component amplitudes at the same pump fluence threshold where we observe femtosecond magnetization photoexcitation. We attribute this correlation between nonlinear femtosecond spin and charge dynamics to spin/charge/lattice coupling and population inversion between the polaronic majority carriers and metallic quasielectron minority carriers as the lattice displacement becomes smaller than the critical value required to maintain an insulating state following laser-induced spin canting.

  14. Large-amplitude chirped coherent phonons in tellurium mediated by ultrafast photoexcited carrier diffusion

    NASA Astrophysics Data System (ADS)

    Kamaraju, N.; Kumar, Sunil; Anija, M.; Sood, A. K.

    2010-11-01

    We report femtosecond time-resolved reflectivity measurements of coherent phonons in tellurium performed over a wide range of temperatures (3-296 K) and pump-laser intensities. A totally symmetric A1 coherent phonon at 3.6 THz responsible for the oscillations in the reflectivity data is observed to be strongly positively chirped (i.e., phonon time period decreases at longer pump-probe delay times) with increasing photoexcited carrier density, more so at lower temperatures. We show that the temperature dependence of the coherent phonon frequency is anomalous (i.e, increasing with increasing temperature) at high photoexcited carrier density due to electron-phonon interaction. At the highest photoexcited carrier density of ˜1.4×1021cm-3 and the sample temperature of 3 K, the lattice displacement of the coherent phonon mode is estimated to be as high as ˜0.24Å . Numerical simulations based on coupled effects of optical absorption and carrier diffusion reveal that the diffusion of carriers dominates the nonoscillatory electronic part of the time-resolved reflectivity. Finally, using the pump-probe experiments at low carrier density of 6×1018cm-3 , we separate the phonon anharmonicity to obtain the electron-phonon coupling contribution to the phonon frequency and linewidth.

  15. Probing Microenvironment in Ionic Liquids by Time-Resolved EPR of Photoexcited Triplets.

    PubMed

    Ivanov, M Yu; Veber, S L; Prikhod'ko, S A; Adonin, N Yu; Bagryanskaya, E G; Fedin, M V

    2015-10-22

    Unusual physicochemical properties of ionic liquids (ILs) open vistas for a variety of new applications. Herewith, we investigate the influence of microviscosity and nanostructuring of ILs on spin dynamics of the dissolved photoexcited molecules. We use two most common ILs [Bmim]PF6 and [Bmim]BF4 (with its close analogue [C10mim]BF4) as solvents and photoexcited Zn tetraphenylporphyrin (ZnTPP) as a probe. Time-resolved electron paramagnetic resonance (TR EPR) is employed to investigate spectra and kinetics of spin-polarized triplet ZnTPP in the temperature range 100-270 K. TR EPR data clearly indicate the presence of two microenvironments of ZnTPP in frozen ILs at 100-200 K, being manifested in different spectral shapes and different spin relaxation rates. For one of these microenvironments TR EPR data is quite similar to those obtained in common frozen organic solvents (toluene, glycerol, N-methyl-2-pyrrolidone). However, the second one favors the remarkably slow relaxation of spin polarization, being much longer than in the case of common solvents. Additional experiments using continuous wave EPR and stable nitroxide as a probe confirmed the formation of heterogeneities upon freezing of ILs and complemented TR EPR results. Thus, TR EPR of photoexcited triplets can be effectively used for probing heterogeneities and nanostructuring in frozen ILs. In addition, the increase of polarization lifetime in frozen ILs is an interesting finding that might allow investigation of short-lived intermediates inaccessible otherwise.

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

    NASA Astrophysics Data System (ADS)

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

    2013-03-01

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

  17. Bandgap modulation in photoexcited topological insulator Bi2Te3 via atomic displacements.

    PubMed

    Hada, Masaki; Norimatsu, Katsura; Tanaka, Sei Ichi; Keskin, Sercan; Tsuruta, Tetsuya; Igarashi, Kyushiro; Ishikawa, Tadahiko; Kayanuma, Yosuke; Miller, R J Dwayne; Onda, Ken; Sasagawa, Takao; Koshihara, Shin-Ya; Nakamura, Kazutaka G

    2016-07-14

    The atomic and electronic dynamics in the topological insulator (TI) Bi2Te3 under strong photoexcitation were characterized with time-resolved electron diffraction and time-resolved mid-infrared spectroscopy. Three-dimensional TIs characterized as bulk insulators with an electronic conduction surface band have shown a variety of exotic responses in terms of electronic transport when observed under conditions of applied pressure, magnetic field, or circularly polarized light. However, the atomic motions and their correlation between electronic systems in TIs under strong photoexcitation have not been explored. The artificial and transient modification of the electronic structures in TIs via photoinduced atomic motions represents a novel mechanism for providing a comparable level of bandgap control. The results of time-domain crystallography indicate that photoexcitation induces two-step atomic motions: first bismuth and then tellurium center-symmetric displacements. These atomic motions in Bi2Te3 trigger 10% bulk bandgap narrowing, which is consistent with the time-resolved mid-infrared spectroscopy results.

  18. On sulfur core level binding energies in thiol self-assembly and alternative adsorption sites: An experimental and theoretical study

    SciTech Connect

    Jia, Juanjuan; Kara, Abdelkader E-mail: vladimir.esaulov@u-psud.fr; Pasquali, Luca; Bendounan, Azzedine; Sirotti, Fausto; Esaulov, Vladimir A. E-mail: vladimir.esaulov@u-psud.fr

    2015-09-14

    Characteristic core level binding energies (CLBEs) are regularly used to infer the modes of molecular adsorption: orientation, organization, and dissociation processes. Here, we focus on a largely debated situation regarding CLBEs in the case of chalcogen atom bearing molecules. For a thiol, this concerns the case when the CLBE of a thiolate sulfur at an adsorption site can be interpreted alternatively as due to atomic adsorption of a S atom, resulting from dissociation. Results of an investigation of the characteristics of thiol self-assembled monolayers (SAMs) obtained by vacuum evaporative adsorption are presented along with core level binding energy calculations. Thiol ended SAMs of 1,4-benzenedimethanethiol (BDMT) obtained by evaporation on Au display an unconventional CLBE structure at about 161.25 eV, which is close to a known CLBE of a S atom on Au. Adsorption and CLBE calculations for sulfur atoms and BDMT molecules are reported and allow delineating trends as a function of chemisorption on hollow, bridge, and atop sites and including the presence of adatoms. These calculations suggest that the 161.25 eV peak is due to an alternative adsorption site, which could be associated to an atop configuration. Therefore, this may be an alternative interpretation, different from the one involving the adsorption of atomic sulfur resulting from the dissociation process of the S–C bond. Calculated differences in S(2p) CLBEs for free BDMT molecules, SH group sulfur on top of the SAM, and disulfide are also reported to clarify possible errors in assignments.

  19. Core-level positive-ion and negative-ion fragmentation of gaseous and condensed HCCl3 using synchrotron radiation

    NASA Astrophysics Data System (ADS)

    Lu, K. T.; Chen, J. M.; Lee, J. M.; Haw, S. C.; Liang, Y. C.; Deng, M. J.

    2011-07-01

    We investigated the dissociation dynamics of positive-ion and negative-ion fragments of gaseous and condensed HCCl3 following photoexcitation of Cl 2p electrons to various resonances. Based on ab initio calculations at levels HF/cc-pVTZ and QCISD/6-311G*, the first doublet structures in Cl L-edge x-ray absorption spectrum of HCCl3 are assigned to transitions from the Cl (2P3/2,1/2) initial states to the 10a1* orbitals. The Cl 2p → 10a1* excitation of HCCl3 induces a significant enhancement of the Cl+ desorption yield in the condensed phase and a small increase in the HCCl+ yield in the gaseous phase. Based on the resonant photoemission of condensed HCCl3, excitations of Cl 2p electrons to valence orbitals decay predominantly via spectator Auger transitions. The kinetic energy distributions of Cl+ ion via the Cl 2p → 10a1* excitation are shifted to higher energy ˜0.2 eV and ˜0.1 eV relative to those via the Cl 2p → 10e* excitation and Cl 2p → shape resonance excitation, respectively. The enhancement of the yields of ionic fragments at specific core-excited resonance states is assisted by a strongly repulsive surface that is directly related to the spectator electrons localized in the antibonding orbitals. The Cl- anion is significantly reinforced in the vicinity of Cl 2p ionization threshold of gaseous HCCl3, mediated by photoelectron recapture through post-collision interaction.

  20. Core-Level Photoemission Investigations of the CADMIUM-TELLURIDE(100) and INDIUM-ANTIMONY(100) Surface and Interfacial Structures.

    NASA Astrophysics Data System (ADS)

    John, Peter James

    1988-12-01

    Photoemission techniques, utilizing a synchrotron light source, were used to analyze the clean (100) surfaces of the zinc-blende semiconductor materials CdTe and InSb. Several interfacial systems involving the surfaces of these materials were also studied, including the CdTe(100)-Ag interface, the CdTe(100)-Sb system, and the InSb(100)-Sn interface. High -energy electron diffraction was also employed to acquire information about of surface structure. A one-domain (2x1) structure was observed for the CdTe(100) surface. Analysis of photoemission spectra of the Cd 4d core level for this surface structure revealed two components resulting from Cd surface atoms. The total intensity of these components accounts for a full monolayer of Cd atoms on the surface. A structural model is discussed commensurate with these results. Photoemission spectra of the Cd and Te 4d core levels indicate that Ag or Sb deposited on the CdTe(100)-(2x1) surface at room temperature do not bound strongly to the surface Cd atoms. The room temperature growth characteristics for these two elements on the CdTe(100)-(2x1) are discussed. The growth at elevated substrate temperatures was also studied for Sb deposition. The InSb(100) surface differed from the CdTe(100) surface. Using molecular beam epitaxy, several structures could be generated for the InSb(100) surface, including a c(8x2), a c(4x4), an asymmetric (1x3), a symmetric (1x3), and a (1x1). Analysis of photoemission intensities and line shapes indicates that the c(4x4) surface is terminated with 1{3 over 4} monolayers of Sb atoms. The c(8x2) surface is found to be terminated with {3over 4} monolayer of In atoms. Structural models for both of these surfaces are proposed based upon the photoemission results and upon models of the similar GaAs(100) structures. The room temperature growth characteristics of grey Sn on the InSb(100)-c(4x4) and InSb(100)-c(8x2) surfaces were studied with photoemission. The discontinuity in the valence band maximum

  1. Skin-depth lattice strain, core-level trap depression and valence charge polarization of Al surfaces

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Bo, Maolin; Liu, Yonghui; Guo, Yongling; Wang, Haibin; Yue, Jian; Huang, Yongli

    2016-01-01

    Clarifying the origin for surface core-level shift (SCLS) and gaining quantitative information regarding the coordination-resolved local strain, binding energy (BE) shift and cohesive energy change have been a challenge. Here, we show that a combination of the bond order-length-strength (BOLS) premise, X-ray photoelectron spectroscopy (XPS) and the ab initio density functional theory (DFT) calculations of aluminum (Al) 2p3/2 energy shift of Al surfaces has enabled us to derive such information, namely, (i) the 2p3/2 energy of an isolated Al atom (72.146 ± 0.003eV) and its bulk shift (0.499 eV); (ii) the skin lattice contracts by up to 12.5% and the BE density increases by 70%; and (iii) the cohesive energy drops up to 38%. It is affirmed that the shorter and stronger bonds between under-coordinated atoms provide a perturbation to the Hamiltonian and hence lead to the local strain, quantum entrapment and valence charge polarization. Findings should help in understanding the phenomena of surface pre-melting and skin-high elasticity, in general.

  2. Ce Core-Level Spectroscopy, and Magnetic and Electrical Transport Properties of Lightly Ce-Doped YCoO3

    NASA Astrophysics Data System (ADS)

    Kobayashi, Yoshihiko; Koike, Tsuyoshi; Okawa, Mario; Takayanagi, Ryohei; Takei, Shohei; Minohara, Makoto; Kobayashi, Masaki; Horiba, Koji; Kumigashira, Hiroshi; Yasui, Akira; Ikenaga, Eiji; Saitoh, Tomohiko; Asai, Kichizo

    2016-11-01

    We have investigated the Ce and Co core level spectroscopy, and the magnetic and electrical transport properties of lightly Ce-doped YCoO3. We have successfully synthesized single-phase Y1-xCexCoO3 for 0.0 ≤ x ≤ 0.1 by the sol-gel method. Hard X-ray photoelectron and X-ray absorption spectroscopy experiments reveal that the introduced Ce ions are tetravalent, which is considered to be the first case of electron doping into bulk trivalent Co oxides with perovskite RECoO3 (RE: rare-earth element or Y) caused by RE site substitution. The magnitude of the effective magnetic moment peff obtained from the temperature dependence of magnetic susceptibility χ(T) at higher temperatures is close to that for high-spin Co2+ introduced by the Ce doping, implying that the electrons doped into the Co site induce Co2+ with a high-spin state. For x = 0.1, ferromagnetic ordering is observed below about 7 K. Electrical transport properties such as resistivity and thermoelectric power show that negative electron-like carriers are introduced by Ce substitution.

  3. Core-level Photoemission Study for Cuprates with a Dynamical Mean-Field Approach Considering Realistic Crystal Structure

    NASA Astrophysics Data System (ADS)

    Hariki, Atsushi; Uozumi, Takayuki

    2013-03-01

    Recently, remarkable experimental progress reveals some characteristic spectral features in the 2p3/2main line of Cu 2p core-level X-ray photoemission spectra (XPS). The structures show strong material dependence and drastic changes for electron or hole doping. Van Veenendaal et al., pointed out that the main line shape is strongly affected by the so-called nonlocal screening which is accompanied by a formation of a Zhang-Rice singlet (ZRS) in the XPS final state. On the other hand, Taguchi et al., shows these features are reproduced by introducing an phenomenological extended impurity model. We consider that this topic on 2pXPS of cuprates still remain controversial. In this study, we propose another approach based on the dynamical mean field theory(DMFT) considering the realistic crystal structure. Many-particle effects including the ZRS is appropriately embedded in the hybridization function of a single impurity Anderson model through the DMFT self-consistent cycle. Our approach reproduces experimental results and shows that the Cu 2p3/2 main line is closely related with the quasi-particle structure near the Fermi energy.

  4. Ab initio study of 2p core-level x-ray photoemission spectra in ferromagnetic transition metals

    NASA Astrophysics Data System (ADS)

    Takahashi, Manabu; Igarashi, Jun-Ichi

    2012-02-01

    We study the 2p core-level x-ray photoemission spectra in ferromagnetic transition metals, Fe, Co, and Ni using a recently developed ab initio method. The excited final states are set up by distributing electrons on the one-electron states calculated under the fully screened potential in the presence of the core hole. We evaluate the overlap between these excited states and the ground state by using one-electron wave functions, and obtain the spectral curves as a function of binding energy. The calculated spectra reproduce well the observed spectra displaying interesting dependence on the element and on the spin of the removed core electron. The origin of the spectral shapes is elucidated in terms of the one-electron states screening the core hole. The magnetic splitting of the threshold energy is also estimated by using the coherent potential approximation within the fully screened potential approximation. It decreases more rapidly than the local spin moment with moving from Fe to Ni. It is estimated to be almost zero for Ni despite the definite local moment about 0.6μB, in agreement with the experiment.

  5. Characteristic analysis of a photoexcited metamaterial perfect absorber at terahertz frequencies

    NASA Astrophysics Data System (ADS)

    Bing, Pibin; Huang, Shichao; Li, Zhongyang; Yu, Zhou; Lu, Ying; Yao, Jianquan

    2017-06-01

    The absorption characteristics of a photoexcited metamaterial absorber at terahertz frequencies were analyzed in this study. Filling photosensitive semiconductor silicon into the gap between the resonator arms leads to modulation of its electromagnetic response through a pump beam which changes conductivity of silicon. Comparisons of terahertz absorbing properties which were caused by different thicknesses and dielectric constants of polyimide, cell sizes and widths of SRRs, and lengths and conductivities of the photosensitive silicon, were studied by using Finite Difference Time Domain (FDTD) from 0.4 THz to 1.6 THz. The results of this study will facilitate the design and preparation of terahertz modulator, filters and absorbers.

  6. Intense terahertz field effects on photoexcited carrier dynamics in gated graphene

    NASA Astrophysics Data System (ADS)

    Hafez, Hassan A.; Lévesque, Pierre L.; Al-Naib, Ibraheem; Dignam, Marc M.; Chai, Xin; Choubak, Saman; Desjardins, Patrick; Martel, Richard; Ozaki, Tsuneyuki

    2015-12-01

    We study nonlinear effects of intense terahertz (THz) field on photoexcited carrier dynamics in gated monolayer graphene. By employing optical-pump/intense-THz-probe spectroscopy on lightly doped graphene, we observe a crossover from negative to positive photo-induced THz differential transmission as the THz probe field is increased. We attribute this qualitative change in the response to a crossover from a regime where the photo-induced increase in the carrier density dominates the differential response to one where a THz-field-induced increase in the scattering rate dominates.

  7. Observation of standing waves of electron-hole sound in a photoexcited semiconductor.

    PubMed

    Padmanabhan, P; Young, S M; Henstridge, M; Bhowmick, S; Bhattacharya, P K; Merlin, R

    2014-07-11

    Three-dimensional multicomponent plasmas composed of species with very different masses support a new branch of charge-density fluctuations known as acoustic plasmons. Here, we report on an ultrafast optical method to generate and probe coherent states of acoustic plasmons in a slab of GaAs, which relies on strong photoexcitation to create a large population of light electrons and heavy holes. Consistent with the random-phase-approximation theory, the data reveal standing plasma waves confined to these slabs, similar to those of conventional sound but with associated velocities that are significantly larger.

  8. Charge transfer dynamics between photoexcited CdS nanorods and mononuclear Ru water-oxidation catalysts.

    PubMed

    Tseng, Huan-Wei; Wilker, Molly B; Damrauer, Niels H; Dukovic, Gordana

    2013-03-06

    We describe the charge transfer interactions between photoexcited CdS nanorods and mononuclear water oxidation catalysts derived from the [Ru(bpy)(tpy)Cl](+) parent structure. Upon excitation, hole transfer from CdS oxidizes the catalyst (Ru(2+) → Ru(3+)) on a 100 ps to 1 ns timescale. This is followed by 10-100 ns electron transfer (ET) that reduces the Ru(3+) center. The relatively slow ET dynamics may provide opportunities for the accumulation of multiple holes at the catalyst, which is necessary for water oxidation.

  9. Neutral dissociation of hydrogen following photoexcitation of HCl at the chlorine K edge

    SciTech Connect

    Hansen, D.L.; Arrasate, M.E.; Martin, R.; Vanderford, B.; Lindle, D.W.; Cotter, J.; Neill, P.; Fisher, G.R.; Perera, R.C.; Leung, K.T.; Levin, J.C.; Sellin, I.A.; Simon, M.; Simon, M.; Uehara, Y.; Whitfield, S.B.

    1998-04-01

    Time-of-flight mass spectroscopy was used to study the relaxation dynamics of HCl following photoexcitation in the vicinity of the Cl K edge ({approximately}2.8keV) using monochromatic synchrotron radiation. At the lowest resonant excitation to the 6{sigma}{sup {asterisk}} antibonding orbital, almost half of the excited molecules decay by emission of a neutral H atom, mostly in coincidence with a highly charged Cl{sup n+} ion. The present work demonstrates that neutral-atom emission can be a significant decay channel for excited states with very short lifetimes (1 fs). {copyright} {ital 1998} {ital The American Physical Society}

  10. X-ray resonant photoexcitation: linewidths and energies of Kα transitions in highly charged Fe ions.

    PubMed

    Rudolph, J K; Bernitt, S; Epp, S W; Steinbrügge, R; Beilmann, C; Brown, G V; Eberle, S; Graf, A; Harman, Z; Hell, N; Leutenegger, M; Müller, A; Schlage, K; Wille, H-C; Yavaş, H; Ullrich, J; Crespo López-Urrutia, J R

    2013-09-06

    Photoabsorption by and fluorescence of the Kα transitions in highly charged iron ions are essential mechanisms for x-ray radiation transfer in astrophysical environments. We study photoabsorption due to the main Kα transitions in highly charged iron ions from heliumlike to fluorinelike (Fe24+ to Fe17+) using monochromatic x rays around 6.6 keV at the PETRA III synchrotron photon source. Natural linewidths were determined with hitherto unattained accuracy. The observed transitions are of particular interest for the understanding of photoexcited plasmas found in x-ray binary stars and active galactic nuclei.

  11. Method And Apparatus For Examining A Tissue Using The Spectral Wing Emission Therefrom Induced By Visible To Infrared Photoexcitation.

    DOEpatents

    Alfano, Robert R.; Demos, Stavros G.; Zhang, Gang

    2003-12-16

    Method and an apparatus for examining a tissue using the spectral wing emission therefrom induced by visible to infrared photoexcitation. In one aspect, the method is used to characterize the condition of a tissue sample and comprises the steps of (a) photoexciting the tissue sample with substantially monochromatic light having a wavelength of at least 600 nm; and (b) using the resultant far red and near infrared spectral wing emission (SW) emitted from the tissue sample to characterize the condition of the tissue sample. In one embodiment, the substantially monochromatic photoexciting light is a continuous beam of light, and the resultant steady-state far red and near infrared SW emission from the tissue sample is used to characterize the condition of the tissue sample. In another embodiment, the substantially monochromatic photoexciting light is a light pulse, and the resultant time-resolved far red and near infrared SW emission emitted from the tissue sample is used to characterize the condition of the tissue sample. In still another embodiment, the substantially monochromatic photoexciting light is a polarized light pulse, and the parallel and perpendicular components of the resultant polarized time-resolved SW emission emitted from the tissue sample are used to characterize the condition of the tissue sample.

  12. Model of ultrafast demagnetization driven by spin-orbit coupling in a photoexcited antiferromagnetic insulator Cr2O3.

    PubMed

    Guo, Feng; Zhang, Na; Jin, Wei; Chang, Jun

    2017-06-28

    We theoretically study the dynamic time evolution following laser pulse pumping in an antiferromagnetic insulator Cr2O3. From the photoexcited high-spin quartet states to the long-lived low-spin doublet states, the ultrafast demagnetization processes are investigated by solving the dissipative Schrödinger equation. We find that the demagnetization times are of the order of hundreds of femtoseconds, in good agreement with recent experiments. The switching times could be strongly reduced by properly tuning the energy gaps between the multiplet energy levels of Cr(3+). Furthermore, the relaxation times also depend on the hybridization of atomic orbitals in the first photoexcited state. Our results suggest that the selective manipulation of the electronic structure by engineering stress-strain or chemical substitution allows effective control of the magnetic state switching in photoexcited insulating transition-metal oxides.

  13. Model of ultrafast demagnetization driven by spin-orbit coupling in a photoexcited antiferromagnetic insulator Cr2O3

    NASA Astrophysics Data System (ADS)

    Guo, Feng; Zhang, Na; Jin, Wei; Chang, Jun

    2017-06-01

    We theoretically study the dynamic time evolution following laser pulse pumping in an antiferromagnetic insulator Cr2O3. From the photoexcited high-spin quartet states to the long-lived low-spin doublet states, the ultrafast demagnetization processes are investigated by solving the dissipative Schrödinger equation. We find that the demagnetization times are of the order of hundreds of femtoseconds, in good agreement with recent experiments. The switching times could be strongly reduced by properly tuning the energy gaps between the multiplet energy levels of Cr3+. Furthermore, the relaxation times also depend on the hybridization of atomic orbitals in the first photoexcited state. Our results suggest that the selective manipulation of the electronic structure by engineering stress-strain or chemical substitution allows effective control of the magnetic state switching in photoexcited insulating transition-metal oxides.

  14. Catalyst-free activation of peroxides under visible LED light irradiation through photoexcitation pathway.

    PubMed

    Gao, Yaowen; Li, Yixi; Yao, Linyu; Li, Simiao; Liu, Jin; Zhang, Hui

    2017-05-05

    Catalysts are known to activate peroxides to generate active radicals (i.e., hydroxyl radical (OH) and sulfate radical (SO4(-))) under certain conditions, but the activation of peroxides in the absence of catalysts under visible light irradiation has been rarely reported. This work demonstrates a catalyst-free activation of peroxides for the generation of OH and/or SO4(-) through photoexcited electron transfer from organic dyes to peroxides under visible LED light irradiation, where Rhodamine B (RhB) and Eosin Y (EY) were selected as model dyes. The formation of OH and/or SO4(-) in the reactions and the electron transfer from the excited dyes to peroxides were validated via electron paramagnetic resonance (EPR), photoluminescence (PL) spectra and cyclic voltammetry (CV). The performance of the peroxide/dye/Vis process was demonstrated to be altered depending on the target substrate. Meanwhile, the peroxide/dye/Vis process was effective for simultaneous decolorization of dyes and production of active radicals under neutral even or basic conditions. The findings of this study clarified a novel photoexcitation pathway for catalyst-free activation of peroxides under visible light irradiation, which could avoid the secondary metal ion (dissolved or leached) pollution from the metal-based catalysts and expand the application range of the peroxide-based catalytic process.

  15. Theoretical and experimental study of dynamics of photoexcited carriers in GaN

    SciTech Connect

    Shishehchi, Sara; Bellotti, Enrico; Rudin, Sergey; Garrett, Gregory A.; Wraback, Michael

    2013-12-21

    We present a theoretical and experimental study of the sub-picosecond dynamics of photo-excited carriers in GaN. In the theoretical model, interaction with an external ultrafast laser pulse is treated coherently and to account for the scattering mechanisms and dephasing processes, a generalized Monte-Carlo simulation is used. The scattering mechanisms included are carrier interactions with polar optical phonons and acoustic phonons, and carrier-carrier Coulomb interactions. We study the effect of different scattering mechanisms on the carrier densities. In the case that the excitation energy satisfies the threshold for polar optical scattering, phonon contribution is the dominant process in relaxing the system, otherwise, carrier-carrier mechanism is dominant. Furthermore, we present the temperature and pulse power dependent normalized luminescence intensity. The results are presented over a range of temperatures, electric field, and excitation energy of the laser pulse. For comparison, we also report the experimental time-resolved photoluminescence studies on GaN samples. There is a good agreement between the simulation and experiment in normalized luminescence intensity results. Therefore, we show that we can explain the dynamics of the photo-excited carriers in GaN by including only carrier-carrier and carrier-phonon interactions and a relatively simple two-band electronic structure model.

  16. Theoretical and experimental study of dynamics of photoexcited carriers in GaN

    NASA Astrophysics Data System (ADS)

    Shishehchi, Sara; Rudin, Sergey; Garrett, Gregory A.; Wraback, Michael; Bellotti, Enrico

    2013-12-01

    We present a theoretical and experimental study of the sub-picosecond dynamics of photo-excited carriers in GaN. In the theoretical model, interaction with an external ultrafast laser pulse is treated coherently and to account for the scattering mechanisms and dephasing processes, a generalized Monte-Carlo simulation is used. The scattering mechanisms included are carrier interactions with polar optical phonons and acoustic phonons, and carrier-carrier Coulomb interactions. We study the effect of different scattering mechanisms on the carrier densities. In the case that the excitation energy satisfies the threshold for polar optical scattering, phonon contribution is the dominant process in relaxing the system, otherwise, carrier-carrier mechanism is dominant. Furthermore, we present the temperature and pulse power dependent normalized luminescence intensity. The results are presented over a range of temperatures, electric field, and excitation energy of the laser pulse. For comparison, we also report the experimental time-resolved photoluminescence studies on GaN samples. There is a good agreement between the simulation and experiment in normalized luminescence intensity results. Therefore, we show that we can explain the dynamics of the photo-excited carriers in GaN by including only carrier-carrier and carrier-phonon interactions and a relatively simple two-band electronic structure model.

  17. The photoexcited triplet state as a probe of chromophore-protein interaction in myoglobin.

    PubMed Central

    Angiolillo, P J; Vanderkooi, J M

    1998-01-01

    The photoexcited metastable triplet state of Mg(2+)-mesoporphyrin IX (MgMPIX) or Mg(2+)-protoporphyrin IX (MgPPIX) located in the heme pocket of horse myoglobin (Mb) was investigated by optical and electron paramagnetic resonance (EPR) spectroscopy, and its properties were compared with the model complexes, MgMPIX, MgPPIX, and Mg2+ etioporphyrin I (MgETIOI), in noncoordinating and coordinating organic glasses. Zero-field splitting parameters, line shape, and Jahn-Teller distortion in the temperature range of 3.8-110 K are discussed in terms of porphyrin-protein interactions. The triplet line shapes for MgMPIXMb and MGPPIXMb show no temperature-dependent spectral line shape changes suggestive of Jahn-Teller dynamics, and it is concluded that the energy splitting is >> 150 cm-1, suggesting symmetry breaking from the anisotropy of intermal electric fields of the protein, and consistent with previous predictions (Geissinger et al. 1995. J. Phys. Chem. 99:16527-16529). Both MgMPIXMb and MgPPIXMb demonstrate electron spin polarization at low temperature, and from the polarization pattern it can be concluded that intersystem crossing occurs predominantly into in-plane spin sublevels of the triplet state. The splitting in the Q0.0 absorption band and the temperature dependence and splitting of the photoexcited triplet state of myoglobin in which the iron was replaced by Mg2+ are interpreted in terms of effects produced by electric field asymmetry in the heme pocket. PMID:9726951

  18. Interactions between photoexcited NIR emitting CdHgTe quantum dots and graphene oxide

    NASA Astrophysics Data System (ADS)

    Jagtap, Amardeep M.; Varade, Vaibhav; Konkena, Bharathi; Ramesh, K. P.; Chatterjee, Abhijit; Banerjee, Arup; Pendyala, Naresh Babu; Koteswara Rao, K. S. R.

    2016-02-01

    Hydrothermally grown mercury cadmium telluride quantum dots (CdHgTe QDs) are decorated on graphene oxide (GO) sheets through physisorption. The structural change of GO through partial reduction of oxygen functional groups is observed with X-ray photoelectron spectroscopy in GO-QDs composites. Raman spectroscopy provides relatively a small change (˜1.1 times) in D/G ratio of band intensity and red shift in G band from 1606 cm-1 to 1594 cm-1 in GO-CdHgTe QDs (2.6 nm) composites, which indicates structural modification of GO network. Steady state and time resolved photoluminescence (PL) spectroscopy shows the electronic interactions between photoexcited near infrared emitting CdHgTe QDs and GO. Another interesting observation is PL quenching in the presence of GO, and it is quite effective in the case of smaller size QDs (2.6 nm) compared to the larger size QDs (4.2 nm). Thus, the observed PL quenching is attributed to the photogenerated electron transfer from QDs to GO. The photoexcited electron transfer rate decreases from 2.2 × 109 to 1.5 × 108 s-1 with increasing particle size from 2.6 to 4.2 nm. Photoconductivity measurements on QDs-GO composite devices show nearly 3 fold increase in the current density under photo-illumination, which is a promising aspect for solar energy conversion and other optoelectronic applications.

  19. Pentacene appended to a TEMPO stable free radical: the effect of magnetic exchange coupling on photoexcited pentacene.

    PubMed

    Chernick, Erin T; Casillas, Rubén; Zirzlmeier, Johannes; Gardner, Daniel M; Gruber, Marco; Kropp, Henning; Meyer, Karsten; Wasielewski, Michael R; Guldi, Dirk M; Tykwinski, Rik R

    2015-01-21

    Understanding the fundamental spin dynamics of photoexcited pentacene derivatives is important in order to maximize their potential for optoelectronic applications. Herein, we report on the synthesis of two pentacene derivatives that are functionalized with the [(2,2,6,6-tetramethylpiperidin-1-yl)oxy] (TEMPO) stable free radical. The presence of TEMPO does not quench the pentacene singlet excited state, but does quench the photoexcited triplet excited state as a function of TEMPO-to-pentacene distance. Time-resolved electron paramagnetic resonance experiments confirm that triplet quenching is accompanied by electron spin polarization transfer from the pentacene excited state to the TEMPO doublet state in the weak coupling regime.

  20. On the pathway of photoexcited electrons: probing photon-to-electron and photon-to-phonon conversions in silicon by ATR-IR.

    PubMed

    Karabudak, Engin; Yüce, Emre; Schlautmann, Stefan; Hansen, Ole; Mul, Guido; Gardeniers, Han J G E

    2012-08-21

    Photoexcitation and charge carrier thermalization inside semiconductor photocatalysts are two important steps in solar fuel production. Here, photoexcitation and charge carrier thermalization in a silicon wafer are for the first time probed by a novel, yet simple and user-friendly Attenuated Total Reflectance Infrared spectroscopy (ATR-IR) system.

  1. Study on dynamics of photoexcited charge injection and trapping in CdS quantum dots sensitized TiO{sub 2} nanowire array film electrodes

    SciTech Connect

    Pang, Shan; Cheng, Ke; Yuan, Zhanqiang; Xu, Suyun; Cheng, Gang; Du, Zuliang

    2014-05-19

    The photoexcited electrons transfer dynamics of the CdS quantum dots (QDs) deposited in TiO{sub 2} nanowire array films are studied using surface photovoltage (SPV) and transient photovoltage (TPV) techniques. By comparing the SPV results with different thicknesses of QDs layers, we can separate the dynamic characteristics of photoexcited electrons injection and trapping. It is found that the TPV signals of photoexcited electrons trapped in the CdS QDs occur at timescales of about 2 × 10{sup −8} s, which is faster than that of the photoexcited electrons injected from CdS into TiO{sub 2}. More than 90 nm of the thickness of the CdS QDs layer will seriously affect the photoexcited electrons transfer and injection.

  2. Role of photoexcited nitrogen dioxide chemistry on ozone formation and emission control strategy over the Pearl River Delta, China

    EPA Science Inventory

    A new hydroxyl radical formation pathway via photo-excited nitrogen dioxide chemistry is incorporated into a chemistry-only box model as well as a 3D air quality model to examine its potential role on ozone formation and emission control strategy over the Pearl River Delta region...

  3. Photoexcitation of electron wave packets in quantum spin Hall edge states: Effects of chiral anomaly from a localized electric pulse

    NASA Astrophysics Data System (ADS)

    Dolcini, Fabrizio; Iotti, Rita Claudia; Montorsi, Arianna; Rossi, Fausto

    2016-10-01

    We show that, when a spatially localized electric pulse is applied at the edge of a quantum spin Hall system, electron wave packets of the helical states can be photoexcited by purely intrabranch electrical transitions, without invoking the bulk states or the magnetic Zeeman coupling. In particular, as long as the electric pulse remains applied, the photoexcited densities lose their character of right and left movers, whereas after the ending of the pulse they propagate in opposite directions without dispersion, i.e., maintaining their space profile unaltered. Notably we find that, while the momentum distribution of the photoexcited wave packets depends on the temperature T and the chemical potential μ of the initial equilibrium state and displays a nonlinear behavior on the amplitude of the applied pulse, in the mesoscopic regime the space profile of the wave packets is independent of T and μ . Instead, it depends purely on the applied electric pulse, in a linear manner, as a signature of the chiral anomaly characterizing massless Dirac electrons. We also discuss how the photoexcited wave packets can be tailored with the electric pulse parameters, for both low and finite frequencies.

  4. Role of photoexcited nitrogen dioxide chemistry on ozone formation and emission control strategy over the Pearl River Delta, China

    EPA Science Inventory

    A new hydroxyl radical formation pathway via photo-excited nitrogen dioxide chemistry is incorporated into a chemistry-only box model as well as a 3D air quality model to examine its potential role on ozone formation and emission control strategy over the Pearl River Delta region...

  5. Detecting the Photoexcited Carrier Distribution Across GaAs/Transition Metal Oxide Interfaces by Coherent Longitudinal Acoustic Phonons.

    PubMed

    Pollock, Kevin L; Doan, Hoang Q; Rustagi, Avinash; Stanton, Christopher J; Cuk, Tanja

    2017-03-02

    A prominent architecture for solar energy conversion layers diverse materials, such as traditional semiconductors (Si, III-V) and transition metal oxides (TMOs), into a monolithic device. The efficiency with which photoexcited carriers cross each layer is critical to device performance and dependent on the electronic properties of a heterojunction. Here, by time-resolved changes in the reflectivity after excitation of an n-GaAs/p-GaAs/TMO (Co3O4, IrO2) device, we detect a photoexcited carrier distribution specific to the p-GaAs/TMO interface through its coupling to phonons in both materials. The photoexcited carriers generate two coherent longitudinal acoustic phonons (CLAPs) traveling in opposite directions, one into the TMO and the other into the p-GaAs. This is the first time a CLAP is reported to originate at a semiconductor/TMO heterojunction. Therefore, these experiments seed future modeling of the built-in electric fields, the internal Fermi level, and the photoexcited carrier density of semiconductor/TMO interfaces within multilayered heterostructures.

  6. Ultrafast dynamics of photoexcited coherent phonon in Bi2Te3 thin films

    NASA Astrophysics Data System (ADS)

    Wu, Alexander Q.; Xu, Xianfan; Venkatasubramanian, Rama

    2008-01-01

    Nonequilibrium A1g longitudinal optical phonon with a frequency of 1.84THz in bismuth telluride (Bi2Te3) is coherently excited by ultrafast pulses. Time-resolved reflectivity measurements show a distinct second harmonic vibration around 3.68THz at room temperature caused by the nonlinearity of coherent phonon potentially related to the favorable crystal structure of Bi2Te3. The scattering rate between A1g coherent phonon and room temperature incoherent phonon is derived from the pump-fluence-dependent scattering rate of A1g coherent phonon. It is also observed that energy coupling from photoexcited carriers to lattice through coherent phonon vibration is more efficient and faster at higher pump fluence.

  7. Wavepacket splitting and two-pathway deactivation in the photoexcited visual pigment isorhodopsin.

    PubMed

    Polli, Dario; Weingart, Oliver; Brida, Daniele; Poli, Emiliano; Maiuri, Margherita; Spillane, Katelyn M; Bottoni, Andrea; Kukura, Philipp; Mathies, Richard A; Cerullo, Giulio; Garavelli, Marco

    2014-02-24

    Isorhodopsin is the visual pigment analogue of rhodopsin. It shares the same opsin environment but it embeds 9-cis retinal instead of 11-cis. Its photoisomerization is three times slower and less effective. The mechanistic rationale behind this observation is revealed by combining high-level quantum-mechanical/molecular-mechanical simulations with ultrafast optical spectroscopy with sub-20 fs time resolution and spectral coverage extended to the near-infrared. Whereas in rhodopsin the photoexcited wavepacket has ballistic motion through a single conical intersection seam region between the ground and excited states, in isorhodopsin it branches into two competitive deactivation pathways involving distinct conical intersection funnels. One is rapidly accessed but unreactive. The other is slower, as it features extended steric interactions with the environment, but it is productive as it follows forward bicycle pedal motion. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

    SciTech Connect

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

    2016-08-02

    Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups. Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.

  9. Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

    SciTech Connect

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

    2016-08-02

    Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups. Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.

  10. Photoexcited escape probability, optical gain, and noise in quantum well infrared photodetectors

    NASA Technical Reports Server (NTRS)

    Levine, B. F.; Zussman, A.; Gunapala, S. D.; Asom, M. T.; Kuo, J. M.; Hobson, W. S.

    1992-01-01

    We present a detailed and thorough study of a wide variety of quantum well infrared photodetectors (QWIPs), which were chosen to have large differences in their optical and transport properties. Both n- and p-doped QWIPs, as well as intersubband transitions based on photoexcitation from bound-to-bound, bound-to-quasi-continuum, and bound-to-continuum quantum well states were investigated. The measurements and theoretical analysis included optical absorption, responsivity, dark current, current noise, optical gain, hot carrier mean free path; net quantum efficiency, quantum well escape probability, quantum well escape time, as well as detectivity. These results allow a better understanding of the optical and transport physics and thus a better optimization of the QWIP performance.

  11. Two-color photoexcitation of Rydberg states via an electric quadrupole transition

    SciTech Connect

    Li Leping; Gu Quanli; Knee, J. L.; Wright, J. D.; DiSciacca, J. M.; Morgan, T. J.

    2008-03-15

    We report the observation of an electric quadrupole transition between the 4s{sup '}[1/2]{sub 0}{sup o} and 3d[3/2]{sub 2}{sup o} states in the spectrum of argon and use it in the first step of a scheme to excite Rydberg states. The initial identification of the transition is based on one-color, two-photon photoionization. A different experiment utilizing two-color, two-photon photoexcitation to Rydberg states confirms the identification. Despite the unavoidable background of one-color, two-photon photoionization, the latter experimental technique makes possible two-photon spectroscopy of Rydberg states using a resonant intermediate state populated by an electric quadrupole transition.

  12. Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling.

    PubMed

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

    2016-08-18

    Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups. Hitherto, it has not been established if it involves a higher lying "dark" state or vibrational relaxation in the excited S2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic S2 potential.

  13. A Static Picture of the Relaxation and Intersystem Crossing Mechanisms of Photoexcited 2-Thiouracil.

    PubMed

    Mai, Sebastian; Marquetand, Philipp; González, Leticia

    2015-09-10

    Accurate excited-state quantum chemical calculations on 2-thiouracil, employing large active spaces and up to quadruple-ζ quality basis sets in multistate complete active space perturbation theory calculations, are reported. The results suggest that the main relaxation path for 2-thiouracil after photoexcitation should be S2 → S1 → T2 → T1, and that this relaxation occurs on a subpicosecond time scale. There are two deactivation pathways from the initially excited bright S2 state to S1, one of which is nearly barrierless and should promote ultrafast internal conversion. After relaxation to the S1 minimum, small singlet-triplet energy gaps and spin-orbit couplings of about 130 cm(-1) are expected to facilitate intersystem crossing to T2, from where very fast internal conversion to T1 occurs. An important finding is that 2-thiouracil shows strong pyramidalization at the carbon atom of the thiocarbonyl group in several excited states.

  14. Femtosecond and continuous-wave photoexcitations of thiophene-based conjugated polymers

    NASA Astrophysics Data System (ADS)

    Luzzati, Silva; Botta, Chiara; Romanoni, Mariachiara; Comoretto, Davide; Tubino, Riccardo; Nisoli, Mauro; Cybo-Ottone, Alessandro; De Silvestri, Sandro

    1993-12-01

    We present an extensive photoinduced absorption study of alkyl substituted poly (2,5- thienylenevinylene)s in both the solid state and in solution. The optical and conformational properties of the samples are monitored with UV-Vis absorption and emission, IR absorption and Raman scattering. Three photoinduced states are detected under steady state condition which display lifetimes of the order of 100 ms in the solid state. The two low-energy bands are assigned to bipolarons, while a third band peaked near the band edge has a different origin. In solution very lone-lived photoexcitated states are observed and they are assumed to recombine via a solvent-assisted photo-doping mechanism.

  15. Transient reflectance of photoexcited Cd{sub 3}As{sub 2}

    SciTech Connect

    Weber, C. P. Berggren, Bryan S.; Arushanov, Ernest; Nateprov, Alex; Hosseini, Tahereh; Kouklin, Nikolai

    2015-06-08

    We report ultrafast transient-grating measurements of crystals of the three-dimensional Dirac semimetal cadmium arsenide, Cd{sub 3}As{sub 2}, at both room temperature and 80 K. After photoexcitation with 1.5-eV photons, charge-carriers relax by two processes, one of duration 500 fs and the other of duration 3.1 ps. By measuring the complex phase of the change in reflectance, we determine that the faster signal corresponds to a decrease in absorption, and the slower signal to a decrease in the light's phase velocity, at the probe energy. We attribute these signals to electrons' filling of phase space, first near the photon energy and later at lower energy. We attribute their decay to cooling by rapid emission of optical phonons, then slower emission of acoustic phonons. We also present evidence that both the electrons and the lattice are strongly heated.

  16. Magnetic-field cycling instrumentation for dynamic nuclear polarization-nuclear magnetic resonance using photoexcited triplets.

    PubMed

    Kagawa, Akinori; Negoro, Makoto; Takeda, Kazuyuki; Kitagawa, Masahiro

    2009-04-01

    To advance static solid-state NMR with hyperpolarized nuclear spins, a system has been developed enabling dynamic nuclear polarization (DNP) using electron spins in the photoexcited triplet state with X-band microwave apparatus, followed by static solid-state nuclear magnetic resonance (NMR) experiments using the polarized nuclear-spin system with a goniometer. In order to perform the DNP and NMR procedures in different magnetic fields, the DNP system and the NMR system are spatially separated, between which the sample can be shuttled while its orientation is controlled in a reproducible fashion. We demonstrate that the system developed in this work is operational for solid-state NMR with hyperpolarized nuclear-spin systems in static organic materials, and also discuss the application of our system.

  17. A Static Picture of the Relaxation and Intersystem Crossing Mechanisms of Photoexcited 2-Thiouracil

    PubMed Central

    2015-01-01

    Accurate excited-state quantum chemical calculations on 2-thiouracil, employing large active spaces and up to quadruple-ζ quality basis sets in multistate complete active space perturbation theory calculations, are reported. The results suggest that the main relaxation path for 2-thiouracil after photoexcitation should be S2 → S1 → T2 → T1, and that this relaxation occurs on a subpicosecond time scale. There are two deactivation pathways from the initially excited bright S2 state to S1, one of which is nearly barrierless and should promote ultrafast internal conversion. After relaxation to the S1 minimum, small singlet–triplet energy gaps and spin–orbit couplings of about 130 cm–1 are expected to facilitate intersystem crossing to T2, from where very fast internal conversion to T1 occurs. An important finding is that 2-thiouracil shows strong pyramidalization at the carbon atom of the thiocarbonyl group in several excited states. PMID:26284285

  18. Photoexcited chemical wave in the ruthenium-catalyzed Belousov-Zhabotinsky reaction.

    PubMed

    Nakata, Satoshi; Matsushita, Mariko; Sato, Taisuke; Suematsu, Nobuhiko J; Kitahata, Hiroyuki; Amemiya, Takashi; Mori, Yoshihito

    2011-07-07

    The excitation of the photosensitive Belousov-Zhabotinsky (BZ) reaction induced by light stimulation was systematically investigated. A stepwise increase in the light intensity induced the excitation, whereas a stepwise decrease did not induce the excitation. The threshold values for the excitation were found to be a function of the initial and final light intensities, time variation in light intensity, and the concentration of NaBrO(3). The experimental results were qualitatively reproduced by a theoretical calculation based on a three-variable Oregonator model modified for the photosensitive BZ reaction. These results suggest that although the steady light irradiation is known to inhibit oscillation and chemical waves in the BZ system under almost all conditions, the stepwise increase in the light irradiation leads to the rapid production of an activator, resulting in the photoexcitation.

  19. Photo-ionization and photo-excitation of curcumin investigated by laser flash photolysis.

    PubMed

    Qian, Tingting; Kun, Li; Gao, Bo; Zhu, Rongrong; Wu, Xianzheng; Wang, Shilong

    2013-12-01

    Curcumin (Cur) has putative antitumor properties. In the current study, we examined photophysical and photochemical properties of Cur using laser flash photolysis. The results demonstrated that Cur could be photo-ionized at 355 nm laser pulse to produce radical cation (Cur(+)) and solvated electron e(sol)(-) in 7:3 ethanol-water mixtures. The quantum yield of Cur photo-ionization and the ratio of photo-ionization to photo-excitation were also determined. Cur(+) could be transferred into neutral radical of Cur (Cur) via deprotonation with the pKa 4.13. The excited singlet of Cur ((1)Cur* could be transferred into excited triplet ((3)Cur*, which could be quenched by oxygen to produce singlet oxygen (1)O2*. Reaction of (3)Cur* with tryptophan was confirmed. The results encourage developing curcumin as a photosensitive antitumor agent.

  20. Shape transformation and relaxation dynamics of photoexcited TiO2/Ag nanocomposites.

    PubMed

    Kim, Mee Rahn; Ah, Chil Seong; Shin, Dongha; Lee, Sang Kyung; Lee, Wan In; Jang, Du-Jeon

    2008-06-01

    The laser-induced sintering of TiO2 nanoparticles into larger nanospheres is accelerated by adsorbed silver particles. For the same weight fraction of silver, silver nanoparticles of 5 nm in diameter modify TiO2 nanoparticles more effectively than those of 1.5 nm do, suggesting that the photocatalysis of TiO2 nanoparticles as well as their stability is highly dependent on the sizes, the shapes, and the distribution of adsorbed metal nanoparticles. The photoexcited electrons of TiO2 nanoparticles are quenched at trap sites and surface states by transfer to the conduction band of silver, implying that the presence of adsorbed silver nanoparticles enhances the photocatalytic effect of TiO2.

  1. Transient Magnetophotoinduced Absorption Studies of Photoexcitations in π -Conjugated Donor-Acceptor Copolymers

    NASA Astrophysics Data System (ADS)

    Huynh, Uyen N. V.; Basel, Tek P.; Ehrenfreund, Eitan; Li, Gang; Yang, Yang; Mazumdar, S.; Vardeny, Z. Valy

    2017-07-01

    We have utilized a plethora of transient and steady state optical and magneto-optical spectroscopies in a broad spectral range (0.25-2.5 eV) for elucidating the primary and long-lived photoexcitations in a low band-gap π -conjugated donor-acceptor (DA) copolymer used for efficient photovoltaic solar cells. We show that both singlet excitons (SE) and intrachain triplet-triplet (TT) pairs are photogenerated in the DA-copolymer chains. From the picosecond transient magnetic field response of these species we conclude that the SE and TT spin states are coupled. The TT decomposition into two intrachain geminate triplet excitons maintains spin coherence and thus their spin entanglement lasts into the microsecond time domain.

  2. Diffuse scattering from liquid solutions with white-beam undulator radiation for photoexcitation studies.

    PubMed

    Plech, Anton; Randler, Rudolf; Geis, Armin; Wulff, Michael

    2002-09-01

    Scattering from molecules in solution is a natural way to study fast reactions in solution with X-ray probes. With the availability of reliable femtosecond laser systems and pulsed synchrotron sources with high brilliance, it has become possible to study picosecond time-resolved photoexcitation in condensed matter. Owing to the low scattering cross section and the high background from the non-excited solvent, high flux and long exposure times are required to obtain information about isolated molecules in the conventional monochromatic scattering scheme. It is proposed that the full spectrum of a single-line undulator be used to obtain the diffuse scattering distribution. The bandwidth of 2-5% of the first harmonic, which is easily achievable in current insertion devices, is sufficient to allow the derivation of molecular form factors even in diluted systems. The relaxed bandwidth augments the usable flux drastically.

  3. Ultrafast lattice response of photoexcited thin films studied by X-ray diffraction

    PubMed Central

    Herzog, Marc; Bojahr, André; Leitenberger, Wolfram; Hertwig, Andreas; Bargheer, Matias

    2014-01-01

    Using ultrafast X-ray diffraction, we study the coherent picosecond lattice dynamics of photoexcited thin films in the two limiting cases, where the photoinduced stress profile decays on a length scale larger and smaller than the film thickness. We solve a unifying analytical model of the strain propagation for acoustic impedance-matched opaque films on a semi-infinite transparent substrate, showing that the lattice dynamics essentially depend on two parameters: One for the spatial profile and one for the amplitude of the strain. We illustrate the results by comparison with high-quality ultrafast X-ray diffraction data of SrRuO3 films on SrTiO3 substrates. PMID:26798784

  4. Highly efficient terahertz wave modulators by photo-excitation of organics/silicon bilayers

    SciTech Connect

    Yoo, Hyung Keun; Kang, Chul; Hwang, In-Wook; Yoon, Youngwoon; Lee, Kiejin; Kee, Chul-Sik; Lee, Joong Wook

    2014-07-07

    Using hybrid bilayer systems comprising a molecular organic semiconductor and silicon, we achieve optically controllable active terahertz (THz) modulators that exhibit extremely high modulation efficiencies. A modulation efficiency of 98% is achieved from thermally annealed C{sub 60}/silicon bilayers, due to the rapid photo-induced electron transfer from the excited states of the silicon onto the C{sub 60} layer. Furthermore, we demonstrate the broadband modulation of THz waves. The cut-off condition of the system that is determined by the formation of efficient charge separation by the photo-excitation is highly variable, changing the system from insulating to metallic. The phenomenon enables an extremely high modulation bandwidth and rates of electromagnetic waves of interest. The realization of near-perfect modulation efficiency in THz frequencies opens up the possibilities of utilizing active modulators for THz spectroscopy and communications.

  5. Non-Band-Gap Photoexcitation of Hydroxylated TiO2.

    PubMed

    Zhang, Yu; Payne, Daniel T; Pang, Chi L; Fielding, Helen H; Thornton, Geoff

    2015-09-03

    The photochemistry of TiO2 has been studied intensively since it was discovered that TiO2 can act as a photocatalyst. Nevertheless, it has proven difficult to establish the detailed charge-transfer processes involved, partly because the excited states involved are difficult to study. Here we present evidence of the existence of hydroxyl-induced excited states in the conduction band region. Using two-photon photoemission, we show that stepwise photoexcitation from filled band gap states lying 0.8 eV below the Fermi level of rutile TiO2(110) excites hydroxyl-induced states 2.73 eV above the Fermi level that has an onset energy of ∼3.1 eV. The onset is shifted to lower energy by the coadsorption of molecular water, which suggests a means of tuning the energy of the excited state.

  6. Absolute measurement of spatial and spectral characteristics of bremsstrahlung using the photoexcitation of nuclear isomers

    NASA Astrophysics Data System (ADS)

    Carroll, J. J.; Richmond, D. G.; Sinor, T. W.; Taylor, K. N.; Hong, C.; Standifird, J. D.; Collins, C. B.; Huxel, N.; von Neumann-Cosel, P.; Richter, A.

    1993-08-01

    A method of obtaining absolute, direct measurements of the spatial and spectral characteristics of bremsstrahlung is discussed. This technique, called x-ray activation of nuclei (XAN) is based on the use of well-known photonuclear reactions which populate long-lived nuclear isomers. These populations sample incident photon continua at discrete excitation energies and effectively store this information for convenient retrieval following the irradiation of gram-sized targets. Recently a series of experiments has been conducted which has significantly expanded the available data for the photoexcitation of a wide range of isomers at higher energies. Thus it has become feasible to extend the use of XAN to energies approaching 4 MeV. The utility of this technique is demonstrated by the characterization of bremsstrahlung from the newly installed research linac at the University of Texas at Dallas.

  7. First-Principles Calculation of Femtosecond Symmetry-Breaking Atomic Forces in Photoexcited Bismuth

    NASA Astrophysics Data System (ADS)

    Murray, Éamonn D.; Fahy, Stephen

    2015-02-01

    We present a first-principles method for the calculation of the polarization-dependent atomic forces resulting from optical excitation in a solid. We calculate the induced force driving the Eg phonon mode in bismuth immediately after absorption of polarized light. When radiation with polarization perpendicular to the c axis is absorbed, the photoexcited charge density breaks the threefold rotational symmetry, leading to an atomic force component perpendicular to the axis. We calculate the initial excited electronic distribution as a function of photon energy and polarization and find the resulting atomic force components parallel and perpendicular to the axis. The magnitude of the calculated force is in excellent agreement with that derived from recent measurements of the amplitude of Eg atomic motion and the decay time of several femtoseconds for the driving force.

  8. Photo-ionization and photo-excitation of curcumin investigated by laser flash photolysis

    NASA Astrophysics Data System (ADS)

    Qian, Tingting; Kun, Li; Gao, Bo; Zhu, Rongrong; Wu, Xianzheng; Wang, ShiLong

    2013-12-01

    Curcumin (Cur) has putative antitumor properties. In the current study, we examined photophysical and photochemical properties of Cur using laser flash photolysis. The results demonstrated that Cur could be photo-ionized at 355 nm laser pulse to produce radical cation (Currad +) and solvated electron esol- in 7:3 ethanol-water mixtures. The quantum yield of Cur photo-ionization and the ratio of photo-ionization to photo-excitation were also determined. Currad + could be transferred into neutral radical of Cur (Currad ) via deprotonation with the pKa 4.13. The excited singlet of Cur (1Cur*) could be transferred into excited triplet (3Cur*), which could be quenched by oxygen to produce singlet oxygen 1O2∗. Reaction of 3Cur* with tryptophan was confirmed. The results encourage developing curcumin as a photosensitive antitumor agent.

  9. Anomalous Above-Gap Photoexcitations and Optical Signatures of Localized Charge Puddles in Monolayer Molybdenum Disulfide.

    PubMed

    Borys, Nicholas J; Barnard, Edward S; Gao, Shiyuan; Yao, Kaiyuan; Bao, Wei; Buyanin, Alexander; Zhang, Yingjie; Tongay, Sefaattin; Ko, Changhyun; Suh, Joonki; Weber-Bargioni, Alexander; Wu, Junqiao; Yang, Li; Schuck, P James

    2017-02-28

    Broadband optoelectronics such as artificial light harvesting technologies necessitate efficient and, ideally, tunable coupling of excited states over a wide range of energies. In monolayer MoS2, a prototypical two-dimensional layered semiconductor, the excited state manifold spans the visible electromagnetic spectrum and is comprised of an interconnected network of excitonic and free-carrier excitations. Here, photoluminescence excitation spectroscopy is used to reveal the energetic and spatial dependence of broadband excited state coupling to the ground-state luminescent excitons of monolayer MoS2. Photoexcitation of the direct band gap excitons is found to strengthen with increasing energy, demonstrating that interexcitonic coupling across the Brillouin zone is more efficient than previously reported, and thus bolstering the import and appeal of these materials for broadband optoelectronic applications. Narrow excitation resonances that are superimposed on the broadband photoexcitation spectrum are identified and coincide with the energetic positions of the higher-energy excitons and the electronic band gap as predicted by first-principles calculations. Identification of such features outlines a facile route to measure the optical and electronic band gaps and thus the exciton binding energy in the more sophisticated device architectures that are necessary for untangling the rich many-body phenomena and complex photophysics of these layered semiconductors. In as-grown materials, the excited states exhibit microscopic spatial variations that are characteristic of local carrier density fluctuations, similar to charge puddling phenomena in graphene. Such variations likely arise from substrate inhomogeneity and demonstrate the possibility to use substrate patterning to tune local carrier density and dynamically control excited states for designer optoelectronics.

  10. Electronic Charges and Electric Potential at LaAlO3/SrTiO3 Interfaces Studied by Core-Level Photoemission Spectroscopy

    SciTech Connect

    Hwang, Harold

    2011-08-19

    We studied LaAlO{sub 3}/SrTiO{sub 3} interfaces for varying LaAlO{sub 3} thickness by core-level photoemission spectroscopy. In Ti 2p spectra for conducting 'n-type' interfaces, Ti{sup 3+} signals appeared, which were absent for insulating 'p-type' interfaces. The Ti{sup 3+} signals increased with LaAlO{sub 3} thickness, but started well below the critical thickness of 4 unit cells for metallic transport. Core-level shifts with LaAlO{sub 3} thickness were much smaller than predicted by the polar catastrophe model. We attribute these observations to surface defects/adsorbates providing charges to the interface even below the critical thickness.

  11. Spin-Orbit Effects in Spin-Resolved L2,3 Core Level Photoemission of 3d Ferromagnetic Thin Films

    SciTech Connect

    Komesu, T; Waddill, G D; Yu, S W; Butterfield, M; Tobin, J G

    2007-10-02

    We present spin-resolved 2p core level photoemission for the 3d transition metal films of Fe and Co grown on Cu(100). We observe clear spin asymmetry in the main 2p core level photoemission peaks of Fe and Co films consistent with trends in the bulk magnetic moments. The spin polarization can be strongly enhanced, by variation of the experimental geometry, when the photoemission is undertaken with circularly polarized light, indicating that spin-orbit interaction can have a profound in spin polarized photoemission. Further spin polarized photoemission studies using variable circularly polarized light at high photon energies, high flux are indicated, underscoring the value of synchrotron measurements at facilities with increased beam stability.

  12. O 1s core-level shifts at the anatase TiO2(101)/N3 photovoltaic interface: Signature of H-bonded supramolecular assembly

    NASA Astrophysics Data System (ADS)

    Patrick, Christopher E.; Giustino, Feliciano

    2011-08-01

    We here report an atomic-scale first-principles investigation of the O 1s core-level shifts at the interface between TiO2 and the dye N3 found in dye-sensitized solar cells. We first perform extensive validation of our computational setup in the case of small molecules containing carboxylic acid groups in the gas phase. Then we calculate the O 1s core-level shifts for a variety of atomistic models of the TiO2/N3 interface. We investigate in detail the effects of water contamination, dye packing density, exchange and correlation functionals, and hydrogen-bonding interactions on the calculated core-level spectra. The quantitative comparison between our calculated core-level shifts and measured photoemission spectra [Johansson , J. Phys. Chem. BJPCBFK1520-610610.1021/jp0525282 109, 22256 (2005)] leads us to propose a new atomic-scale model of the TiO2/N3 interface, where the dyes are arranged in supramolecular H-bonded assemblies. Our interface models describe dry TiO2/N3 films as in [Johansson , J. Phys. Chem. BJPCBFK1520-610610.1021/jp0525282 109, 22256 (2005)], and are of direct relevance to solid-state dye-sensitized solar cells. Our present work suggests that the adsorption energetics is not a reliable indicator of the quality of an interface model, and highlights the importance of combining experimental and computational spectroscopy for determining the atomic-scale structure of nanostructured solar cell interfaces.

  13. Observation of core-level binding energy shifts between (100) surface and bulk atoms of epitaxial CuInSe{sub 2}

    SciTech Connect

    Nelson, A.J.; Berry, G.; Rockett, A.

    1997-04-01

    Core-level and valence band photoemission from semiconductors has been shown to exhibit binding energy differences between surface atoms and bulk atoms, thus allowing one to unambiguously distinguish between the two atomic positions. Quite clearly, surface atoms experience a potential different from the bulk due to the lower coordination number - a characteristic feature of any surface is the incomplete atomic coordination. Theoretical accounts of this phenomena are well documented in the literature for III-V and II-VI semiconductors. However, surface state energies corresponding to the equilibrium geometry of (100) and (111) surfaces of Cu-based ternary chalcopyrite semiconductors have not been calculated or experimental determined. These compounds are generating great interest for optoelectronic and photovoltaic applications, and are an isoelectronic analog of the II-VI binary compound semiconductors. Surface core-level binding energy shifts depend on the surface cohesive energies, and surface cohesive energies are related to surface structure. For ternary compound semiconductor surfaces, such as CuInSe{sub 2}, one has the possibility of variations in surface stoichiometry. Applying standard thermodynamical calculations which consider the number of individual surface atoms and their respective chemical potentials should allow one to qualitatively determine the magnitude of surface core-level shifts and, consequently, surface state energies.

  14. Quenching of photoexcited states of the proteins chromophores and introduced into the protein macromolecules fluorescent probes by heavy metal ions

    NASA Astrophysics Data System (ADS)

    Melnikov, A. G.; Dyachuk, O. A.; Melnikov, G. V.

    2015-03-01

    We have studied the processes of quenching of photoexcited states of fluorescent probes and quenching of the fluorescence of the chromophores of human serum albumin (HSA) by heavy metal ions (HM): cations Tl+, Pb2+, Cu2+, Cd2+, and the anion of iodine (I-). We used the dye from xanthene series - eosin as a fluorescent probe. By quenching of the fluorescence of protein chromophores we found an influence of HM on the structure of proteins, resulting in a shift of the peak of the fluorescence of HSA tryptophanyl. This can be explained by proteins denaturation under the influence of heavy metals and penetration of water into the inner environment of HSA tryptophan. It was established that the constant of the quenching of the probe phosphorescence is much higher than the fluorescence, which is explained by significantly longer lifetime of the photoexcited states of fluorescent probes in the triplet state than in the singlet.

  15. EXAFS studies on the structure of photoexcited cyclopentadienylnickelnitrosyl(C{sub 5}H{sub 5}NiNO)

    SciTech Connect

    Chen, L.X.; Bowman, M.K.; Montano, A.; Norris, J.R. |

    1993-05-01

    The structures of C{sub 5}H{sub 5}NiNO in a reversible photochemical reaction were studied via EXAFS, FTIR, and optical absorption spectroscopies. A photoexcited intermediate with distinctively different EXAFS, IR, and optical absorption spectra from those of the ground state molecules was generated upon irradiation using 365 mn light at 20K in a 3-methylpentane solution. The reverse reaction was induced by irradiation with 310 mn light. The EXAFS data analysis has shown a 0.12 {Angstrom} elongation of the Ni-N bond and the bending, of Ni-N-0 in the photoexcited intermediate. Several ZINDO calculations were conducted based on the structures obtained from the EXAFS spectroscopy. These calculations reproduced the changes in the optical spectra and the intramolecular electron transfer in C{sub 5}H{sub 5}NiNO.

  16. EXAFS studies on the structure of photoexcited cyclopentadienylnickelnitrosyl(C[sub 5]H[sub 5]NiNO)

    SciTech Connect

    Chen, L.X.; Bowman, M.K.; Montano, A. ); Norris, J.R. Chicago Univ., IL . Dept. of Chemistry)

    1993-01-01

    The structures of C[sub 5]H[sub 5]NiNO in a reversible photochemical reaction were studied via EXAFS, FTIR, and optical absorption spectroscopies. A photoexcited intermediate with distinctively different EXAFS, IR, and optical absorption spectra from those of the ground state molecules was generated upon irradiation using 365 mn light at 20K in a 3-methylpentane solution. The reverse reaction was induced by irradiation with 310 mn light. The EXAFS data analysis has shown a 0.12 [Angstrom] elongation of the Ni-N bond and the bending, of Ni-N-0 in the photoexcited intermediate. Several ZINDO calculations were conducted based on the structures obtained from the EXAFS spectroscopy. These calculations reproduced the changes in the optical spectra and the intramolecular electron transfer in C[sub 5]H[sub 5]NiNO.

  17. Effects of interchain coupling on photoexcitation in two coupled polymer chains in the presence of an electric field

    NASA Astrophysics Data System (ADS)

    Meng, Y.; An, Z.

    2010-04-01

    Within an extended Su-Schrieffer-Heeger model including interchain interactions and the extended Hubbard model (EHM), the dynamical relaxation of photoexcitations in the presence of an external electric field is investigated using a nonadiabatic evolution method. Under the action of the interchain interactions both intrachain excitons and interchain excitons are generated after photoexcitation in two coupled polymer chains. Our results show that the field required to dissociate the excitons depends sensitively on the strength of the interchain coupling. As the interchain coupling strength increases, the dissociation field decreases. By analyzing the relation between the yield of intrachain and interchain excitons and the interchain coupling strength, we explain the dependence between the dissociation field and the strength of the interchain interactions. The theoretical results are expected to provide useful predictions concerning which polymers with properly strong interchain interactions are likely to be most suitable for use in organic solar cells.

  18. Ultrafast Terahertz Probe of Transient Evolution of Charged and Neutral Phase of Photoexcited Electron-hole Gas in Monolayer Semiconductor

    NASA Astrophysics Data System (ADS)

    Liu, Xuefeng; Ji, Qingqing; Gao, Zhihan; Ge, Shaofeng; Qiu, Jun; Liu, Zhongfan; Zhang, Yanfeng; Sun, Dong

    2015-03-01

    We investigate the dynamical formation of excitons from photoexcited electron-hole plasma and its subsequent decay dynamics in monolayer MoS2 grown by chemical vapor deposition using ultrafast pump and terahertz probe spectroscopy under temperature down to 78 K. The observed transient THz transmission can be fit with two decay components: a fast component with decay lifetime of 20 ps, which is attributed to exciton life time including the exciton formation and subsequent intraexciton relaxation; a slow component with extremely long decay lifetime of several ns which is attributed to long live dark exciton or localized exciton state. Further temperature and pump fluence dependent studies of the two decay components verify the above relaxation dynamics. The measured time resolved evolution of photoexcited carriers provides new opportunities in developing novel optoelectronic and excitonic devices based on monolayer transition-metal dichalcogenides.

  19. Visualization of Photoexcited Carrier Responses in a Solar Cell Using Optical Pump—Terahertz Emission Probe Technique

    NASA Astrophysics Data System (ADS)

    Nakanishi, Hidetoshi; Ito, Akira; Takayama, Kazuhisa; Kawayama, Iwao; Murakami, Hironaru; Tonouchi, Masayoshi

    2016-05-01

    We observed photoexcited carrier responses in solar cells excited by femtosecond laser pulses with spatial and temporal resolution using an optical pump-terahertz emission probe technique. We visualized the ultrafast local variation of the intensity of terahertz emission from a polycrystalline silicon solar cell using this technique and clearly observed the change in signals between a grain boundary and the inside of a grain in the solar cell. Further, the time evolution of the pump-probe signals of the polycrystalline and monocrystalline silicon solar cells was observed, and the relaxation times of photoexcited carriers in the emitter layers of crystalline silicon solar cells were estimated using this technique. The estimated relaxation time was consistent with the lifetime of the Auger recombination process that was dominant in heavily doped silicon used as an emitter layer for the silicon solar cells, which is difficult to obtain with photoluminescence method commonly used for the evaluation of solar cells.

  20. Characteristics of terahertz wave modulation using wavelength-selective photoexcitation in pentacene/Si and TIPS pentacene/Si bilayers

    NASA Astrophysics Data System (ADS)

    Yoo, Hyung Keun; Kang, Chul; Kee, Chul-Sik; Hwang, In-Wook; Lee, Joong Wook

    2016-11-01

    We demonstrate the characteristics of the optical control of terahertz (THz) wave transmission in photoexcited bilayers of pentacene/Si and 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene)/Si. The modulation efficiency is influenced significantly by the photoexcitation wavelength of the optical beams. Lower optical absorption of organic materials leads to higher modulation efficiency because the photocarriers excited on Si with a higher diffusion rate and mobility are far more instrumental in increasing the modulation than the excitons generated on the organic layers. Securing a sufficient depth for carrier diffusion on organic layers is also important for increasing the THz modulation efficiency. These findings may be useful for designing highly efficient and spectrally controllable THz wave modulators.

  1. Delayed fluorescence spectra of intact leaves photoexcited by sunlight measured with a multichannel Fourier-transform chemiluminescence spectrometer

    NASA Astrophysics Data System (ADS)

    Akita, Saeka; Yano, Ayako; Ishii, Hiroshi; Satoh, Chikahiro; Akai, Nobuyuki; Nakata, Munetaka

    2013-06-01

    Delayed fluorescence spectra of intact leaves of Green pak choi (Brassica rapa var. chinensis) were measured with a multichannel Fourier-transform chemiluminescence spectrometer, which we developed recently. The intact samples, photoexcited by sunlight without artificial light sources, showed delayed fluorescence around 740 nm with a lifetime of ˜6 s. The observed spectra were deconvoluted into two Gaussian bands: the delayed fluorescence from photosystem II and photosystem I complexes. Their relative intensities depended on the chlorophyll concentration, but their wavelengths were unchanged.

  2. X-ray absorption structural study of a reversible, photoexcited charge-transfer state

    SciTech Connect

    Chen, L.X.; Bowman, M.K.; Norris, J.R. Univ. of Chicago, IL ); Montano, P.A. )

    1993-05-19

    Electron-transfer reactions can be accompanied by significant nuclear movements. Nuclear motion appears to be especially vital to the reversible, photoinduced charge-transfer chemistry of cyclopentadienylnickel nitrosyl (C[sub 5]H[sub 5]NiNO). Although extended X-ray absorption fine structure (EXAFS) spectroscopy has recorded photoinduced changes in the ligation of myoglobins, similar X-ray studies of electron-transfer chemistry have not been reported. Here we examine reversible, photoinduced structural changes in C[sub 5]H[sub 5]NiNO by EXAFS and propose a mechanism for the electron-transfer chemistry. This work demonstrates that EXAFS can measure distance changes accompanying photoinduced electron transfer to provide new details of the geometry of photoexcited state and suggests that electron transfer occurs in the transient, optically excited states of C[sub 5]H[sub 5]NiNO and C[sub 5]H[sub 5]NiNO[sup CT] as dictated by NO movement that produces either C[sub 5]H[sub 5]NiNO[sup CT] or C[sub 5]H[sub 5]NiNO[sup GS]. 14 refs., 2 figs.

  3. Photoexcited State Molecular Structures in Solution Studied by Pump-Probe XAFS

    NASA Astrophysics Data System (ADS)

    Chen, Lin

    2002-03-01

    The photoexcitation causes displacement of electron densities within or among molecules, which consequently leads to nuclear movements. Such nuclear displacements often occur in transient states with short lifetimes. Knowing transient molecular structures during photochemical reactions is important for understanding fundamental aspects of solar energy conversion and storage. Fast x-ray techniques provide direct probes for these transient structures. Using x-ray pulses from the Advanced Photon Source at Argonne, a laser pulse pump, x-ray pulse probe XAFS technique has been developed to capture transient molecular structures in disordered media with nanosecond time resolution. We have carried out several pump-probe XAFS measurements on 1)identifying a transient molecular structure of the photodissociation product of nickel-tetraphenylporphyrin with piperidine axial ligands (NiTPP-L2); 2)determination of the MLCT state structure of Bis(2,9-dimethyl-1,10-phenanthroline) Copper(I) [Cu(I)(dmp)2]+, and 3) triplet state molecular structures of metalloporphyrins. These studies not only prove the feasibility of the technique, but also gain structural information that otherwise will not be available. Future studies include probing transient structures in electron donor-acceptor complexes and optical polarization selected XAFS (OPS-XAFS) using the same technique with a 100-ps time resolution. This work is supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, U. S. Department of Energy, under contract W-31-109-Eng-38.

  4. Ultrafast Relaxation Dynamics of Photoexcited Zinc-Porphyrin: Electronic-Vibrational Coupling

    DOE PAGES

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

    2016-08-02

    Cyclic tetrapyrroles are the active core of compounds with crucial roles in living systems, such as hemoglobin and chlorophyll, and in technology as photocatalysts and light absorbers for solar energy conversion. Zinc-tetraphenylporphyrin (Zn-TPP) is a prototypical cyclic tetrapyrrole that has been intensely studied in past decades. Because of its importance for photochemical processes the optical properties are of particular interest, and, accordingly, numerous studies have focused on light absorption and excited-state dynamics of Zn-TPP. Relaxation after photoexcitation in the Soret band involves internal conversion that is preceded by an ultrafast process. This relaxation process has been observed by several groups.more » Until now, it has not been established if it involves a higher lying ”dark” state or vibrational relaxation in the excited S2 state. Here we combine high time resolution electronic and vibrational spectroscopy to show that this process constitutes vibrational relaxation in the anharmonic 2 potential.« less

  5. Distinguishing between plasmon-induced and photoexcited carriers in a device geometry

    PubMed Central

    Zheng, Bob Y.; Zhao, Hangqi; Manjavacas, Alejandro; McClain, Michael; Nordlander, Peter; Halas, Naomi J.

    2015-01-01

    The use of surface plasmons, charge density oscillations of conduction electrons of metallic nanostructures, to boost the efficiency of light-harvesting devices through increased light-matter interactions could drastically alter how sunlight is converted into electricity or fuels. These excitations can decay directly into energetic electron–hole pairs, useful for photocurrent generation or photocatalysis. However, the mechanisms behind plasmonic carrier generation remain poorly understood. Here we use nanowire-based hot-carrier devices on a wide-bandgap semiconductor to show that plasmonic carrier generation is proportional to internal field-intensity enhancement and occurs independently of bulk absorption. We also show that plasmon-induced hot electrons have higher energies than carriers generated by direct excitation and that reducing the barrier height allows for the collection of carriers from plasmons and direct photoexcitation. Our results provide a route to increasing the efficiency of plasmonic hot-carrier devices, which could lead to more efficient devices for converting sunlight into usable energy. PMID:26165521

  6. Two-Photon Photoexcited Photodynamic Therapy and Contrast Agent with Antimicrobial Graphene Quantum Dots.

    PubMed

    Kuo, Wen-Shuo; Chang, Chia-Yuan; Chen, Hua-Han; Hsu, Chih-Li Lilian; Wang, Jiu-Yao; Kao, Hui-Fang; Chou, Lawrence Chao-Shan; Chen, Yi-Chun; Chen, Shean-Jen; Chang, Wen-Tsan; Tseng, Shih-Wen; Wu, Ping-Ching; Pu, Ying-Chih

    2016-11-09

    A graphene quantum dot (GQD) used as the photosensitizer with high two-photon absorption in the near-infrared region, a large absolute cross section of two-photon excitation (TPE), strong two-photon luminescence, and impressive two-photon stability could be used for dual modality two-photon photodynamic therapy (PDT) and two-photon bioimaging with an ultrashot pulse laser (or defined as TPE). In this study, a GQD efficiently generated reactive oxygen species coupled with TPE, which highly increased the effective PDT ability of both Gram-positive and -negative bacteria, with ultralow energy and an extremely short photoexcitation time generated by TPE. Because of its two-photon properties, a GQD could serve as a promising two-photon contrast agent for observing specimens in depth in three-dimensional biological environments while simultaneously proceeding with PDT action to eliminate bacteria, particularly in multidrug-resistant (MDR) strains. This procedure would provide an efficient alternative approach to easily cope with MDR bacteria.

  7. Visualization of coherent nuclear motion between different geometries in photoexcited 2,4-difluorophenol

    NASA Astrophysics Data System (ADS)

    Ling, Fengzi; Li, Shuai; Song, Xinli; Tang, Ying; Wang, Yanmei; Zhang, Bing

    2017-04-01

    The coherent nuclear motion in photoexcited 2,4-difluorophenol (2,4-DFP) has been visualized in real time using femtosecond time-resolved ion-yield spectroscopy and time-resolved photoelectron imaging. A coherent vibrational packet is created by the simultaneous excitation of the out-of-plane bending modes in the first excited electronic state (S1) in 2,4-DFP. By virtue of the geometry change upon photoionization, the wave packets around the planar geometry are ionized exclusively with selective probe wavelengths, exhibiting the pronounced quantum beats superimposed on the parent-ion transients. Furthermore, photoionization signals of the planar and nonplanar geometries are both acquired in the photoelectron spectra but dispersed with respect to kinetic energy via resonances with different intermediate Rydberg states. The time dependences of the photoelectron peaks originating from the planar and nonplanar geometries exhibit the clear beats with similar periodicities but a phase shift of π rad, offering an unambiguous picture of the oscillating nuclear motion between the planar geometry and the nonplanar minimum.

  8. Semiclassical molecular dynamics simulations of intramolecular proton transfer in photoexcited 2-(2'-hydroxyphenyl)-oxazole

    NASA Astrophysics Data System (ADS)

    Guallar, Victor; Batista, Victor S.; Miller, William H.

    2000-12-01

    A full-dimensional excited state potential energy surface is constructed, and the proton transfer dynamics associated with the keto-enolic tautomerization reaction in photoexcited 2-(2'-hydroxyphenyl)-oxazole is simulated according to an approximate version of the semiclassical initial value representation method introduced by Miller and co-workers [V. Guallar, V. S. Batista, and W. H. Miller, J. Chem. Phys. 110, 9922 (1999)]. The full-dimensional potential energy surface is developed according to an ab initio reaction surface model obtained at the CIS level of quantum chemistry. Proton transfer is found to be substantially affected by isotopic substitution, and significantly coupled to the internal oxazole-hydroxyphenyl in-the-plane bending mode. The nascent tautomer is found to be stabilized primarily through vibrational energy redistribution into all of the remaining in-the-plane vibrational modes. The accuracy of the methodology is verified by reducing the dimensionality of the system and comparing our semiclassical results with full quantum mechanical calculations.

  9. Structural and electronic properties of photoexcited TiO2 nanoparticles from first principles.

    PubMed

    Nunzi, Francesca; Agrawal, Saurabh; Selloni, Annabella; De Angelis, Filippo

    2015-02-10

    The structure and energetics of excitons and individual electron and hole polarons in a model anatase TiO2 nanoparticle (NP) are investigated by means of Density Functional Theory (DFT) and Time Dependent (TD)-DFT calculations. The effect of the Hartree-Fock exchange (HF-exc) contribution in the description of TiO2 NPs with unpaired electrons is examined by comparing the results from semilocal and hybrid DFT functionals with different HF-exc percentages, including a long-range corrected hybrid functional. The performances of TD-DFT and ground state (SCF) DFT approaches in the description of the photoexcited polaron states in TiO2 NPs are also analyzed. Our results confirm that the HF-exc contribution is essential to properly describe the self-trapping of the charge carriers. They also suggest that long-range corrected functionals are needed to properly describe excited state relaxation in TiO2 NPs. TD-DFT geometry optimization of the lowest excited singlet and triplet states deliver photoluminescence values in close agreement with the experimental data.

  10. Kh a 1,2 hyperesatellites of 3d transition metals and their photoexcitation energy dependence.

    SciTech Connect

    Diamant, R.; Kao, C.; Huotari, S; Hamalainen, K; Sharon, R; Deutsch, M.

    2009-06-25

    Hollow atoms in which the K shell is empty while the outer shells are populated allow studying a variety of important and unusual properties of atoms. The diagram x-ray emission lines of such atoms, the K{sup h} {alpha}{sub 1,2} hypersatellites (HSs), were measured for the 3d transition metals, Z = 23-30, with a high energy resolution using photoexcitation by monochromatized synchrotron radiation. Good agreement with ab initio relativistic multiconfigurational Dirac-Fock calculations was found. The measured HS intensity variation with the excitation energy yields accurate values for the excitation thresholds, excludes contributions from shake-up processes, and indicates domination near threshold of a nonshake process. The Z variation of the HS shifts from the diagram line K{alpha}{sub 1,2}, the K{sup h}{alpha}{sub 1}-K{sup h}{alpha}{sub 2} splitting, and the K{sup h}{alpha}{sub 1}/K{sup h}{alpha}{sub 2} intensity ratio, derived from the measurements, are also discussed with a particular emphasis on the QED corrections and Breit interaction.

  11. Long-lived photoexcitations in intercalated, partially and predominantly non-intercalated polymer:fullerene blends

    NASA Astrophysics Data System (ADS)

    Dou, Fei; Buchaca-Domingo, Ester; Sakowicz, Maciej; Zhang, Xinping; Stingelin, Natalie; Silva, Carlos

    2013-09-01

    In this work, we study the nature of long-lived photoexcitations in intercalated, partially and predominantly non-intercalated semicrystalline poly(2,5-bis(3-tetradecyl-thiophen-2-yl)thieno [3,2,-b]thiophene) (pBTTT):phenyl-C61 -butyric acid methyl ester (PC61BM) blend films by quasi-steady-state photoinduced absorption (PIA) spectroscopy. We find that polarons are generated in these microstructures. However, the polarons generated in partially and predominantly non-intercalated films (1.7 eV) are at higher energy than in intercalated film (1.4 eV). After comparing with the polaron generation in neat pBTTT polymer film, we propose that the polarons generated in partially and predominantly non-intercalated film are delocalized charges, and the polarons generated in intercalated film are localized charges. Furthermore, we also find that the polarons generated in the partially non-intercalated film have the longest lifetime.

  12. Photoexcitation and Photochemical Stability of Organic Photovoltaic Materials from First Principles

    NASA Astrophysics Data System (ADS)

    Sai, Na; Leung, Kevin

    2013-03-01

    The development of high efficiency organic photovoltaics (OPV) has recently become enabled by the synthesis of new conjugated polymers with low band gap that allow light absorption over a broader range of the spectrum. Stability of these new polymers, a key requirement for commercialization, has not yet received sufficient attention. Here, we report first-principles theoretical modeling of photo-induced degradation of OPV polymers carried out using ab-initio density functional theory (DFT). We report photooxidation routes and reaction products for reactive species including superoxide oxygen anions and hydroxyl groups interacting with the standard workhorse OPV polymer, poly(3-hexyl-thiophene) (P3HT). We discuss theoretical issues and challenges affecting the modeling such reactions in OPV polymers. We also discuss the application of theoretical methods to low-band-gap polymers, and in particular, the effect of the chemical substitution on the photoexcitation properties of these new polymers. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Deparment of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This work is supported by the Energy Frontier Research Center funded by the U.S. DOE Office of Basic Energy Sciences under Award number DE-SC0001091.

  13. Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B12

    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 B12, 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 contributions andmore » 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–NIm 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

  14. Ultrafast reflectance of photoexcited Weyl and Dirac semimetals TaAs and ZrSiS

    NASA Astrophysics Data System (ADS)

    Weber, Christopher; Berggren, Bryan; Dani, Keshav; Ali, Mazhar; Parkin, Stuart; Schoop, Leslie; Lotsch, Bettina; Zhao, Lingxiao; Chen, Genfu

    We report ultrafast pump-probe and transient-grating (TG) measurements of the Weyl semimetal TaAs and the Dirac line-node semimetal ZrSiS, and contrast these results with prior measurements on the Dirac semimetal Cd3As2. After absorption of photons from the pump pulse, we monitor the samples' recovery to equilibrium by measuring the change in reflectance of a time-delayed probe pulse. For TaAs, the reflectance recovers in just 1.2 ps, significantly faster than the 3.1 ps measured in Cd3As2. This rapid recovery appears not to change when temperature is varied from 300 K to 8 K, when a magnetic field of order 0.3 T is applied, or when the excitation fluence is increased by a factor of 20. TG measurements allow us to assign the changes in reflectance to changes in either the dispersive (real) or absorptive (imaginary) parts of the index of refraction. Intriguingly, and in contrast to Cd3As2, the initial change in reflectance is caused by an abrupt reduction in the dispersive part, followed by a slower reduction in the absorptive part. For ZrSiS, the recovery after photoexcitation is even faster, at 0.3 ps. We will discuss the implications of these findings for carrier dynamics in topological semimetals.

  15. Spatially Resolved Photoexcited Charge-Carrier Dynamics in Phase-Engineered Monolayer MoS2

    DOE PAGES

    Yamaguchi, Hisato; Blancon, Jean-Christophe; Kappera, Rajesh; ...

    2014-12-18

    A fundamental understanding of the intrinsic optoelectronic properties of atomically thin transition metal dichalcogenides (TMDs) is crucial for its integration into high performance semiconductor devices. We investigate the transport properties of chemical vapor deposition (CVD) grown monolayer molybdenum disulfide (MoS2) under photo-excitation using correlated scanning photocurrent microscopy and photoluminescence imaging. We examined the effect of local phase transformation underneath the metal electrodes on the generation of photocurrent across the channel length with diffraction-limited spatial resolution. While maximum photocurrent generation occurs at the Schottky contacts of semiconducting (2H-phase) MoS2, after the metallic phase transformation (1T-phase), the photocurrent peak is observed towardsmore » the center of the device channel, suggesting a strong reduction of native Schottky barriers. Analysis using the bias and position dependence of the photocurrent indicates that the Schottky barrier heights are few meV for 1T- and ~200 meV for 2H-contacted devices. We also demonstrate that a reduction of native Schottky barriers in a 1T device enhances the photo responsivity by more than one order of magnitude, a crucial parameter in achieving high performance optoelectronic devices. The obtained results pave a pathway for the fundamental understanding of intrinsic optoelectronic properties of atomically thin TMDs where Ohmic contacts are necessary for achieving high efficiency devices with low power consumption.« less

  16. Photoexcited carrier trapping and recombination at Fe centers in GaN

    SciTech Connect

    Uždavinys, T. K.; Marcinkevičius, S.; Leach, J. H.; Evans, K. R.; Look, D. C.

    2016-06-07

    Fe doped GaN was studied by time-resolved photoluminescence (PL) spectroscopy. The shape of PL transients at different temperatures and excitation powers allowed discrimination between electron and hole capture to Fe{sup 3+} and Fe{sup 2+} centers, respectively. Analysis of the internal structure of Fe ions and intra-ion relaxation rates suggests that for high repetition rates of photoexciting laser pulses the electron and hole trapping takes place in the excited state rather than the ground state of Fe ions. Hence, the estimated electron and hole capture coefficients of 5.5 × 10{sup −8} cm{sup 3}/s and 1.8 × 10{sup −8} cm{sup 3}/s should be attributed to excited Fe{sup 3+} and Fe{sup 2+} states. The difference in electron capture rates determined for high (MHz) and low (Hz) (Fang et al., Appl. Phys. Lett. 107, 051901 (2015)) pulse repetition rates may be assigned to the different Fe states participating in the carrier capture. A weak temperature dependence of the electron trapping rate shows that the potential barrier for the multiphonon electron capture is small. A spectral feature observed at ∼420 nm is assigned to the radiative recombination of an electron in the ground Fe{sup 2+} state and a bound hole.

  17. Delocalisation of photoexcited triplet states probed by transient EPR and hyperfine spectroscopy

    NASA Astrophysics Data System (ADS)

    Richert, Sabine; Tait, Claudia E.; Timmel, Christiane R.

    2017-07-01

    Photoexcited triplet states play a crucial role in photochemical mechanisms: long known to be of paramount importance in the study of photosynthetic reaction centres, they have more recently also been shown to play a major role in a number of applications in the field of molecular electronics. Their characterisation is crucial for an improved understanding of these processes with a particular focus on the determination of the spatial distribution of the triplet state wavefunction providing information on charge and energy transfer efficiencies. Currently, active research in this field is mostly focussed on the investigation of materials for organic photovoltaics (OPVs) and organic light emitting diodes (OLEDs). As the properties of triplet states and their spatial extent are known to have a major impact on device performance, a detailed understanding of the factors governing triplet state delocalisation is at the basis of the further development and improvement of these devices. Electron Paramagnetic Resonance (EPR) has proven a valuable tool in the study of triplet state properties and both experimental methods as well as data analysis and interpretation techniques have continuously improved over the last few decades. In this review, we discuss the theoretical and practical aspects of the investigation of triplet states and triplet state delocalisation by transient continuous wave and pulse EPR and highlight the advantages and limitations of the presently available techniques and the current trends in the field. Application of EPR in the study of triplet state delocalisation is illustrated on the example of linear multi-porphyrin chains designed as molecular wires.

  18. Photoexcited Properties of Tin Sulfide Nanosheet-Decorated ZnO Nanorod Heterostructures

    NASA Astrophysics Data System (ADS)

    Liang, Yuan-Chang; Lung, Tsai-Wen; Xu, Nian-Cih

    2017-04-01

    In this study, ZnO-Sn2S3 core-shell nanorod heterostructures were synthesized by sputtering Sn2S3 shell layers onto ZnO rods. The Sn2S3 shell layers consisted of sheet-like crystallites. A structural analysis revealed that the ZnO-Sn2S3 core-shell nanorod heterostructures were highly crystalline. In comparison with ZnO nanorods, the ZnO-Sn2S3 nanorods exhibited a broadened optical absorption edge that extended to the visible light region. The ZnO-Sn2S3 nanorods exhibited substantial visible photodegradation efficiency of methylene blue organic dyes and high photoelectrochemical performance under light illumination. The unique three-dimensional sheet-like Sn2S3 crystallites resulted in the high light-harvesting efficiency of the nanorod heterostructures. Moreover, the efficient spatial separation of photoexcited carriers, attributable to the band alignment between ZnO and Sn2S3, accounted for the superior photocatalytic and photoelectrochemical properties of the ZnO-Sn2S3 core-shell nanorod heterostructures.

  19. Femtosecond pulses and dynamics of molecular photoexcitation: RbCs example

    NASA Astrophysics Data System (ADS)

    Londoño, B. E.; Derevianko, A.; Mahecha, J. E.; Crubellier, A.; Luc-Koenig, E.

    2012-03-01

    We investigate the dynamics of molecular photoexcitation by unchirped femtosecond laser pulses using RbCs as a model system. This study is motivated by a goal of optimizing a two-color scheme of transferring vibrationally excited ultracold molecules to their absolute ground state. In this scheme the molecules are initially produced by photoassociation or magnetoassociation in bound vibrational levels close to the first dissociation threshold. We analyze here the first step of the two-color path as a function of pulse intensity from the low-field to the high-field regime. We use two different approaches, a global one, the “wave-packet” method, and a restricted one, the “level-by-level” method, where the number of vibrational levels is limited to a small subset. The comparison between the results of the two approaches allows one to gain qualitative insights into the complex dynamics of the high-field regime. In particular, we emphasize the nontrivial and important role of far-from-resonance levels which are adiabatically excited through “vertical” transitions with a large Franck-Condon factor. We also point out the spectacular excitation blockade due to the presence of a quasidegenerate level in the lower electronic state. We conclude that selective transfer with femtosecond pulses is possible in the low-field regime only. Finally, we extend our single-pulse analysis and examine population transfer induced by coherent trains of low-intensity femtosecond pulses.

  20. Optically controlled coherent X-ray radiations from photo-excited nanotubes

    NASA Astrophysics Data System (ADS)

    Shin, Young-Min

    2017-09-01

    Relativistic electrons propagating through a plasmonic medium such as photo-excited plasma channels with negative permittivities undergo betatron motions, emitting photons at oscillating resonance modes. The similar betatron radiation can be generated in X-ray regimes from electrons transported through optically pumped carbon nanotubes (CNTs). The X-ray radiation condition of 0.5 and 6 MeV electrons phase-matched with plasmonic waves in CNTs is analyzed with a theoretical model of the CNT dispersion relation. Based on the dispersion analysis, radiation intensities and the brilliance of the coherent X-ray source averaged over the pulse duration are estimated using a typical range of system parameters of conventional electron sources and tabletop femtosecond lasers. The assessment indicates that the average brilliance of the harmonic radiation can reach 1010-1013 photons/s/mm2/mrad2/0.1%BW with 0.5-6 MeV electrons and X-ray energy up to a few keV.

  1. Nonequilibrium dynamics of photoexcited electrons in graphene: Collinear scattering, Auger processes, and the impact of screening

    NASA Astrophysics Data System (ADS)

    Tomadin, Andrea; Brida, Daniele; Cerullo, Giulio; Ferrari, Andrea C.; Polini, Marco

    2013-07-01

    We present a combined analytical and numerical study of the early stages (sub-100-fs) of the nonequilibrium dynamics of photoexcited electrons in graphene. We employ the semiclassical Boltzmann equation with a collision integral that includes contributions from electron-electron (e-e) and electron-optical phonon interactions. Taking advantage of circular symmetry and employing the massless Dirac fermion (MDF) Hamiltonian, we are able to perform an essentially analytical study of the e-e contribution to the collision integral. This allows us to take particular care of subtle collinear scattering processes—processes in which incoming and outgoing momenta of the scattering particles lie on the same line—including carrier multiplication (CM) and Auger recombination (AR). These processes have a vanishing phase space for two-dimensional MDF bare bands. However, we argue that electron-lifetime effects, seen in experiments based on angle-resolved photoemission spectroscopy, provide a natural pathway to regularize this pathology, yielding a finite contribution due to CM and AR to the Coulomb collision integral. Finally, we discuss in detail the role of physics beyond the Fermi golden rule by including screening in the matrix element of the Coulomb interaction at the level of the random phase approximation (RPA), focusing in particular on the consequences of various approximations including static RPA screening, which maximizes the impact of CM and AR processes, and dynamical RPA screening, which completely suppresses them.

  2. Photoexcited Carrier Dynamics of Cu2S Thin Films

    SciTech Connect

    Riha, Shannon C.; Schaller, Richard D.; Gosztola, David J.; Wiederrecht, Gary P.; Martinson, Alex B. F.

    2014-11-11

    Copper sulfide is a simple binary material with promising attributes for low-cost thin film photovoltaics. However, stable Cu2S-based device efficiencies approaching 10% free from cadmium have yet to be realized. In this paper, transient absorption spectroscopy is used to investigate the dynamics of the photoexcited state of isolated Cu2S thin films prepared by atomic layer deposition or vapor-based cation exchange of ZnS. While a number of variables including film thickness, carrier concentration, surface oxidation, and grain boundary passivation were examined, grain structure alone was found to correlate with longer lifetimes. A map of excited state dynamics is deduced from the spectral evolution from 300 fs to 300 μs. Finally, revealing the effects of grain morphology on the photophysical properties of Cu2S is a crucial step toward reaching high efficiencies in operationally stable Cu2S thin film photovoltaics.

  3. Photoexcitation of the O-intermediate in bacteriorhodopsin mutant L93A.

    PubMed

    Tóth-Boconádi, R; Keszthelyi, L; Stoeckenius, W

    2003-06-01

    During the extended lifetime of the O-state in bacteriorhodopsin (bR) mutant L93A, two substates have been distinguished. The first O-intermediate (OI) is in rapid equilibrium with N and apparently still has a 13-cis chromophore. OI undergoes a photoreaction with a small absorbance change, positive charge transport in the pumping direction, and proton release and uptake. None of these effects was detected after photoexcitation of the late O (OII). The most likely interpretation of the effects seen is an accelerated return of the molecule from the OI- to the bR-state. However, with a lifetime approximately 140 ms, the reaction cannot account for the observed high pumping efficiency of the mutant under continuous illumination. We suggest that OII corresponds to the O-intermediate with a twisted all-trans chromophore seen in the photocycle of wild-type bR, where the 13-cis OI-intermediate under the usual conditions does not accumulate in easily detectable amounts and, therefore, has generally been overlooked. Both the OI- and OII-decays are apparently strongly inhibited in the mutant.

  4. Common thresholds and the role of deformations in the photoexcitation of isomers

    SciTech Connect

    Collins, C.B.; Carroll, J.J.; Taylor, K.N.; Richmond, D.G.; Sinor, T.W. ); Huber, M.; von Neumann-Cosel, P.; Richter, A.; Ziegler, W. )

    1992-09-01

    Photoexcitations of the short-lived isomers {sup 167}Er{sup {ital m}}, {ital T}{sub 1/2}=2.28 s, {sup 179}Hf{sup {ital m}}, {ital T}{sub 1/2}=18.68 s, {sup 191}Ir{sup {ital m}}, {ital T}{sub 1/2}=4.94 s, and {sup 197}Au{sup {ital m}}, {ital T}{sub 1/2}=7.8 s, were produced with bremsstrahlung from the superconducting Darmstadt linear accelerator. Excitation functions were measured for the population of these isomers by ({gamma},{gamma}{prime}) reactions between 2 and 7 MeV. They indicated that the isomers were excited by resonant absorption through isolated intermediate states having integrated cross sections in excess of 10{sup {minus}26} cm{sup 2} keV, i.e., values about 1000 times larger than most ({gamma},{gamma}{prime}) activation reactions reported previously although they were comparable to those reported earlier for the depopulating reaction {sup 180}Ta{sup {ital m}}({gamma},{gamma}{prime}){sup 180}Ta. In all four nuclei a common onset was observed near 2.5 MeV for intermediate states with strengths much larger than those occurring at lower energies. The summed cross sections exhibit a clear correlation with the ground state deformations.

  5. Common thresholds and the role of deformations in the photoexcitation of isomers

    SciTech Connect

    Carroll, J.J.; Collins, C.B.; Taylor, K.N.

    1992-12-01

    The photoexcitation of the isomers of {sup 167}Er, {sup 179}Hf, {sup 191}Ir and {sup 197}Au by ({gamma},{gamma}{prime}) reactions was studied using bremsstrahlung from the injector to the superconducting Darmstadt linear accelerator. Over 1800 irradiations were performed to determine the excitation energies of gateway states mediating the reactions in the range from 2 to 5 MeV. Incident photon spectra were characterized with the EGS4 coupled electron-photon transport code and were cross-checked against the calibration reaction {sup 115}In({gamma},{gamma}{prime}){sup 115}In{sup m}. Large integrated cross sections of the gateway levels were obtained with values which varied from 10{sup {minus}26} to 10{sup {minus}25} cm{sup 2} keV, on the same order-of-magnitude as those found for intermediate states for the deexcitation reaction {sup 180}Ta{sup m}({gamma},{gamma}{prime}){sup 180}Ta studied previously. The reduced transition probabilities deduced from these measurements show a clear correlation with the ground-state deformations of the nuclides. The slow variation of gateway parameters for nuclei neighboring {sup 180}Ta provides important support to models for an optically pumped gamma-ray laser.

  6. Amoeba-inspired nanoarchitectonic computing: solving intractable computational problems using nanoscale photoexcitation transfer dynamics.

    PubMed

    Aono, Masashi; Naruse, Makoto; Kim, Song-Ju; Wakabayashi, Masamitsu; Hori, Hirokazu; Ohtsu, Motoichi; Hara, Masahiko

    2013-06-18

    Biologically inspired computing devices and architectures are expected to overcome the limitations of conventional technologies in terms of solving computationally demanding problems, adapting to complex environments, reducing energy consumption, and so on. We previously demonstrated that a primitive single-celled amoeba (a plasmodial slime mold), which exhibits complex spatiotemporal oscillatory dynamics and sophisticated computing capabilities, can be used to search for a solution to a very hard combinatorial optimization problem. We successfully extracted the essential spatiotemporal dynamics by which the amoeba solves the problem. This amoeba-inspired computing paradigm can be implemented by various physical systems that exhibit suitable spatiotemporal dynamics resembling the amoeba's problem-solving process. In this Article, we demonstrate that photoexcitation transfer phenomena in certain quantum nanostructures mediated by optical near-field interactions generate the amoebalike spatiotemporal dynamics and can be used to solve the satisfiability problem (SAT), which is the problem of judging whether a given logical proposition (a Boolean formula) is self-consistent. SAT is related to diverse application problems in artificial intelligence, information security, and bioinformatics and is a crucially important nondeterministic polynomial time (NP)-complete problem, which is believed to become intractable for conventional digital computers when the problem size increases. We show that our amoeba-inspired computing paradigm dramatically outperforms a conventional stochastic search method. These results indicate the potential for developing highly versatile nanoarchitectonic computers that realize powerful solution searching with low energy consumption.

  7. Photoexcited State Confinement in Two-Dimensional Crystalline Anthracene Monolayer at Room Temperature.

    PubMed

    Shibuta, Masahiro; Hirata, Naoyuki; Eguchi, Toyoaki; Nakajima, Atsushi

    2017-04-13

    Organic thin film electronics place a high demand on bottom-up technology to form a two-dimensionally (2D) functional unit consisting of a single molecular crystalline layer bound to a layered structure. As the strong interaction between a substrate and molecules makes it difficult to evaluate the electronic properties of organic films, the nature of electronic excited states has not been elucidated. Here, we study a 2D crystalline anthracene monolayer electronically decoupled by alkanethiolates on a gold substrate using scanning tunneling microscopy and time-resolved two-photon photoemission spectroscopy and unravel the geometric/electronic structures and excited electron dynamics. Our data reveal that dispersive 2D excited electrons on the surface can be highly coupled with an annihilation of nondispersive excitons that facilitate electron emission with vibronic interaction. Our results provide a fundamental framework for understanding photoexcited anthracene monolayer and show how the coupling between dispersive and nondispersive excited states may assist charge separation in crystalline molecular layers.

  8. Polarized XANES Monitors Femtosecond Structural Evolution of Photoexcited Vitamin B12.

    PubMed

    Miller, Nicholas A; Deb, Aniruddha; Alonso-Mori, Roberto; Garabato, Brady D; Glownia, James M; Kiefer, Laura M; Koralek, Jake; Sikorski, Marcin; Spears, Kenneth G; Wiley, Theodore E; Zhu, Diling; Kozlowski, Pawel M; Kubarych, Kevin J; Penner-Hahn, James E; Sension, Roseanne J

    2017-02-08

    Ultrafast, polarization-selective time-resolved X-ray absorption near-edge structure (XANES) was used to characterize the photochemistry of vitamin B12, 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 contributions 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-NIm bond on a 110 fs time scale is followed by corrin ring relaxation on a 260 fs time scale. These observations expose features of the potential energy surfaces controlling cobalamin reactivity and deactivation.

  9. Photoexcited electron and hole dynamics in semiconductor quantum dots: phonon-induced relaxation, dephasing, multiple exciton generation and recombination

    NASA Astrophysics Data System (ADS)

    Hyeon-Deuk, Kim; Prezhdo, Oleg V.

    2012-09-01

    Photoexcited dynamics of electrons and holes in semiconductor quantum dots (QD), including phonon-induced relaxation, multiple exciton generation, fission and recombination (MEG, MEF and MER), were simulated by combining ab initio time-dependent density functional theory and non-adiabatic molecular dynamics. These nonequilibrium phenomena govern the optical properties and photoexcited dynamics of QDs, determining the branching between electronic processes and thermal energy losses. Our approach accounts for QD size and shape as well as defects, core-shell distribution, surface ligands and charge trapping, which significantly influence the properties of photoexcited QDs. The method creates an explicit time-domain representation of photoinduced processes and describes various kinetic regimes owing to the non-perturbative treatment of quantum dynamics. QDs of different sizes and materials, with and without ligands, are considered. The simulations provide direct evidence that the high-frequency ligand modes on the QD surface play a pivotal role in the electron-phonon relaxation, MEG, MEF and MER. The insights reported here suggest novel routes for controlling the photoinduced processes in semiconductor QDs and lead to new design principles for increasing the efficiencies of photovoltaic devices.

  10. Alterations of transmembrane currents in frog atrial heart muscle induced by photoexcited gymnochrome A purified from the crinoid, Gymnochrinus richeri.

    PubMed

    Sauviat, M P; Benoit, A G; Debitus, C; Pouny, I; Laurent, D

    2001-08-01

    The effects of gymnochrome A were tested on the electrical activity of the frog atrial heart muscle. Gymnochrome A (1-5 microM) did not alter the resting potential. Gymnochrome A (5 microM) slowed the initial depolarizing phase of the spontaneously beating action potential. Under voltage-clamp conditions gymnochrome A (5 microM) did not affect the electrical constant of the membrane and the kinetic parameters of the peak Na+ current (INa) recorded in the Ringer solution containing tetraethylammonium (2 mM) and Cd2+ (1 mM) but shifted the membrane potential at which the current both activated and reached its maximal value toward more negative membrane potentials. It did not alter the reversal potential for INa, indicating that the selectivity of the Na+ channels had not changed. These observations suggest that gymnochrome A binds to the membrane and shifts the activation of INa on the voltage axis by modifying the free negative fixed charges present at the membrane surface rather than by occupying a specific site on the Na+ channel. Photoexcited gymnochrome A transiently triggered an early outward current which lengthened the time-to-peak of INa and decreased its amplitude. In addition, photoexcited gymnochrome A blocked the background K+ current. This is, to our knowledge, the first time that such effects are reported on the cardiac muscle. These observations suggest that the photoexcitation of gymnochrome produces physico-chemical effects which lead to intracellular changes. Further experiments are required to determine their nature.

  11. Ultrafast relaxation dynamics of photoexcited Dirac fermions in the three-dimensional Dirac semimetal C d3A s2

    NASA Astrophysics Data System (ADS)

    Lu, Wei; Ge, Shaofeng; Liu, Xuefeng; Lu, Hong; Li, Caizhen; Lai, Jiawei; Zhao, Chuan; Liao, Zhimin; Jia, Shuang; Sun, Dong

    2017-01-01

    Three-dimensional (3D) Dirac semimetals that can be seen as 3D analogues of graphene have attracted enormous interest in research recently. In order to apply these ultra-high-mobility materials in future electronic/optoelectronic devices, it is crucial to understand the relaxation dynamics of photoexcited carriers and their coupling with lattice. In this paper, we report ultrafast transient reflection measurements of the photoexcited carrier dynamics in cadmium arsenide (C d3A s2 ), which is one of the most stable Dirac semimetals that have been confirmed experimentally. By using the low-energy probe photon of 0.3 eV, we probed the dynamics of the photoexcited carriers that are Dirac-Fermi-like approaching the Dirac point. We systematically studied the transient reflection on bulk and nanoplate samples that have different doping intensities by tuning the probe wavelength, pump power, and lattice temperature and find that the dynamical evolution of carrier distributions can be retrieved qualitatively by using a two-temperature model. This result is very similar to that of graphene, but the carrier cooling through the optical phonon couplings is slower and lasts over larger electron temperature range because the optical phonon energies in C d3A s2 are much lower than those in graphene.

  12. Deep Earthquakes.

    ERIC Educational Resources Information Center

    Frohlich, Cliff

    1989-01-01

    Summarizes research to find the nature of deep earthquakes occurring hundreds of kilometers down in the earth's mantle. Describes further research problems in this area. Presents several illustrations and four references. (YP)

  13. Layer-dependent Debye temperature and thermal expansion of Ru(0001) by means of high-energy resolution core-level photoelectron spectroscopy

    SciTech Connect

    Ferrari, Eugenio; Galli, Lorenzo; Miniussi, Elisa; Morri, Maurizio; Panighel, Mirko; Ricci, Maria; Lacovig, Paolo; Lizzit, Silvano; Baraldi, Alessandro

    2010-11-15

    The layer-dependent Debye temperature of Ru(0001) is determined by means of high-energy resolution core-level photoelectron spectroscopy measurements. The possibility to disentangle three different components in the Ru 3d{sub 5/2} spectrum of Ru(0001), originating from bulk, first-, and second-layer atoms, allowed us to follow the temperature evolution of their photoemission line shapes and binding energies. Temperature effects were detected, namely, a lattice thermal expansion and a layer-dependent phonon broadening, which was interpreted within the framework of the Hedin-Rosengren formalism based on the Debye theory. The resulting Debye temperature of the top-layer atoms is 295{+-}10 K, lower than that of the bulk (T=668{+-}5 K) and second-layer (T=445{+-}10 K) atoms. While these results are in agreement with the expected phonon softening at the surface, we show that a purely harmonic description of the motion of the surface atoms is not valid, since anharmonic effects contribute significantly to the position and line shape of the different core-level components.

  14. Structural origin of Si-2p core-level shifts from Si(100)-c[4x2] surface: A spectral x-ray photoelectron diffraction study

    SciTech Connect

    Chen, X.; Tonner, B.P.; Denlinger, J.

    1997-04-01

    The authors have performed angle-resolved x-ray photoelectron diffraction (XPD) from a Si(100)-c(4x2) surface to study the structural origin of Si-2p core-level shifts. In the experiment, the highly resolved surface Si-2p core-level spectra were measured as a fine grid of hemisphere and photon energies, using the SpectroMicroscopy Facility {open_quotes}ultraESCA{close_quotes} instrument. By carefully decomposing the spectra into several surface peaks, the authors are able to obtain surface-atom resolved XPD patterns. Using a multiple scattering analysis, they derived a detailed atomic model for the Si(100)-c(4x2) surface. In this model, the asymmetric dimers were found tilted by 11.5 plus/minus 2.0 degrees with bond length of 2.32 plus/minus 0.05{angstrom}. By matching model XPD patterns to experiment, the authors can identify which atoms in the reconstructed surface are responsible for specific photoemission lines in the 2p spectrum.

  15. Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine

    NASA Astrophysics Data System (ADS)

    Sadybekov, Arman; Krylov, Anna I.

    2017-07-01

    A theoretical approach for calculating core-level states in condensed phase is presented. The approach is based on the equation-of-motion coupled-cluster (EOM-CC) theory and effective fragment potential (EFP) method. By introducing approximate treatment of double excitations in the EOM-CC with single and double substitutions ansatz, we address poor convergence issues that are encountered for the core-level states and significantly reduce computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to reference systems, are reproduced reasonably well. By using different protonation forms of solvated glycine as a benchmark system, we show that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of a solvent, such as within EFP framework, is essential for achieving quantitative accuracy.

  16. Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine

    DOE PAGES

    Sadybekov, Arman; Krylov, Anna I.

    2017-07-07

    A theoretical approach for calculating core-level states in condensed phase is presented. The approach is based on equation-of-motion coupled-cluster theory (EOMCC) and effective fragment potential (EFP) method. By introducing an approximate treatment of double excitations in the EOM-CCSD (EOM-CC with single and double substitutions) ansatz, we address poor convergence issues that are encountered for the core-level states and significantly reduce computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to reference systems, are reproduced reasonably well. By using different protonation formsmore » of solvated glycine as a benchmark system, we show that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of solvent, such as EFP, is essential for achieving quantitative accuracy.« less

  17. Core-level spectra and binding energies of transition metal nitrides by non-destructive x-ray photoelectron spectroscopy through capping layers

    NASA Astrophysics Data System (ADS)

    Greczynski, G.; Primetzhofer, D.; Lu, J.; Hultman, L.

    2017-02-01

    We present the first measurements of x-ray photoelectron spectroscopy (XPS) core level binding energies (BE:s) for the widely-applicable group IVb-VIb polycrystalline transition metal nitrides (TMN's) TiN, VN, CrN, ZrN, NbN, MoN, HfN, TaN, and WN as well as AlN and SiN, which are common components in the TMN-based alloy systems. Nitride thin film samples were grown at 400 °C by reactive dc magnetron sputtering from elemental targets in Ar/N2 atmosphere. For XPS measurements, layers are either (i) Ar+ ion-etched to remove surface oxides resulting from the air exposure during sample transfer from the growth chamber into the XPS system, or (ii) in situ capped with a few nm thick Cr or W overlayers in the deposition system prior to air-exposure and loading into the XPS instrument. Film elemental composition and phase content is thoroughly characterized with time-of-flight elastic recoil detection analysis (ToF-E ERDA), Rutherford backscattering spectrometry (RBS), and x-ray diffraction. High energy resolution core level XPS spectra acquired with monochromatic Al Kα radiation on the ISO-calibrated instrument reveal that even mild etching conditions result in the formation of a nitrogen-deficient surface layer that substantially affects the extracted binding energy values. These spectra-modifying effects of Ar+ ion bombardment increase with increasing the metal atom mass due to an increasing nitrogen-to-metal sputter yield ratio. The superior quality of the XPS spectra obtained in a non-destructive way from capped TMN films is evident from that numerous metal peaks, including Ti 2p, V 2p, Zr 3d, and Hf 4f, exhibit pronounced satellite features, in agreement with previously published spectra from layers grown and analyzed in situ. In addition, the N/metal concentration ratios are found to be 25-90% higher than those obtained from the corresponding ion-etched surfaces, and in most cases agree very well with the RBS and ToF-E ERDA values. The N 1 s BE:s extracted from

  18. Photoexcited Surface Frustrated Lewis Pairs for Heterogeneous Photocatalytic CO2 Reduction.

    PubMed

    Ghuman, Kulbir Kaur; Hoch, Laura B; Szymanski, Paul; Loh, Joel Y Y; Kherani, Nazir P; El-Sayed, Mostafa A; Ozin, Geoffrey A; Singh, Chandra Veer

    2016-02-03

    In this study we investigated, theoretically and experimentally, the unique photoactive behavior of pristine and defected indium oxide surfaces providing fundamental insights into their excited state properties as well as an explanation for the experimentally observed enhanced activity of defected indium oxide surfaces for the gas-phase reverse water gas shift reaction, CO2 + H2 + hν→ CO + H2O in the light compared to the dark. To this end, a detailed excited-state study of pristine and defected forms of indium oxide (In2O3, In2O3-x, In2O3(OH)y and In2O3-x(OH)y) surfaces was performed using time dependent density functional theory (TDDFT) calculations, the results of which were supported experimentally by transient absorption spectroscopy and photoconductivity measurements. It was found that the surface frustrated Lewis pairs (FLPs) created by a Lewis acidic coordinately unsaturated surface indium site proximal to an oxygen vacancy and a Lewis basic surface hydroxide site in In2O3-x(OH)y become more acidic and basic and hence more active in the ES compared to the GS. This provides a theoretical mechanism responsible for the enhanced activity and reduced activation energy of the photochemical reverse water gas shift reaction observed experimentally for In2O3-x(OH)y compared to the thermochemical reaction. This fundamental insight into the role of photoexcited surface FLPs for catalytic CO2 reduction could lead to improved photocatalysts for solar fuel production.

  19. Unraveling the mechanisms of nonradiative deactivation in model peptides following photoexcitation of a phenylalanine residue.

    PubMed

    Mališ, Momir; Loquais, Yohan; Gloaguen, Eric; Biswal, Himansu S; Piuzzi, François; Tardivel, Benjamin; Brenner, Valérie; Broquier, Michel; Jouvet, Christophe; Mons, Michel; Došlić, Nađa; Ljubić, Ivan

    2012-12-19

    The mechanisms of nonradiative deactivation of a phenylalanine residue after near-UV photoexcitation have been investigated in an isolated peptide chain model (N-acetylphenylalaninylamide, NAPA) both experimentally and theoretically. Lifetime measurements at the origin of the first ππ* state of jet-cooled NAPA molecules have shown that (i) among the three most stable conformers of the molecule, the folded conformer NAPA B is ∼50-times shorter lived than the extended major conformer NAPA A and (ii) this lifetime is virtually insensitive to deuteration at the NH(2) and NH sites. Concurrent time-dependent density functional theory (TDDFT) based nonadiabatic dynamics simulations in the full dimensionality, carried out for the NAPA B conformer, provided direct insights on novel classes of ultrafast deactivation mechanisms, proceeding through several conical intersections and leading in fine to the ground state. These mechanisms are found to be triggered either (i) by a stretch of the N(Phe)H bond, which leads to an H-transfer to the ring, or (ii) by specific backbone amide distortions. The potential energy surfaces of the NAPA conformers along these critical pathways have been characterized more accurately using the coupled cluster doubles (CC2) method and shown to exhibit barriers that can be overcome with moderate excess energies. These results analyzed in the light of the experimental findings enabled us to assign the short lifetime of NAPA B conformer to a number of easily accessible exit channels from the initial ππ* surface, most importantly the one involving a transfer of electronic excitation to an nπ* surface, induced by distortions of the backbone peptide bond.

  20. Photodissociation and photoexcitation of simple molecules with 1576 A f2 laser

    NASA Astrophysics Data System (ADS)

    Slanger, T. G.; Taherian, M. R.

    The Fluorine laser, operating at 1576 A, is the shortest wavelength laser with which one photon photochemical experiments are currently practical. This paper studies experiments carried out on C2N2 and on NO, the former case involving photodissociation, the latter, photoexcitation. At 1576 A, photodissociation of C2N2 leads to production of CN(A 2Pi) and CN(X2 Sigma(+)), with the CN(A) being produced in a range of vibrational levels, up to the thermodynamic limit of v=5. Radiative lifetimes have been measured for each of the six levels, and the lifetimes become shorter with increasing v, which agrees with theoretical predictions, but with no previous experimental studies. Rates coefficients for quenching the CN(A) state by the parent molecule show a correlation with the size of the energy gap between the A level and the closest lower X level, although the effect is linear and not exponetial in energy. The laser radiation is resonant with a transition in the B'-X band of NO. This results, in the collision-free case, in emission in three band systems, B' and B, whereas upon He addition, several other band systems appear. We have determined which rotational levels are involved in the initial step, and find the match to be within 0.25/cm of resonance. The branching ratio between the B'-X and B'-B systems has been found to be 155. The resonance between the laser radiation and the NO transition establishes NO as a unique monitor of the laser power.

  1. Relaxation Process of Photoexcited meso-Naphthylporphyrins while Interacting with DNA and Singlet Oxygen Generation.

    PubMed

    Hirakawa, Kazutaka; Taguchi, Makoto; Okazaki, Shigetoshi

    2015-10-15

    Electron donor-connecting cationic porphyrins meso-(1-naphthyl)-tris(N-methyl-p-pyridinio)porphyrin (1-NapTMPyP) and meso-(2-naphthyl)-tris(N-methyl-p-pyridinio)porphyrin (2-NapTMPyP) were designed and synthesized. DFT calculations speculate that the photoexcited states of 1- and 2-NapTMPyPs can be deactivated via intramolecular electron transfer from the naphthyl moiety to the porphyrin moiety. However, the quenching effect through the intramolecular electron transfer is insufficient, possibly due to the orthogonal position of the electron donor and the porphyrin ring and the relatively small driving force: Gibbs energies are 0.11 and 0.07 eV for 1- and 2-NapTMPyPs, respectively. It was speculated that more than 0.3 eV of the driving force is required to realize effective electron transfer in similar electron-donor connecting porphyrin systems. These porphyrins aggregated around the DNA strand, accelerating the deactivation of their excited singlet state and decreasing their photosensitized singlet oxygen-generating activities. In the presence of a sufficiently large concentration of DNA, these porphyrins can bind to a DNA strand stably, leading to an increased fluorescence quantum yield and lifetime. Singlet oxygen generation was also suppressed by the aggregation of porphyrins around DNA. Although the quantum yield of singlet oxygen generation was recovered in the presence of sufficient DNA, the singlet oxygen generated by DNA-binding porphyrins was significantly smaller than that without DNA. These results suggest that DNA-binding drugs limit the generation of photosensitized singlet oxygen by quenching the DNA strand.

  2. Relaxation pathways of photoexcited iodide-methanol clusters: a computational investigation.

    PubMed

    Mak, Chun C; Peslherbe, Gilles H

    2014-06-26

    Upon photoexcitation of iodide-methanol clusters, I(-)(CH3OH)n, to a charge-transfer-to-solvent (CTTS) excited state, extensive relaxation was found to occur, accompanied by a convoluted modulation of the stability of the excited electron, which ultimately decreases substantially. In order to develop a molecular-level understanding of the relaxation processes of CTTS excited I(-)(CH3OH)n, high-level quantum chemical calculations are first used to investigate the ground, excited, and ionized states of I(-)(CH3OH)n (n = 2). Because of the relatively small size of I(-)(CH3OH)2, it was possible to characterize the contributions of solvent-solvent interactions to the stability of the CTTS excited cluster relative to dissociation into methanol, iodine, and a free electron, which exhibits a substantial dependence on the cluster geometric configuration. Ab initio molecular dynamics simulations of CTTS excited I(-)(CH3OH)3 are then performed to shed some light onto the nature of the relaxation pathways involved in the modulation of the stability of the excited electron in larger clusters. Simulation results suggest that separation of I and (CH3OH)3(-) accompanied by solvent reorganization in the latter can initially stabilize the excited electron, while gradual cluster fragmentation to I, (CH3OH)2(-), and CH3OH ultimately destabilizes it. This work shows, for the first time, that the inability of small CTTS excited I(-)(CH3OH)n to retain a solvated electron may be attributed to the limited hydrogen-bonding capacity of CH3OH, which increases the propensity for fragmentation to smaller clusters with lower excess-electron binding energies, and highlights the critical role of intricate molecular interactions in the electron solvation process.

  3. Relaxation dynamics of photoexcited resorcinol: internal conversion versus H atom tunnelling.

    PubMed

    Young, Jamie D; Staniforth, Michael; Chatterley, Adam S; Paterson, Martin J; Roberts, Gareth M; Stavros, Vasilios G

    2014-01-14

    The excited state dynamics of resorcinol (1,3-dihydroxybenzene) following UV excitation at a range of pump wavelengths, 278 ≥ λ ≥ 255 nm, have been investigated using a combination of time-resolved velocity map ion imaging and ultrafast time-resolved ion yield measurements coupled with complementary ab initio calculations. After excitation to the 1(1)ππ* state we extract a timescale, τ1, for excited state relaxation that decreases as a function of excitation energy from 2.70 ns to ~120 ps. This is assigned to competing relaxation mechanisms. Tunnelling beneath the 1(1)ππ*/(1)πσ* conical intersection, followed by coupling onto the dissociative (1)πσ* state, yields H atoms born with high kinetic energy (~5000 cm(-1)). This mechanism is in competition with an internal conversion process that is able to transfer population from the photoexcited 1(1)ππ* state back to a vibrationally excited ground state, S0*. When exciting between 264-260 nm a second decay component, τ2, is observed and we put forth several possible explanations as to the origins of τ2, including conformer specific dynamics. Excitation with 237 nm light (above the 1(1)ππ*/(1)πσ* conical intersection) yields high kinetic energy H atoms (~11,000 cm(-1)) produced in ~260 fs, in line with a mechanism involving ultrafast coupling between the 1(1)ππ* (or 2(1)ππ*) and (1)πσ* state followed by dissociation. The results presented highlight the profound effect the presence of additional functional groups, and more specifically the precise location of the functional groups, can have on the excited state dynamics of model heteroaromatic systems following UV excitation.

  4. Light to Electrons to Bonds: Imaging Water Splitting and Collecting Photoexcited Electrons

    NASA Astrophysics Data System (ADS)

    Leenheer, Andrew Jay

    Photoelectrochemical devices can store solar energy as chemical bonds in fuels, but more control over the materials involved is needed for economic feasibility. Both efficient capture of photon energy into electron energy and subsequent electron transfer and bond formation are necessary, and this thesis explores various steps of the process. To look at the electrochemical fuel formation step, the spatially-resolved reaction rate on a water-splitting electrode was imaged during operation at a few-micron scale using optical microscopy. One method involved localized excitation of a semiconductor photoanode and recording the growth rate of bubbles to determine the local reaction rate. A second method imaged the reactant profile with a pH-sensitive fluorophore in the electrolyte to determine the local three-dimensional pH profile at patterned electrocatalysts in a confocal microscope. These methods provide insight on surface features optimal for efficient electron transfer into fuel products. A second set of studies examined the initial process of photoexcited electron transport and collection. An independent method to measure the minority carrier diffusion length in semiconductor photoelectrodes was developed, in which a wedge geometry is back illuminated with a small scanned spot. The diffusion length can be determined from the exponential decrease of photocurrent with thickness, and the method was demonstrated on solid-state silicon wedge diodes, as well as tungsten oxide thin-film wedge photoanodes. Finally, the possibility of absorbing and collecting sub-bandgap illumination via plasmon-enhanced hot carrier internal photoemission was modeled to predict the energy conversion efficiency. The effect of photon polarization on emission yield was experimentally tested using gold nanoantennas buried in silicon, and the correlation was found to be small.

  5. Deep learning

    NASA Astrophysics Data System (ADS)

    Lecun, Yann; Bengio, Yoshua; Hinton, Geoffrey

    2015-05-01

    Deep learning allows computational models that are composed of multiple processing layers to learn representations of data with multiple levels of abstraction. These methods have dramatically improved the state-of-the-art in speech recognition, visual object recognition, object detection and many other domains such as drug discovery and genomics. Deep learning discovers intricate structure in large data sets by using the backpropagation algorithm to indicate how a machine should change its internal parameters that are used to compute the representation in each layer from the representation in the previous layer. Deep convolutional nets have brought about breakthroughs in processing images, video, speech and audio, whereas recurrent nets have shone light on sequential data such as text and speech.

  6. Deep earthquakes

    SciTech Connect

    Frohlich, C.

    1989-01-01

    Earthquakes are often recorded at depths as great as 650 kilometers or more. These deep events mark regions where plates of the earth's surface are consumed in the mantle. But the earthquakes themselves present a conundrum: the high pressures and temperatures at such depths should keep rock from fracturing suddenly and generating a tremor. This paper reviews the research on this problem. Almost all deep earthquakes conform to the pattern described by Wadati, namely, they generally occur at the edge of a deep ocean and define an inclined zone extending from near the surface to a depth of 600 kilometers of more, known as the Wadati-Benioff zone. Several scenarios are described that were proposed to explain the fracturing and slipping of rocks at this depth.

  7. Deep learning.

    PubMed

    LeCun, Yann; Bengio, Yoshua; Hinton, Geoffrey

    2015-05-28

    Deep learning allows computational models that are composed of multiple processing layers to learn representations of data with multiple levels of abstraction. These methods have dramatically improved the state-of-the-art in speech recognition, visual object recognition, object detection and many other domains such as drug discovery and genomics. Deep learning discovers intricate structure in large data sets by using the backpropagation algorithm to indicate how a machine should change its internal parameters that are used to compute the representation in each layer from the representation in the previous layer. Deep convolutional nets have brought about breakthroughs in processing images, video, speech and audio, whereas recurrent nets have shone light on sequential data such as text and speech.

  8. Deep Lysimeter

    DOEpatents

    Hubbell, Joel M.; Sisson, James B.

    2004-06-01

    A deep lysimeter including a hollow vessel having a chamber, a fill conduit extending into the chamber through apertures, a semi-permeable member mounted on the vessel and in fluid communication with the fill conduit, and a line connection for retrieving the lysimeter.

  9. Deep Trouble.

    ERIC Educational Resources Information Center

    Popke, Michael

    2002-01-01

    Discusses how the safety-related ruling by the National Federation of State High School Associations to eliminate the option of using 18-inch starting platforms in pools less than 4 feet deep may affect operators of swimming pools and the swim teams who use them. (EV)

  10. Deep Fish.

    PubMed

    Ishaq, Omer; Sadanandan, Sajith Kecheril; Wählby, Carolina

    2017-01-01

    Zebrafish ( Danio rerio) is an important vertebrate model organism in biomedical research, especially suitable for morphological screening due to its transparent body during early development. Deep learning has emerged as a dominant paradigm for data analysis and found a number of applications in computer vision and image analysis. Here we demonstrate the potential of a deep learning approach for accurate high-throughput classification of whole-body zebrafish deformations in multifish microwell plates. Deep learning uses the raw image data as an input, without the need of expert knowledge for feature design or optimization of the segmentation parameters. We trained the deep learning classifier on as few as 84 images (before data augmentation) and achieved a classification accuracy of 92.8% on an unseen test data set that is comparable to the previous state of the art (95%) based on user-specified segmentation and deformation metrics. Ablation studies by digitally removing whole fish or parts of the fish from the images revealed that the classifier learned discriminative features from the image foreground, and we observed that the deformations of the head region, rather than the visually apparent bent tail, were more important for good classification performance.

  11. Charge-Separation Kinetics of Photoexcited Oxygen Vacancies in ZnO Nanowire Field-Effect Transistors

    NASA Astrophysics Data System (ADS)

    Lu, Ming-Pei; Chen, Chieh-Wei; Lu, Ming-Yen

    2016-11-01

    Photoinduced atomic structural transitions of negative-U defects: neutral oxygen vacancies (VO 0 ), accompanied by lattice relaxation, can form ionized 1 + and 2 + vacancy defects in ZnO materials, giving rise to an optoelectronic phenomenon named "persistent photoconductivity," thereby limiting the applications of ZnO materials in optoelectronic fields. Nevertheless, very little is known about the kinetics of the separation-recombination interactions between an electron and an ionized oxygen vacancy, constituting a photoexcited charge pair, in nanoscale ZnO material systems, especially when considering the effect of electric fields. In this report, we describe the charge-separation kinetics of photoexcited VO 0 defects in ZnO nanowire (NW) field-effect transistor (FET) systems, examined through modulation of the surface electric field of the ZnO NW. We apply oxygen plasma treatment to tailor the doping concentration within the ZnO NWs with the goal of modulating the electric field within their surface space-charge layers. X-ray photoelectron spectroscopy and low-frequency current-noise spectroscopy are applied to identify the change in the density of oxygen-vacancy defects near the NW surface after oxygen plasma treatment. A model describing the initial stage of the photoconductance responses associated with the formation of the photoinduced ionized 1 + state of the oxygen-vacancy defects (VO + ) in the fully depleted ZnO NW FETs in the low-photoconductance regime upon UV excitation is proposed to extract the charge-separation probabilities of the photoexcited electron/VO + pair. Accordingly, the charge-separation probability increases from approximately 0.0012 to 0.042 upon increasing the electric field at the NW surface from approximately 7.5 ×106 to 5.0 ×107 V m-1 . Moreover, we employ modified Braun empirical theory to model the effect of the electric field on the charge-separation behavior of photoexcited electron/VO + pairs in ZnO NWs, obtaining a

  12. Assessing the ability of DFT methods to describe static electron correlation effects: CO core level binding energies as a representative case

    NASA Astrophysics Data System (ADS)

    Pueyo Bellafont, Noèlia; Bagus, Paul S.; Sousa, Carmen; Illas, Francesc

    2017-07-01

    We use a total energy difference approach to explore the ability of various density functional theory based methods in accounting for the differential effect of static electron correlation on the C(1s) and O(1s) core level binding energies (BEs) of the CO molecule. In particular, we focus on the magnitude of the errors of the computed C(1s) and O(1s) BEs and on their relative difference as compared to experiment and to previous results from explicitly correlated wave functions. Results show that the different exchange-correlation functionals studied here behave rather erratically and a considerable number of them lead to large errors in the BEs and/or the BE shifts. Nevertheless, the TPSS functional, its TPSSm and RevTPSS derivations, and its corresponding hybrid counterpart, TPSSh, perform better than average and provide BEs and BE shifts in good agreement with experiment.

  13. Li induced effects in the core level and π-band electronic structure of graphene grown on C-face SiC

    SciTech Connect

    Johansson, Leif I. Xia, Chao; Virojanadara, Chariya

    2015-11-15

    Studies of the effects induced in the electronic structure after Li deposition, and subsequent heating, on graphene samples prepared on C-face SiC are reported. The as prepared graphene samples are essentially undoped, but after Li deposition, the Dirac point shifts down to 1.2 eV below the Fermi level due to electron doping. The shape of the C 1s level also indicates a doping concentration of around 10{sup 14 }cm{sup −2} after Li deposition, when compared with recent calculated results of core level spectra of graphene. The C 1s, Si 2p, and Li 1s core level results show little intercalation directly after deposition but that most of the Li has intercalated after heating at 280 °C. Heating at higher temperatures leads to desorption of Li from the sample, and at 1030 °C, Li can no longer be detected on the sample. The single π-band observable from multilayer C-face graphene samples in conventional angle resolved photoelectron spectroscopy is reasonably sharp both on the initially prepared sample and after Li deposition. After heating at 280 °C, the π-band appears more diffuse and possibly split. The Dirac point becomes located at 0.4 eV below the Fermi level, which indicates occurrence of a significant reduction in the electron doping concentration. Constant energy photoelectron distribution patterns extracted from the as prepared graphene C-face sample and also after Li deposition and heating at 280 °C look very similar to earlier calculated distribution patterns for monolayer graphene.

  14. sp2/sp3 hybridization ratio in amorphous carbon from C 1s core-level shifts: X-ray photoelectron spectroscopy and first-principles calculation

    NASA Astrophysics Data System (ADS)

    Haerle, Rainer; Riedo, Elisa; Pasquarello, Alfredo; Baldereschi, Alfonso

    2002-01-01

    Using a combined experimental and theoretical approach, we address C 1s core-level shifts in amorphous carbon. Experimental results are obtained by x-ray photoelectron spectroscopy (XPS) and electron-energy-loss spectroscopy (EELS) on thin-film samples of different atomic density, obtained by a pulsed-laser deposition growth process. The XPS spectra are deconvoluted into two contributions, which are attributed to sp2- and sp3-hybridized atoms, respectively, separated by 0.9 eV, independent of atomic density. The sp3 hybridization content extracted from XPS is consistent with the atomic density derived from the plasmon energy in the EELS spectrum. In our theoretical study, we generate several periodic model structures of amorphous carbon of different densities applying two schemes of increasing accuracy in sequence. We first use a molecular-dynamics approach, based on an environmental-dependent tight-binding Hamiltonian to quench the systems from the liquid phase. The final model structures are then obtained by further atomic relaxation using a first-principles pseudopotential plane-wave approach within density-functional theory. Within the latter framework, we also calculate carbon 1s core-level shifts for our disordered model structures. We find that the shifts associated to threefold- and fourfold- coordinated carbon atoms give rise to two distinct peaks separated by about 1.0 eV, independent of density, in close agreement with experimental observations. This provides strong support for decomposing the XPS spectra into two peaks resulting from sp2- and sp3-hybridized atoms. Core-hole relaxations effects account for about 30% of the calculated shifts.

  15. SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism.

    PubMed

    Hattori, Shohei; Schmidt, Johan A; Johnson, Matthew S; Danielache, Sebastian O; Yamada, Akinori; Ueno, Yuichiro; Yoshida, Naohiro

    2013-10-29

    Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of (32)SO2, (33)SO2, (34)SO2, and (36)SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ(33)S/δ(34)S and Δ(36)S/Δ(33)S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events.

  16. SO2 photoexcitation mechanism links mass-independent sulfur isotopic fractionation in cryospheric sulfate to climate impacting volcanism

    PubMed Central

    Hattori, Shohei; Schmidt, Johan A.; Johnson, Matthew S.; Danielache, Sebastian O.; Yamada, Akinori; Ueno, Yuichiro; Yoshida, Naohiro

    2013-01-01

    Natural climate variation, such as that caused by volcanoes, is the basis for identifying anthropogenic climate change. However, knowledge of the history of volcanic activity is inadequate, particularly concerning the explosivity of specific events. Some material is deposited in ice cores, but the concentration of glacial sulfate does not distinguish between tropospheric and stratospheric eruptions. Stable sulfur isotope abundances contain additional information, and recent studies show a correlation between volcanic plumes that reach the stratosphere and mass-independent anomalies in sulfur isotopes in glacial sulfate. We describe a mechanism, photoexcitation of SO2, that links the two, yielding a useful metric of the explosivity of historic volcanic events. A plume model of S(IV) to S(VI) conversion was constructed including photochemistry, entrainment of background air, and sulfate deposition. Isotopologue-specific photoexcitation rates were calculated based on the UV absorption cross-sections of 32SO2, 33SO2, 34SO2, and 36SO2 from 250 to 320 nm. The model shows that UV photoexcitation is enhanced with altitude, whereas mass-dependent oxidation, such as SO2 + OH, is suppressed by in situ plume chemistry, allowing the production and preservation of a mass-independent sulfur isotope anomaly in the sulfate product. The model accounts for the amplitude, phases, and time development of Δ33S/δ34S and Δ36S/Δ33S found in glacial samples. We are able to identify the process controlling mass-independent sulfur isotope anomalies in the modern atmosphere. This mechanism is the basis of identifying the magnitude of historic volcanic events. PMID:23417298

  17. Conformational changes in photoexcited (R)-(+)-1,1'-bi-2-naphthol studied by time-resolved circular dichroism.

    PubMed

    Niezborala, Claire; Hache, François

    2008-09-24

    Conformational changes following photoexcitation of ( R)-(+)-1,1'-bi-2-naphthol are studied with a time-resolved circular dichroism (CD) experiment. Two wavelengths are investigated. For lambda = 237 nm, we observe a bleaching of the ground-state absorption and a transient CD structure. Thanks to a coupled-oscillator calculation, we can attribute this effect to a decrease of the dihedral angle. For lambda = 245 nm, excited-state absorption and CD are observed. All these effects are solvent-dependent. In particular, it is shown that dynamics is slower in a protic solvent, which is attributed to hydrogen-bonding of the hydroxy groups with the solvent.

  18. Ultrafast, correlated multidimensional shell dynamics of neon matrices after photoexcitation of an NO impurity: An MCTDH approach

    NASA Astrophysics Data System (ADS)

    Uranga-Piña, L.; Meier, C.; Rubayo-Soneira, J.

    2012-08-01

    Photoexcitation of NO embedded in rare gas matrices triggers a shock-wave like radial perturbation of the surrounding rare gas atoms. In this Letter, we present quantum dynamical studies of this process, based on a radial shell model. The high-dimensional quantum dynamics is preformed with the multi-configuration time dependent Hartree (MCTDH) method. By comparison with time-dependent Hartree (TDH) results, we study the effects of dynamical correlations. Their inclusion modifies the high-dimensional wavefunction, however, mean values are well described within the TDH ansatz. Finally, pump-probe signals are simulated and shown to lead to small but measurable effects when including the correlations.

  19. Ultrafast Control of Magnetism in Ferromagnetic Semiconductors via Photoexcited Transient Carriers

    SciTech Connect

    Cotoros, Ingrid A.

    2008-12-01

    The field of spintronics offers perspectives for seamless integration of coupled and inter-tunable electrical and magnetic properties in a single device. For integration of the spin degree of freedom with current electronic technology, new semiconductors are needed that show electrically-tunable magnetic properties at room temperature and above. Dilute magnetic semiconductors derived from III-V compounds, like GaMnAs and InMnAs, show coupled and tunable magnetic, transport, and optical properties, due to the fact that their ferromagnetism is hole-mediated. These unconventional materials are ideal systems for manipulating the magnetic order by changing the carrier polarization, population density, and energy band distribution of the complementary subsystem of holes. This is the main theme we cover in this thesis. In particular, we develop a unique setup by use of ultraviolet pump, near-infrared probe femtosecond laser pulses, that allows for magneto-optical Kerr effect (MOKE) spectroscopy experiments. We photo-excite transient carriers in our samples, and measure the induced transient magnetization dynamics. One set of experiments performed allowed us to observe for the first time enhancement of the ferromagnetic order in GaMnAs, on an ultrafast time scale of hundreds of picoseconds. The corresponding transient increase of Curie temperature (Tc, the temperature above which a ferromagnetic material loses its permanent magnetism) of about 1 K for our experimental conditions is a very promising result for potential spintronics applications, especially since it is seconded by observation of an ultrafast ferromagnetic to paramagnetic phase transition above Tc. In a different set of experiments, we "write" the magnetization in a particular orientation in the sample plane. Using an ultrafast scheme, we alter the distribution of holes in the system and detect signatures of the particular memory state in the subsequent magnetization dynamics, with unprecedented hundreds of

  20. Electron-hole exchange blockade and memory-less recombination in photoexcited films of colloidal quantum dots

    NASA Astrophysics Data System (ADS)

    Fidler, Andrew F.; Gao, Jianbo; Klimov, Victor I.

    2017-06-01

    Understanding charge transport and recombination dynamics in photoexcited colloidal quantum dot (QD) solids is key to their applications in optoelectronic devices. Towards this end, we conduct transient photocurrent studies of films of electronically coupled, device-grade PbSe QD films. We observe that the photocurrent amplitude detected following excitation with a short 100 fs pulse is virtually temperature independent down to 6 K, suggesting a tunnelling mechanism of early-time photoconductance. The later-time signal exhibits clear signatures of thermal activation with characteristic energies that are surprisingly robust and independent of the exact type of QD surface treatment. We attribute this behaviour to the involvement of intrinsic fine-structure states and specifically the electron-hole exchange interaction, which creates an energetic barrier to electron-hole separation between adjacent QDs. At room temperature, which is well above the largest activation energy, relaxation of photoconductivity is dominated by non-geminate recombination involving mobile band-edge carriers of one sign and low-mobility carriers of the opposite sign (pre-existing and photoexcited) residing in intragap states. This process leads to memory-less dynamics when the photocurrent relaxation time is directly linked to the instantaneous carrier density.

  1. Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3.

    PubMed

    Carneiro, Lucas M; Cushing, Scott K; Liu, Chong; Su, Yude; Yang, Peidong; Alivisatos, A Paul; Leone, Stephen R

    2017-08-01

    Small polaron formation is known to limit ground-state mobilities in metal oxide photocatalysts. However, the role of small polaron formation in the photoexcited state and how this affects the photoconversion efficiency has yet to be determined. Here, transient femtosecond extreme-ultraviolet measurements suggest that small polaron localization is responsible for the ultrafast trapping of photoexcited carriers in haematite (α-Fe2O3). Small polaron formation is evidenced by a sub-100 fs splitting of the Fe 3p core orbitals in the Fe M2,3 edge. The small polaron formation kinetics reproduces the triple-exponential relaxation frequently attributed to trap states. However, the measured spectral signature resembles only the spectral predictions of a small polaron and not the pre-edge features expected for mid-gap trap states. The small polaron formation probability, hopping radius and lifetime varies with excitation wavelength, decreasing with increasing energy in the t2g conduction band. The excitation-wavelength-dependent localization of carriers by small polaron formation is potentially a limiting factor in haematite's photoconversion efficiency.

  2. Observation of photoexcitation of Fe-oxide grown on TiO2(100) by visible light irradiation

    NASA Astrophysics Data System (ADS)

    Kawauchi, Taizo; Nagatsuka, Naoki; Fukutani, Katsuyuki

    2016-12-01

    Electronic excitation of materials is of fundamental and technological importance and interest in terms of photoinduced phase transition, photovoltaics, and photocatalysis. In the present study, photoexcitation of Fe2 O 3 epitaxially grown on rutile TiO2(100) was investigated with conversion electron Mössbauer spectroscopy (CEMS) under dominantly visible-light irradiation. 57Fe was deposited on the substrate at a substrate temperature of 973 K, and the resulting film was characterized by RHEED and XPS. After deposition of Fe on TiO2(100), it was found that Fe was oxidized to Fe 3+, and the structure was analyzed to be the rhombohedral phase of Fe2 O 3. While the CEMS spectrum without light irradiation showed a quadrupole splitting of 0.80 mm/s with an isomer shift of +0.25 mm/s, an additional component with a quadrupole splitting of 0.85 and an isomer shift of +0.67 mm/s was observed under light irradiation. The latter component corresponds to a reduced state of Fe at the octahedral site surrounded by oxygen atoms. The lifetime of this photoexcited state is discussed.

  3. Femtosecond transient infrared and stimulated Raman spectroscopy shed light on the relaxation mechanisms of photo-excited peridinin

    NASA Astrophysics Data System (ADS)

    Di Donato, Mariangela; Ragnoni, Elena; Lapini, Andrea; Foggi, Paolo; Hiller, Roger G.; Righini, Roberto

    2015-06-01

    By means of one- and two-dimensional transient infrared spectroscopy and femtosecond stimulated Raman spectroscopy, we investigated the excited state dynamics of peridinin, a carbonyl carotenoid occurring in natural light harvesting complexes. The presence of singly and doubly excited states, as well as of an intramolecular charge transfer (ICT) state, makes the behavior of carbonyl carotenoids in the excited state very complex. In this work, we investigated by time resolved spectroscopy the relaxation of photo-excited peridinin in solvents of different polarities and as a function of the excitation wavelength. Our experimental results show that a characteristic pattern of one- and two-dimensional infrared bands in the C=C stretching region allows monitoring the relaxation pathway. In polar solvents, moderate distortions of the molecular geometry cause a variation of the single/double carbon bond character, so that the partially ionic ICT state is largely stabilized by the solvent reorganization. After vertical photoexcitation at 400 nm of the S2 state, the off-equilibrium population moves to the S1 state with ca. 175 fs time constant; from there, in less than 5 ps, the non-Franck Condon ICT state is reached, and finally, the ground state is recovered in 70 ps. That the relevant excited state dynamics takes place far from the Franck Condon region is demonstrated by its noticeable dependence on the excitation wavelength.

  4. A two-step photoexcitation system for photocatalytic water splitting into hydrogen and oxygen under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Abe, Ryu

    2011-10-01

    The developments of water-splitting systems that can efficiently use visible light have been a major challenge for many years in order to realize efficient conversion of solar light. We have developed a new type of photocatalysis system that can split water into H2 and O2 under visible light irradiation, which was inspired by the two-step photoexcitation (Zscheme) mechanism of natural photosynthesis in green plants. In this system, the water splitting reaction is broken up into two stages: one for H2 evolution and the other for O2 evolution; these are combined by using a shuttle redox couple (Red/Ox) in the solution. The introduction of a Z-scheme mechanism reduces the energy required to drive each photocatalysis process, extending the usable wavelengths significantly (~460 nm for H2 evolution and ~600 nm for O2evolution) from that in conventional water splitting systems (~460 nm) based on one-step photoexcitation in single semiconductor material.

  5. Excitation-wavelength-dependent small polaron trapping of photoexcited carriers in α-Fe2O3

    NASA Astrophysics Data System (ADS)

    Carneiro, Lucas M.; Cushing, Scott K.; Liu, Chong; Su, Yude; Yang, Peidong; Alivisatos, A. Paul; Leone, Stephen R.

    2017-08-01

    Small polaron formation is known to limit ground-state mobilities in metal oxide photocatalysts. However, the role of small polaron formation in the photoexcited state and how this affects the photoconversion efficiency has yet to be determined. Here, transient femtosecond extreme-ultraviolet measurements suggest that small polaron localization is responsible for the ultrafast trapping of photoexcited carriers in haematite (α-Fe2O3). Small polaron formation is evidenced by a sub-100 fs splitting of the Fe 3p core orbitals in the Fe M2,3 edge. The small polaron formation kinetics reproduces the triple-exponential relaxation frequently attributed to trap states. However, the measured spectral signature resembles only the spectral predictions of a small polaron and not the pre-edge features expected for mid-gap trap states. The small polaron formation probability, hopping radius and lifetime varies with excitation wavelength, decreasing with increasing energy in the t2g conduction band. The excitation-wavelength-dependent localization of carriers by small polaron formation is potentially a limiting factor in haematite's photoconversion efficiency.

  6. UVA-visible photo-excitation of guanine radical cations produces sugar radicals in DNA and model structures

    PubMed Central

    Adhikary, Amitava; Malkhasian, Aramice Y. S.; Collins, Sean; Koppen, Jessica; Becker, David; Sevilla, Michael D.

    2005-01-01

    This work presents evidence that photo-excitation of guanine radical cations results in high yields of deoxyribose sugar radicals in DNA, guanine deoxyribonucleosides and deoxyribonucleotides. In dsDNA at low temperatures, formation of C1′• is observed from photo-excitation of G•+ in the 310–480 nm range with no C1′• formation observed ≥520 nm. Illumination of guanine radical cations in 2′dG, 3′-dGMP and 5′-dGMP in aqueous LiCl glasses at 143 K is found to result in remarkably high yields (∼85–95%) of sugar radicals, namely C1′•, C3′• and C5′•. The amount of each of the sugar radicals formed varies dramatically with compound structure and temperature of illumination. Radical assignments were confirmed using selective deuteration at C5′ or C3′ in 2′-dG and at C8 in all the guanine nucleosides/tides. Studies of the effect of temperature, pH, and wavelength of excitation provide important information about the mechanism of formation of these sugar radicals. Time-dependent density functional theory calculations verify that specific excited states in G•+ show considerable hole delocalization into the sugar structure, in accord with our proposed mechanism of action, namely deprotonation from the sugar moiety of the excited molecular radical cation. PMID:16204456

  7. Equilibration kinetics in isolated and membrane-bound photosynthetic reaction centers upon illumination: a method to determine the photoexcitation rate.

    PubMed

    Manzo, Anthony J; Goushcha, Alexander O; Barabash, Yuri M; Kharkyanen, Valery N; Scott, Gary W

    2009-07-01

    Kinetics of electron transfer, following variation of actinic light intensity, for photosynthetic reaction centers (RCs) of purple bacteria (isolated and membrane-bound) were analyzed by measuring absorbance changes in the primary photoelectron donor absorption band at 865 nm. The bleaching of the primary photoelectron donor absorption band in RCs, following a sudden increase of illumination from the dark to an actinic light intensity of I(exp), obeys a simple exponential law with the rate constant alphaI(exp) + k(rec), in which alpha is a parameter relating the light intensity, measured in mW/cm(2), to a corresponding theoretical rate in units of reciprocal seconds, and k(rec) is the effective rate constant of the charge recombination in the photosynthetic RCs. In this work, a method for determining the alpha parameter value is developed and experimentally verified for isolated and membrane-bound RCs, allowing for rigorous modeling of RC macromolecule dynamics under varied photoexcitation conditions. Such modeling is necessary for RCs due to alterations of the forward photoexcitation rates and relaxation rates caused by illumination history and intramolecular structural dynamics effects. It is demonstrated that the classical Bouguer-Lambert-Beer formalism can be applied for the samples with relatively low scattering, which is not necessarily the case with strongly scattering media or high light intensity excitation.

  8. Effects of iodine on the relaxation dynamics of a photoexcited I(-)(H(2)O)(4) cluster.

    PubMed

    Sheu, Wen-Shyan; Chiou, Mong-Feng

    2013-12-27

    The Born-Oppenheimer molecular dynamics are used to examine the relaxation dynamics of the charge-transfer-to-solvent (CTTS) photoexcited electron in I(-)(H2O)4. The dynamics are initiated from the C1' cluster configuration, which contains a dangling water molecule. The iodine atom is found to exert a repulsive force on the photoexcited electron at the beginning but an attractive force at later times of the simulation. This dual repulsion-and-attraction role of the iodine atom is found to be dependent on the ratio of the iodine-electron distance to the radius of gyration of the excited electron, d/r. In the region of d/r < ∼0.8, the iodine exerts an exclusion-repulsion force on the excited electron. Conversely, for values of d/r > ∼1.0, the iodine can exert an attractive force on the excited electron due to the induced dipole moment of iodine. However, at large iodine-electron distances, the iodine-electron interaction becomes very weak, and as a result, this attractive force is expected to fade away. Due to the heavy mass of the iodine atom, the evolution of the iodine-electron distance is driven by the motion of solvent molecules and not iodine itself. The dangling water molecules and the dipolar field of water molecules are also important in the solvent dynamics. The influence of temperature on the iodine effects and the experimental implications of the findings are also discussed.

  9. Femtosecond transient infrared and stimulated Raman spectroscopy shed light on the relaxation mechanisms of photo-excited peridinin.

    PubMed

    Di Donato, Mariangela; Ragnoni, Elena; Lapini, Andrea; Foggi, Paolo; Hiller, Roger G; Righini, Roberto

    2015-06-07

    By means of one- and two-dimensional transient infrared spectroscopy and femtosecond stimulated Raman spectroscopy, we investigated the excited state dynamics of peridinin, a carbonyl carotenoid occurring in natural light harvesting complexes. The presence of singly and doubly excited states, as well as of an intramolecular charge transfer (ICT) state, makes the behavior of carbonyl carotenoids in the excited state very complex. In this work, we investigated by time resolved spectroscopy the relaxation of photo-excited peridinin in solvents of different polarities and as a function of the excitation wavelength. Our experimental results show that a characteristic pattern of one- and two-dimensional infrared bands in the C=C stretching region allows monitoring the relaxation pathway. In polar solvents, moderate distortions of the molecular geometry cause a variation of the single/double carbon bond character, so that the partially ionic ICT state is largely stabilized by the solvent reorganization. After vertical photoexcitation at 400 nm of the S2 state, the off-equilibrium population moves to the S1 state with ca. 175 fs time constant; from there, in less than 5 ps, the non-Franck Condon ICT state is reached, and finally, the ground state is recovered in 70 ps. That the relevant excited state dynamics takes place far from the Franck Condon region is demonstrated by its noticeable dependence on the excitation wavelength.

  10. Deep smarts.

    PubMed

    Leonard, Dorothy; Swap, Walter

    2004-09-01

    When a person sizes up a complex situation and rapidly comes to a decision that proves to be not just good but brilliant, you think, "That was smart." After you watch him do this a few times, you realize you're in the presence of something special. It's not raw brainpower, though that helps. It's not emotional intelligence, either, though that, too, is often involved. It's deep smarts. Deep smarts are not philosophical--they're not"wisdom" in that sense, but they're as close to wisdom as business gets. You see them in the manager who understands when and how to move into a new international market, in the executive who knows just what kind of talk to give when her organization is in crisis, in the technician who can track a product failure back to an interaction between independently produced elements. These are people whose knowledge would be hard to purchase on the open market. Their insight is based on know-how more than on know-what; it comprises a system view as well as expertise in individual areas. Because deep smarts are experienced based and often context specific, they can't be produced overnight or readily imported into an organization. It takes years for an individual to develop them--and no time at all for an organization to lose them when a valued veteran walks out the door. They can be taught, however, with the right techniques. Drawing on their forthcoming book Deep Smarts, Dorothy Leonard and Walter Swap say the best way to transfer such expertise to novices--and, on a larger scale, to make individual knowledge institutional--isn't through PowerPoint slides, a Web site of best practices, online training, project reports, or lectures. Rather, the sage needs to teach the neophyte individually how to draw wisdom from experience. Companies have to be willing to dedicate time and effort to such extensive training, but the investment more than pays for itself.

  11. Deep morphea.

    PubMed

    Bielsa, Isabel; Ariza, Aurelio

    2007-06-01

    Deep morphea encompasses a variety of clinical entities in which inflammation and sclerosis are found in the deep dermis, panniculus, fascia, or superficial muscle. Morphea profunda, eosinophilic fasciitis, and disabling pansclerotic morphea of children are included in this group, but overlapping of the extent and depth of cutaneous involvement in these various conditions precludes their distinction on the sole basis of clinical or even histologic examination. Furthermore, the limits between morphea profunda and generalized morphea, which usually are classified outside this group, are not clear. Histologically, all these disorders show similar inflammatory and sclerotic findings, the primary difference being the depth of these changes. Associated clinical findings, including arthralgias, arthritis, contractures, or carpal tunnel syndrome, are frequent. Although visceral complications are uncommon, pulmonary, esophageal, and even cardiac abnormalities have been reported. Eosinophilia, hypergammaglobulinemia, and increased erythrocyte sedimentation rate may be present with disease activity. Laboratory studies may demonstrate autoantibody production. Treatment is nonstandardized but UVA irradiation and antiinflammatory or immunosuppressive drugs (mainly antimalarial agents and corticosteroids) may be beneficial.

  12. Layer-by-layer resolved core-level shifts in CaF2 and SrF2 on Si(111): Theory and experiment

    NASA Astrophysics Data System (ADS)

    Rotenberg, Eli; Denlinger, J. D.; Leskovar, M.; Hessinger, U.; Olmstead, Marjorie A.

    1994-10-01

    Using x-ray-photoelectron spectroscopy and Auger-electron spectroscopy, we have resolved surface, bulk, and interface Ca and F core-level emission in thin films (3-8 triple layers) of CaF2 and SrF2 on Si(111). We confirmed these assignments using x-ray-photoelectron diffraction (XPD) and surface modification. XPD was also used to identify the growth modes of the films as being either laminar or layer plus islands; in the latter case we have resolved buried and uncovered interface F and Ca/Sr emission. We compare the observed energy differences between surface, bulk, and interface emission to theoretical estimates of the extra-atomic contributions to emission energies. We find excellent agreement considering only the Madelung (electrostatic) potentials for the initial-state contribution and polarization response for the final-state contribution, including the effect of tetragonal strain. Small discrepancies for emission from metal atoms bonded to the Si substrate are interpreted in terms of chemical shifts.

  13. The evolution of Ga and As core levels in the formation of Fe/GaAs (001):A high resolution soft x-ray photoelectron spectroscopic study

    SciTech Connect

    Thompson, Jamie; Neal, James; Shen, Tiehan; Morton, Simon; Tobin, James; Waddill, George Dan; Matthew, Jim; Greig, Denis; Hopkinson, Mark

    2008-07-14

    A high resolution soft x-ray photoelectron spectroscopic study of Ga and As 3d core levels has been conducted for Fe/GaAs (001) as a function of Fe thickness. This work has provided unambiguous evidence of substrate disrupting chemical reactions induced by the Fe overlayer--a quantitative analysis of the acquired spectra indicates significantly differing behavior of Ga and As during Fe growth, and our observations have been compared with existing theoretical models. Our results demonstrate that the outdiffusing Ga and As remain largely confined to the interface region, forming a thin intermixed layer. Whereas at low coverages Fe has little influence on the underlying GaAs substrate, the onset of substrate disruption when the Fe thickness reaches 3.5 Angstrom results in major changes in the energy distribution curves (EDCs) of both As and Ga 3d cores. Our quantitative analysis suggests the presence of two additional As environments of metallic character: one bound to the interfacial region and another which, as confirmed by in situ oxidation experiments, surface segregates and persists over a wide range of overlayer thickness. Analysis of the corresponding Ga 3d EDCs found not two, but three additional environments--also metallic in nature. Two of the three are interface resident whereas the third undergoes outdiffusion at low Fe coverages. Based on the variations of the integrated intensities of each component, we present a schematic of the proposed chemical makeup of the Fe/GaAs (001) system.

  14. Synthesis Dependent Core Level Binding Energy Shift in the Oxidation State of Platinum Coated on Ceria–Titania and its Effect on Catalytic Decomposition of Methanol

    SciTech Connect

    Karakoti, A. S.; King, Jessica; Vincent, Abhilash; Seal, Sudipta

    2010-11-20

    Synergistic interaction of catalyst and support has attracted the interest of the catalytic community for several decades. The decomposition/oxidation of alcohols for the production of hydrogen as a source of fuel requires such support catalyst interaction. Recent studies have suggested the active role of oxide based supports on the catalytic ability of noble metals such as gold, platinum and palladium. Herein, we report the effect of synthesis technique on the catalytic activity of platinum coated on mixed ceria-titania support system. Wet impregnation technique followed by calcination was compared with the chemical reduction of platinum during the coating over oxide support. Methanol decomposition studied using an in-house built catalytic reactor coupled to a mass spectrometer showed that catalyst prepared by thermal reduction of platinum demonstrated better catalytic ability than the catalyst prepared by chemical reduction of platinum. Transmission electron microscopy revealed that the size of both platinum and ceria-titania particles remained unchanged, while the X-ray photoelectron spectroscopy (XPS) revealed that the oxidation state of platinum was modified by different coating procedures. A shift in the core level binding energy of the Pt 4f towards lower binding energy was observed with chemical reduction. Based on the XPS data it was found that platinum (on ceria-titania supports) in mixed oxidation state outperformed the Pt in reduced metallic state. Results from catalysis and in situ Fourier transform infra red spectroscopy are presented and discussed.

  15. First-principle calculation of core level binding energies of Li{sub x}PO{sub y}N{sub z} solid electrolyte

    SciTech Connect

    Guille, Émilie; Vallverdu, Germain Baraille, Isabelle

    2014-12-28

    We present first-principle calculations of core-level binding energies for the study of insulating, bulk phase, compounds, based on the Slater-Janak transition state model. Those calculations were performed in order to find a reliable model of the amorphous Li{sub x}PO{sub y}N{sub z} solid electrolyte which is able to reproduce its electronic properties gathered from X-ray photoemission spectroscopy (XPS) experiments. As a starting point, Li{sub 2}PO{sub 2}N models were investigated. These models, proposed by Du et al. on the basis of thermodynamics and vibrational properties, were the first structural models of Li{sub x}PO{sub y}N{sub z}. Thanks to chemical and structural modifications applied to Li{sub 2}PO{sub 2}N structures, which allow to demonstrate the relevance of our computational approach, we raise an issue concerning the possibility of encountering a non-bridging kind of nitrogen atoms (=N{sup −}) in Li{sub x}PO{sub y}N{sub z} compounds.

  16. The evolution of Ga and As core levels in the formation of Fe/GaAs (001): A high resolution soft x-ray photoelectron spectroscopic study

    SciTech Connect

    Thompson, Jamie D. W.; Neal, James R.; Shen, Tiehan H.; Morton, Simon A.; Tobin, James G.; Dan Waddill, G.; Matthew, Jim A. D.; Greig, Denis; Hopkinson, Mark

    2008-07-15

    A high resolution soft x-ray photoelectron spectroscopic study of Ga and As 3d core levels has been conducted for Fe/GaAs (001) as a function of Fe thickness. This work has provided unambiguous evidence of substrate disrupting chemical reactions induced by the Fe overlayer--a quantitative analysis of the acquired spectra indicates significantly differing behavior of Ga and As during Fe growth, and our observations have been compared with existing theoretical models. Our results demonstrate that the outdiffusing Ga and As remain largely confined to the interface region, forming a thin intermixed layer. Whereas at low coverages Fe has little influence on the underlying GaAs substrate, the onset of substrate disruption when the Fe thickness reaches 3.5 A results in major changes in the energy distribution curves (EDCs) of both As and Ga 3d cores. Our quantitative analysis suggests the presence of two additional As environments of metallic character: one bound to the interfacial region and another which, as confirmed by in situ oxidation experiments, surface segregates and persists over a wide range of overlayer thickness. Analysis of the corresponding Ga 3d EDCs found not two, but three additional environments--also metallic in nature. Two of the three are interface resident whereas the third undergoes outdiffusion at low Fe coverages. Based on the variations of the integrated intensities of each component, we present a schematic of the proposed chemical makeup of the Fe/GaAs (001) system.

  17. The Evolution of Ga and As Core Levels in the Formation of Fe/GaAs(001): A High Resolution Soft X-ray Photoelectron Spectroscopic Study

    SciTech Connect

    Thompson, J W; Neal, J R; Shen, T H; Morton, S A; Tobin, J G; Waddill, G D; Matthew, J D; Greig, D; Hopkinson, M

    2006-12-08

    A high resolution soft x-ray photoelectron spectroscopic study of Ga and As 3d core levels has been conducted for Fe/GaAs (001) as a function of Fe thickness. This work has provided unambiguous evidence of substrate disrupting chemical reactions induced by the Fe overlayer--a quantitative analysis of the acquired spectra indicates significantly differing behavior of Ga and As during Fe growth, and our observations have been compared with existing theoretical models. Our results demonstrate that the outdiffusing Ga and As remain largely confined to the interface region, forming a thin intermixed layer. Whereas at low coverages Fe has little influence on the underlying GaAs substrate, the onset of substrate disruption when the Fe thickness reaches 3.5 {angstrom} results in major changes in the energy distribution curves (EDCs) of both As and Ga 3d cores. Our quantitative analysis suggests the presence of two new As environments of metallic character; one bound to the interfacial region and another which, as confirmed by in-situ oxidation experiments, surface segregates and persists over a wide range of overlayer thickness. Analysis of the corresponding Ga 3d EDCs found not two, but three new environments--also metallic in nature. Two of the three are interface-resident whereas the third undergoes outdiffusion at low Fe coverages. Based on the variations of the integrated intensities of each component, we present a schematic of the proposed chemical make-up of the Fe/GaAs (001) system.

  18. Exploring large O 1s and N 1s core level shifts due to intermolecular hydrogen bond formation in organic molecules

    NASA Astrophysics Data System (ADS)

    Garcia-Gil, S.; Arnau, A.; Garcia-Lekue, A.

    2013-07-01

    Core level shifts (CLSs) induced by intermolecular hydrogen bond (H-bond) formation are studied with a recent implementation based on density functional theory using pseudopotentials and localized atomic orbitals, as applied to the SIESTA code. By calculating different CLSs for a set of representative simple systems containing O and/or N atoms as proton donors and/or acceptors, we are able to determine the role of the core hole screening, from the difference of CLS values calculated in the final and initial state approximations. Our calculations show that CLSs are dominated by electrostatic effects, and that the final magnitude of the CLSs, which are positive (higher binding energy) for the proton acceptor and negative for the proton donor, can be larger than 1 eV for strong H-bonds. We also find that core hole screening contribution to final CLS absolute values is always negative, thus being responsible for the difference in the magnitude of the CLS of the proton donor and proton acceptor.

  19. Linear-Response and Real-Time Time-Dependent Density Functional Theory Studies of Core-Level Near-Edge X-Ray Absorption.

    PubMed

    Lopata, K; Van Kuiken, B E; Khalil, M; Govind, N

    2012-09-11

    We discuss our implementation and application of time-dependent density functional theory (TDDFT) to core-level near-edge absorption spectroscopy, using both linear-response (LR) and real-time (RT) approaches. We briefly describe our restricted excitation window TDDFT (REW-TDDFT) approach for core excitations, which has also been reported by other groups. This is followed by a detailed discussion of real-time TDDFT techniques tailored to core excitations, including obtaining spectral information through delta-function excitation, postprocessing time-dependent signals, and resonant excitation through quasi-monochromatic excitation. We present results for the oxygen K-edge of water and carbon monoxide; the carbon K-edge of carbon monoxide; the ruthenium L3-edge for the hexaamminerutheium(III) ion, including scalar relativistic corrections via the zeroth order regular approximation (ZORA); and the carbon and fluorine K-edges for a series of fluorobenzenes. In all cases, the calculated spectra are found to be in reasonable agreement with experimental results, requiring only a uniform shift ranging from -4 eV to +19 eV, i.e., on the order of a few percent of the excitation energy. Real-time TDDFT visualization of excited state charge densities is used to visually examine the nature of each excitation, which gives insight into the effects of atoms bound to the absorbing center.

  20. The influence of oxygen adsorption on the NEXAFS and core-level XPS spectra of the C{sub 60} derivative PCBM

    SciTech Connect

    Brumboiu, Iulia Emilia Eriksson, Olle; Brena, Barbara; Ericsson, Leif; Hansson, Rickard; Moons, Ellen

    2015-02-07

    Fullerenes have been a main focus of scientific research since their discovery due to the interesting possible applications in various fields like organic photovoltaics (OPVs). In particular, the derivative [6,6]-phenyl-C{sub 60}-butyric acid methyl ester (PCBM) is currently one of the most popular choices due to its higher solubility in organic solvents compared to unsubstituted C{sub 60}. One of the central issues in the field of OPVs is device stability, since modules undergo deterioration (losses in efficiency, open circuit voltage, and short circuit current) during operation. In the case of fullerenes, several possibilities have been proposed, including dimerization, oxidation, and impurity related deterioration. We have studied by means of density functional theory the possibility of oxygen adsorption on the C{sub 60} molecular moiety of PCBM. The aim is to provide guidelines for near edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) measurements which can probe the presence of atomic or molecular oxygen on the fullerene cage. By analysing several configurations of PCBM with one or more adsorbed oxygen atoms, we show that a joint core level XPS and O1s NEXAFS investigation could be effectively used not only to confirm oxygen adsorption but also to pinpoint the bonding configuration and the nature of the adsorbate.

  1. The requisite electronic structure theory to describe photoexcited nonadiabatic dynamics: nonadiabatic derivative couplings and diabatic electronic couplings.

    PubMed

    Subotnik, Joseph E; Alguire, Ethan C; Ou, Qi; Landry, Brian R; Fatehi, Shervin

    2015-05-19

    Electronically photoexcited dynamics are complicated because there are so many different relaxation pathways: fluorescence, phosphorescence, radiationless decay, electon transfer, etc. In practice, to model photoexcited systems is a very difficult enterprise, requiring accurate and very efficient tools in both electronic structure theory and nonadiabatic chemical dynamics. Moreover, these theoretical tools are not traditional tools. On the one hand, the electronic structure tools involve couplings between electonic states (rather than typical single state energies and gradients). On the other hand, the dynamics tools involve propagating nuclei on multiple potential energy surfaces (rather than the usual ground state dynamics). In this Account, we review recent developments in electronic structure theory as directly applicable for modeling photoexcited systems. In particular, we focus on how one may evaluate the couplings between two different electronic states. These couplings come in two flavors. If we order states energetically, the resulting adiabatic states are coupled via derivative couplings. Derivative couplings capture how electronic wave functions change as a function of nuclear geometry and can usually be calculated with straightforward tools from analytic gradient theory. One nuance arises, however, in the context of time-dependent density functional theory (TD-DFT): how do we evaluate derivative couplings between TD-DFT excited states (which are tricky, because no wave function is available)? This conundrum was recently solved, and we review the solution below. We also discuss the solution to a second, pesky problem of origin dependence, whereby the derivative couplings do not (strictly) satisfy translation variance, which can lead to a lack of momentum conservation. Apart from adiabatic states, if we order states according to their electronic character, the resulting diabatic states are coupled via electronic or diabatic couplings. The couplings

  2. Deep blast

    NASA Astrophysics Data System (ADS)

    From southern New Mexico to the Great Slave Lake of Canada, scientists from the United States and Canada recently detonated 10 underground chemical explosions to generate a clearer picture of the Earth's crust and upper mantle. Called Project Deep Probe, the experiment is designed to see through the crust and into the upper mantle to a depth of 300 miles.In the United States, Earth scientists from Rice University, Purdue University, and the University of Oregon are participating in the project. “Researchers hope to get a picture of the upper mantle beneath the Rocky Mountains and the Colorado Plateau, to understand the role the mantle played in formation and uplift,” says Alan Levander of Rice. To enhance that “picture,” 750 portable seismographs were placed along a roughly north-south line extending from Crownpoint, New Mexico to Edmonton, Alberta. The seismic recordings will be used to enhance weak seismic waves that penetrated the upper mantle.

  3. Photoexcitation and ionization in carbon dioxide - Theoretical studies in the separated-channel static-exchange approximation

    NASA Technical Reports Server (NTRS)

    Padial, N.; Csanak, G.; Mckoy, B. V.; Langhoff, P. W.

    1981-01-01

    Vertical-electronic static-exchange photoexcitation and ionization cross sections are reported which provide a first approximation to the complete dipole spectrum of CO2. Separated-channel static-exchange calculations of vertical-electronic transition energies and oscillator strengths, and Stieltjes-Chebyshev moment methods were used in the development. Detailed comparisons were made of the static-exchange excitation and ionization spectra with photoabsorption, electron-impact excitation, and quantum-defect estimates of discrete transition energies and intensities, and with partial-channel photoionization cross sections obtained from fluorescence measurements and from tunable-source and (e, 2e) photoelectron spectroscopy. Results show that the separate-channel static-exchange approximation is generally satisfactory in CO2.

  4. Time-dependent transition density matrix for visualizing charge-transfer excitations in photoexcited organic donor-acceptor systems

    NASA Astrophysics Data System (ADS)

    Li, Yonghui; Ullrich, Carsten

    2013-03-01

    The time-dependent transition density matrix (TDM) is a useful tool to visualize and interpret the induced charges and electron-hole coherences of excitonic processes in large molecules. Combined with time-dependent density functional theory on a real-space grid (as implemented in the octopus code), the TDM is a computationally viable visualization tool for optical excitation processes in molecules. It provides real-time maps of particles and holes which gives information on excitations, in particular those that have charge-transfer character, that cannot be obtained from the density alone. Some illustration of the TDM and comparison with standard density difference plots will be shown for photoexcited organic donor-acceptor molecules. This work is supported by NSF Grant DMR-1005651

  5. Overlapping resonances interference-induced transparency: the S0 → S2/S1 photoexcitation spectrum of pyrazine.

    PubMed

    Grinev, Timur; Shapiro, Moshe; Brumer, Paul

    2012-09-07

    The phenomenon of "overlapping resonances interference-induced transparency" (ORIT) is introduced and studied in detail for the S(0) → S(2)/S(1) photoexcitation of cold pyrazine (C(4)H(4)N(2)). In ORIT, a molecule becomes transparent at specific wavelengths due to interferences between envelopes of spectral lines displaying overlapping resonances. An example is the S(2) ↔ S(1) internal conversion in pyrazine where destructive interference between overlapping resonances causes the S(0) → S(2)/S(1) light absorption to disappear at certain wavelengths. ORIT may be of practical importance in multi-component mixtures where it would allow for the selective excitation of some molecules in preference to others. Interference-induced cross section enhancement is also shown.

  6. A photoexcited switchable perfect metamaterial absorber/reflector with polarization-independent and wide-angle for terahertz waves

    NASA Astrophysics Data System (ADS)

    Cheng, Yongzhi; Gong, Rongzhou; Zhao, Jingcheng

    2016-12-01

    We present a photoexcited switchable perfect metamaterial absorber/reflector for terahertz waves. The switchable absorber/reflector is based on a cross-shaped structure (CSS) integrated semiconductor photoconductive silicon (Si). The electric response property of the photoconductive Si can be easily modified through a pump optical beam. The conductivity of Si pads filled in the gap of CSS is tuned efficiently through the incident pump optical beam with different power, resulting in the modulation of absorption magnitude from 0 to 100% at the fixed operation frequency. Thus, the switch ability of the perfect absorber/reflector can be easily realized. Furthermore, the proposed design is polarization insensitive and operated well at wide incidence angles for both TE and TM waves.

  7. Indirect IUE observation of O VI from photoexcited fluorescence lines of Fe II, present in the spectrum of RR Telescopii

    NASA Technical Reports Server (NTRS)

    Johansson, Sveneric

    1988-01-01

    A new, highly excited level of Fe II at 13.7 eV has been established by means of six lines in the laboratory spectrum below 2000 A. Confirming transitions appear in the infrared region. Four of the ultraviolet lines coincide with previously unidentified lines in the IUE spectrum of RR Tel reported by Penston et al. in 1983. One of the remaining UV lines coincides with the resonance line of O VI at 1032 A, outside the range of the IUE. This suggests that the new FE II level is selectively photoexcited by O VI in RR Tel, resulting in the strong fluorescence lines observed. This case of a Bowen mechanism provides an indirect observation of O VI, important for diagnostics of, e.g., symbiotic stars.

  8. Model of the photoexcitation processes of a two-level molecule coherently coupled to an optical antenna.

    PubMed

    Nakatani, Masatoshi; Nobuhiro, Atsushi; Yokoshi, Nobuhiko; Ishihara, Hajime

    2013-06-07

    We theoretically investigate photoexcitation processes of a two-level molecular system coherently coupled with an antenna system having a significant dissipation. The auxiliary antenna enables the whole system to exhibit anomalous optical effects by controlling the coupling with the molecule. For example, in the weak excitation regime, the quantum interference yields a distinctive energy transparency through the antenna, which drastically reduces the energy dissipation. On the other hand, in the strong excitation regime, a population inversion of the two-level molecule appears due to the nonlinear effect. Both phenomena can be explained by regarding the antenna and molecule as one quantum-mechanically coupled system. Such an approach drives further research to exploit the full potential of the coupled systems.

  9. Zero-field magnetic resonance of the photo-excited triplet state of pentacene at room temperature

    NASA Astrophysics Data System (ADS)

    Yang, Tran-Chin; Sloop, David J.; Weissman, S. I.; Lin, Tien-Sung

    2000-12-01

    The pulsed EPR free induction decay (FID) signals of the photo-excited pentacene triplet state are reported for three mixed crystals at room temperature: pentacene-h14 in p-terphenyl, pentacene-h14 in benzoic acid, and pentacene-d14 in p-terphenyl. The recorded FID signals have relatively long decay times of about four microseconds, presumably due to the reduced hyperfine interactions in the zero magnetic field. The time domain FID signals transform to spectral components typically narrower than 500 kHz, allowing us to determine the pentacene triplet zero field splitting parameters to better accuracy than previously reported. Further, a new experimental technique using the high speed magnetic field jumping capability enables us to examine the anisotropic hyperfine and quadrupole interactions.

  10. Dynamics of photoexcited carriers in monolayer epitaxial graphene probed by photoluminescence in the near-infrared region

    SciTech Connect

    Koyama, Takeshi; Ito, Yoshito; Yoshida, Kazuma; Ago, Hiroki; Nakamura, Arao

    2013-12-04

    We investigate the dynamics of photoexcited carriers in a single monolayer graphene at room temperature in air by femtosecond time-resolved luminescence measurements. The luminescence kinetics observed in the near-infrared region from 0.7 to 0.9 eV are analyzed based on the two-temperature model describing the cooling of thermalized carriers due to the carrier-optical-phonon coupling. The observed luminescence kinetics are well reproduced by the model, though the calculated electron temperature increases only to ∼420 K at the maximum, which is much lower than the optical phonon energies. This indicates the predominance of optical phonons over acoustic phonons in the carrier-phonon interaction even at a temperature of ∼400 K.

  11. Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry

    PubMed Central

    2016-01-01

    Unravelling the main initial dynamics responsible for chiral recognition is a key step in the understanding of many biological processes. However, this challenging task requires a sensitive enantiospecific probe to investigate molecular dynamics on their natural femtosecond time scale. Here we show that, in the gas phase, the ultrafast relaxation dynamics of photoexcited chiral molecules can be tracked by recording time-resolved photoelectron circular dichroism (TR-PECD) resulting from the photoionization by a circularly polarized probe pulse. A large forward–backward asymmetry along the probe propagation axis is observed in the photoelectron angular distribution. Its evolution with pump–probe delay reveals ultrafast dynamics that are inaccessible in the angle-integrated photoelectron spectrum or via the usual electron emission anisotropy parameter (β). PECD, which originates from the electron scattering in the chiral molecular potential, appears as a new sensitive observable for ultrafast molecular dynamics in chiral systems. PMID:27786493

  12. Optical Communication among Oscillatory Reactions and Photo-Excitable Systems: UV and Visible Radiation Can Synchronize Artificial Neuron Models.

    PubMed

    Gentili, Pier Luigi; Giubila, Maria Sole; Germani, Raimondo; Romani, Aldo; Nicoziani, Andrea; Spalletti, Anna; Heron, B Mark

    2017-06-19

    Neuromorphic engineering promises to have a revolutionary impact in our societies. A strategy to develop artificial neurons (ANs) is to use oscillatory and excitable chemical systems. Herein, we use UV and visible radiation as both excitatory and inhibitory signals for the communication among oscillatory reactions, such as the Belousov-Zhabotinsky and the chemiluminescent Orban transformations, and photo-excitable photochromic and fluorescent species. We present the experimental results and the simulations regarding pairs of ANs communicating by either one or two optical signals, and triads of ANs arranged in both feed-forward and recurrent networks. We find that the ANs, powered chemically and/or by the energy of electromagnetic radiation, can give rise to the emergent properties of in-phase, out-of-phase, anti-phase synchronizations and phase-locking, dynamically mimicking the communication among real neurons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Temperature dependent photoexcited carrier dynamics in multiferroic BiFeO{sub 3} film: A hidden phase transition

    SciTech Connect

    Zhang, Zeyu; Jin, Zuanming; Pan, Qunfeng; Xu, Yue; Lin, Xian; Ma, Guohong E-mail: cheng@uow.edu.au; Cheng, Zhenxiang E-mail: cheng@uow.edu.au

    2014-04-14

    The ultrafast carrier dynamics of the multiferroic BiFeO{sub 3} film in a broad temperature range is investigated using optical pump-probe spectroscopy. The photoexcited electrons release their energy with optical phonons emission through electron-phonon coupling in about 1 ps. The following intermediate process is identified as dynamical spin-lattice coupling in several picoseconds. Furthermore, the peak values of the optical reflectivity and the time constants of carrier relaxation channels show significant changes while the temperature varies from 137.5 K to around 195 K, this aligns with the previously reported hidden phase transition. Our study demonstrates that ultrafast spectroscopy is a sensitive method to look into the dynamical interactions among the on-site high-energy electrons accumulated in the p conduction band of Bi, coherent optical phonon, as well as the spin degree of freedom. These features play crucial roles in the characterization of phase transitions.

  14. Dissipation of core-hole momentum by phonons in soft-x-ray radiation processes from valence band to core level of wide-gap insulators

    NASA Astrophysics Data System (ADS)

    Minami, Tatsuya; Nasu, Keiichiro

    1998-05-01

    The role of phonons in the soft-x-ray radiation process from a valence band to a core level in an insulator is studied theoretically. A three-band system composed of a dispersionless core band, a conduction band, and a valence band, with wide energy gaps between them, is taken as a typical example. Phonons with a finite dispersion are assumed to couple weakly only with a hole in the core band (core hole). Using this model, we calculate the resonant second-order optical process composed of an excitation of an electron from the core band to the conduction band by an incident x ray, and a subsequent transition from the valence band to the core band by radiating another x ray. Without the phonons, the momentum of the core hole is expected to be well defined by the resonance condition of the incident x ray. However, this momentum is dissipated by the phonons. If the radiation occurs completely after this dissipation, we obtain a so-called luminescence, which is independent of the incident x ray. In this case, the spectral shape fully reflects the density of states (DOS) of the valence band. However, if the radiation occurs long before this dissipation effect, we obtain a resonant Raman scattering that depends on the incident x ray. The spectral shape of this Raman scattering has a sharp peak, quite different from the DOS. The relative intensity between these two components is determined by the phonon dispersion, the lifetime of the core hole, and the core-hole-phonon coupling constant. From this theoretical framework, we have concluded that there are various cases, i.e., Raman-dominant cases and luminescence-dominant cases, as well as intermediate cases, in good agreement with various experimental observations. The B 1s<-->2p transitions of cubic BN are concluded to correspond to a luminescence-dominant case.

  15. Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects

    SciTech Connect

    Matanovic, Ivana; Artyushkova, Kateryna; Strand, Matthew B.; Dzara, Michael J.; Pylypenko, Svitlana; Atanassov, Plamen

    2016-12-07

    A combination of N 1s X-ray photoelectron spectroscopy (XPS) and first principles calculations of nitrogen-containing model electrocatalysts was used to elucidate the nature of the nitrogen defects that contribute to the binding energy (BE) range of the N 1s XPS spectra of these materials above ~400 eV. Experimental core level shifts were obtained for a set of model materials, namely N-doped carbon nanospheres, Fe–N–carbon nanospheres, polypyrrole, polypyridine, and pyridinium chloride, and were compared to the shifts calculated using density functional theory. The results confirm that the broad peak positioned at ~400.7 eV in the N 1s XPS spectra of N-containing catalysts, which is typically assigned to pyrrolic nitrogen, contains contributions from other hydrogenated nitrogen species such as hydrogenated pyridinic functionalities. Namely, N 1s BEs of hydrogenated pyridinic-N and pyrrolic-N were calculated as 400.6 and 400.7 eV, respectively, using the Perdew–Burke–Ernzerhof exchange-correlation functional. A special emphasis was placed on the study of the differences in the XPS imprint of N-containing defects that are situated in the plane and on the edges of the graphene sheet. Density functional theory calculations for BEs of the N 1s of in-plane and edge defects show that hydrogenated N defects are more sensitive to the change in the chemical environment in the carbon matrix than the non-hydrogenated N defects. In conclusion, calculations also show that edge-hydrogenated pyridinic-N and pyrrolic-N defects only contribute to the N 1s XPS peak located at ~400.7 eV if the graphene edges are oxygenated or terminated with bare carbon atoms.

  16. Core Level Shifts of Hydrogenated Pyridinic and Pyrrolic Nitrogen in the Nitrogen-Containing Graphene-Based Electrocatalysts: In-Plane vs Edge Defects

    DOE PAGES

    Matanovic, Ivana; Artyushkova, Kateryna; Strand, Matthew B.; ...

    2016-12-07

    A combination of N 1s X-ray photoelectron spectroscopy (XPS) and first principles calculations of nitrogen-containing model electrocatalysts was used to elucidate the nature of the nitrogen defects that contribute to the binding energy (BE) range of the N 1s XPS spectra of these materials above ~400 eV. Experimental core level shifts were obtained for a set of model materials, namely N-doped carbon nanospheres, Fe–N–carbon nanospheres, polypyrrole, polypyridine, and pyridinium chloride, and were compared to the shifts calculated using density functional theory. The results confirm that the broad peak positioned at ~400.7 eV in the N 1s XPS spectra of N-containingmore » catalysts, which is typically assigned to pyrrolic nitrogen, contains contributions from other hydrogenated nitrogen species such as hydrogenated pyridinic functionalities. Namely, N 1s BEs of hydrogenated pyridinic-N and pyrrolic-N were calculated as 400.6 and 400.7 eV, respectively, using the Perdew–Burke–Ernzerhof exchange-correlation functional. A special emphasis was placed on the study of the differences in the XPS imprint of N-containing defects that are situated in the plane and on the edges of the graphene sheet. Density functional theory calculations for BEs of the N 1s of in-plane and edge defects show that hydrogenated N defects are more sensitive to the change in the chemical environment in the carbon matrix than the non-hydrogenated N defects. In conclusion, calculations also show that edge-hydrogenated pyridinic-N and pyrrolic-N defects only contribute to the N 1s XPS peak located at ~400.7 eV if the graphene edges are oxygenated or terminated with bare carbon atoms.« less

  17. Study on dynamic properties of the photoexcited charge carriers at anatase TiO2 nanowires/fluorine doped tin oxide interface.

    PubMed

    Qiu, Qingqing; Xu, Lingling; Wang, Dejun; Lin, Yanhong; Xie, Tengfeng

    2017-09-01

    The photoexcited electrons transfer dynamics at the TiO2 film/fluorine doped tin oxide (FTO) interface of anatase TiO2 nanowire arrays (NWAs) and QD-sensitized TiO2 NWAs films have been studied by using surface photovoltage (SPV) and transient photovoltage (TPV) techniques. Various SPV and TPV responses were obtained when the laser beam was incident from the front side illumination and back side illumination. Based on the work function values of anatase TiO2 NWAs and FTO, the results indicate that diffusion is the major way for the separation and transfer of the photoexcited charge in the both anatase TiO2 NWAs and QD-sensitized TiO2 NWAs films under front side illumination. And the photoexcited charge were separated by drift under the built-in electric field at the TiO2 film/FTO interface for anatase TiO2 NWAs and QD-sensitized TiO2 NWAs films under back side illumination. In addition, under back side illumination the built-in electric field and band structure of CdS/CdSe QDs and anatase TiO2 NWAs lead to the separation and transfer of the photoexcited charge for CdS/CdSe QDs sensitized TiO2 NWAs/FTO film. As the intensity of illumination increases, the effect of built-in electric field on the separation and transfer of the photoexcited charge in the QD-sensitized TiO2 NWAs film decreases. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Deep breathing after surgery

    MedlinePlus

    ... page: //medlineplus.gov/ency/patientinstructions/000440.htm Deep breathing after surgery To use the sharing features on ... way to do so is by doing deep breathing exercises. Deep breathing keeps your lungs well-inflated ...

  19. Manifestation of screening effects and A-O covalency in the core level spectra of A site elements in the ABO3 structure of Ca1-xSrxRuO3

    NASA Astrophysics Data System (ADS)

    Singh, Ravi Shankar; Maiti, Kalobaran

    2007-08-01

    We investigate the evolution of Ca2p and Sr3d core level spectra in Ca1-xSrxRuO3 using photoemission spectroscopy. Core level spectra in this system exhibit multiple features and unusual evolution with the composition and temperatures. Analysis of the core level spectra in conjunction with the band structure results indicates final state effects due to different core hole screening channels. Such screening in the photoemission final states can be attributed to the large A-O covalency in these systems. Changes in the core level spectra with temperature and composition suggest significant modification in A-O (A=Ca/Sr) covalency in Ca-dominated samples, which gradually reduces with the increase in Sr content and becomes insignificant in SrRuO3 . This study thus provides a direct evidence of cation-oxygen covalency and its evolution with temperature, which may be useful in understanding the unusual ground state properties of these materials.

  20. H elimination and metastable lifetimes in the UV photoexcitation of diacetylene

    PubMed Central

    Silva, R.; Gichuhi, W. K.; Huang, C.; Doyle, M. B.; Kislov, V. V.; Mebel, A. M.; Suits, A. G.

    2008-01-01

    We present an experimental investigation of the UV photochemistry of diacetylene under collisionless conditions. The H loss channel is studied using DC slice ion imaging with two-color reduced-Doppler detection at 243 nm and 212 nm. The photochemistry is further studied deep in the vacuum UV, that is, at Lyman-alpha (121.6 nm). Translational energy distributions for the H + C4H product arising from dissociation of C4H2 after excitation at 243, 212, and 121.6 nm show an isotropic angular distribution and characteristic translational energy profile suggesting statistical dissociation from the ground state or possibly from a low-lying triplet state. From these distributions, a two-photon dissociation process is inferred at 243 nm and 212 nm, whereas at 121.6 nm, a one-photon dissociation process prevails. The results are interpreted with the aid of ab initio calculations on the reaction pathways and statistical calculations of the dissociation rates and product branching. In a second series of experiments, nanosecond time-resolved phototionization measurements yield a direct determination of the lifetime of metastable triplet diacetylene under collisionless conditions, as well as its dependence on excitation energy. The observed submicrosecond lifetimes suggest that reactions of metastable diacetylene are likely to be less important in Titan's atmosphere than previously believed. PMID:18697925

  1. Photoexcited Carrier Dynamics of In 2 S 3 Thin Films

    SciTech Connect

    McCarthy, Robert F.; Schaller, Richard D.; Gosztola, David J.; Wiederrecht, Gary P.; Martinson, Alex B. F.

    2015-07-02

    Indium sulfide (In2S3) is a promising absorber base for substitutionally-doped intermediate band photovoltaics (IBPV). However, the dynamics of charge carriers traversing the electronic density of states that determine the optical and electronic response of thin films under stimuli have yet to be explored. In this letter, the kinetics of photophysical processes in In2S3 grown by oxygen-free atomic layer deposition (ALD) are deduced from photoconductivity, photoluminescence (PL), and transient absorption (TA) spectroscopy. We develop a map of excited state dynamics for polycrystalline thin films including a secondary conduction band ~2.1 eV above the first, plus sulfur vacancy and indium interstitial defect levels resulting in long-lived (~100 ns) transients. Band edge recombination produces PL and stimulated emission, which both intensify and red-shift as deposition temperature and grain size increase. The effect of rapid conduction band electron relaxation (< 30 ps) and deep defect levels on IBPV employing In2S3-based absorbers is finally considered.

  2. Ligand field splittings in core level transitions for transition metal (TM) oxides: Tanabe-Sugano diagrams and (TM) dangling bonds in vacated O-atom defects

    NASA Astrophysics Data System (ADS)

    Lucovsky, Gerry; Wu, Kun; Pappas, Brian; Whitten, Jerry

    2013-04-01

    Defect states in the forbidden band-gap below the conduction band edge are active as electron traps in nano-grain high-) transition metal (TM) oxides with thickness >0.3 nm, e.g., ZrO2 and HfO2. These oxides have received considerable attention as gate-dielectrics in complementary metal oxide semiconductor (CMOS) devices, and more recently are emerging as candidates for charge storage and memory devices. To provide a theoretical basis for device functionality, ab-initio many-electron theory is combined with X-ray absorption spectroscopy (XAS) to study O K edge and TM core level transitions. These studies identify ligand field splittings (ΔLF) for defect state features,. When compared with those obtained from O-atom and TM-atom core spectroscopic transitions, this provides direct information about defect state sun-nm bonding arrangements. comparisons are made for (i) elemental TiO2 and Ti2O3 with different formal ionic charges, Ti4+ and Ti3+ and for (ii) Magneli Phase alloys, TinO2n-1, n is an integer 9>=n>3, and (TiO2)x(HfO2)1-x alloys. The alloys display multi-valent behavior from (i) different ionic-charge states, (ii} local bond-strain, and (iii) metallic hopping transport. The intrinsic bonding defects in TM oxides are identified as pairs of singly occupied dangling bonds. For 6-fold coordinated Ti-oxides defect excited states in 2nd derivative O K pre-edge spectra are essentially the same as single Ti-atom d2 transitions in Tanabe-Sugano (T-S) diagrams. O-vacated site defects in 8-fold coordinated ZrO2 and HfO2 are described by d8 T-S diagrams. T-S defect state ordering and splittings are functions of the coordination and symmetry of vacated site bordering TM atoms. ΔLF values from the analysis of T-S diagrams indicate medium range order (MRO) extending to 3rd and 4th nearest-neighbor (NN) TM-atoms. Values are different for 6-fold Ti, and 8-fold ZrO2 and HfO2, and scale inversely with differences in respective formal ionic radii. O-vacated site bonding

  3. Terahertz dielectric response of photoexcited carriers in Si revealed via single-shot optical-pump and terahertz-probe spectroscopy

    SciTech Connect

    Minami, Yasuo; Horiuchi, Kohei; Masuda, Kaisei; Takeda, Jun; Katayama, Ikufumi

    2015-10-26

    We have demonstrated accurate observations of terahertz (THz) dielectric response due to photoexcited carriers in a Si plate via single-shot optical-pump and THz-probe spectroscopy. In contrast to conventional THz time-domain spectroscopy, this spectroscopic technique allows single-shot detection of the THz response of materials at a given delay time between the pump and THz pulses, thereby sufficiently extending the time interval between the pump pulses. As a result, we can accurately measure the dielectric properties of materials, while avoiding artifacts in the response caused by the accumulation of long-lived photoexcited carriers. Using our single-shot scheme, the transmittance of a Si plate was measured in the range of 0.5–2.5 THz with different pump fluences. Based on a Drude model analysis, the optically induced complex dielectric constant, plasma frequency, and damping rate in the THz region were quantitatively evaluated.

  4. Moving solvated electrons with light: Nonadiabatic mixed quantum/classical molecular dynamics simulations of the relocalization of photoexcited solvated electrons in tetrahydrofuran (THF)

    SciTech Connect

    Bedard-Hearn, Michael J.; Larsen, Ross E.; Schwartz, Benjamin J.

    2006-11-21

    Motivated by recent ultrafast spectroscopic experiments [Martini et al., Science 293, 462 (2001)], which suggest that photoexcited solvated electrons in tetrahydrofuran (THF) can relocalize (that is, return to equilibrium in solvent cavities far from where they started), we performed a series of nonequilibrium, nonadiabatic, mixed quantum/classical molecular dynamics simulations that mimic one-photon excitation of the THF-solvated electron. We find that as photoexcited THF-solvated electrons relax to their ground states either by continuous mixing from the excited state or via nonadiabatic transitions, {approx}30% of them relocalize into cavities that can be over 1 nm away from where they originated, in close agreement with the experiments. A detailed investigation shows that the ability of excited THF-solvated electrons to undergo photoinduced relocalization stems from the existence of preexisting cavity traps that are an intrinsic part of the structure of liquid THF. This explains why solvated electrons can undergo photoinduced relocalization in solvents like THF but not in solvents like water, which lack the preexisting traps necessary to stabilize the excited electron in other places in the fluid. We also find that even when they do not ultimately relocalize, photoexcited solvated electrons in THF temporarily visit other sites in the fluid, explaining why the photoexcitation of THF-solvated electrons is so efficient at promoting recombination with nearby scavengers. Overall, our study shows that the defining characteristic of a liquid that permits the photoassisted relocalization of solvated electrons is the existence of nascent cavities that are attractive to an excess electron; we propose that other such liquids can be found from classical computer simulations or neutron diffraction experiments.

  5. SWCNT Photocatalyst for Hydrogen Production from Water upon Photoexcitation of (8, 3) SWCNT at 680-nm Light

    PubMed Central

    Murakami, Noritake; Tango, Yuto; Miyake, Hideaki; Tajima, Tomoyuki; Nishina, Yuta; Kurashige, Wataru; Negishi, Yuichi; Takaguchi, Yutaka

    2017-01-01

    Single-walled carbon nanotubes (SWCNTs) are potentially strong optical absorbers with tunable absorption bands depending on their chiral indices (n, m). Their application for solar energy conversion is difficult because of the large binding energy (>100 meV) of electron-hole pairs, known as excitons, produced by optical absorption. Recent development of photovoltaic devices based on SWCNTs as light-absorbing components have shown that the creation of heterojunctions by pairing chirality-controlled SWCNTs with C60 is the key for high power conversion efficiency. In contrast to thin film devices, photocatalytic reactions in a dispersion/solution system triggered by the photoexcitation of SWCNTs have never been reported due to the difficulty of the construction of a well-ordered surface on SWCNTs. Here, we show a clear-cut example of a SWCNT photocatalyst producing H2 from water. Self-organization of a fullerodendron on the SWCNT core affords water-dispersible coaxial nanowires possessing SWCNT/C60 heterojunctions, of which a dendron shell can act as support of a co-catalyst for H2 evolution. Because the band offset between the LUMO levels of (8, 3)SWCNT and C60 satisfactorily exceeds the exciton binding energy to allow efficient exciton dissociation, the (8, 3)SWCNT/fullerodendron coaxial photocatalyst shows H2-evolving activity (QY = 0.015) upon 680-nm illumination, which is E22 absorption of (8, 3) SWCNT. PMID:28262708

  6. SWCNT Photocatalyst for Hydrogen Production from Water upon Photoexcitation of (8, 3) SWCNT at 680-nm Light.

    PubMed

    Murakami, Noritake; Tango, Yuto; Miyake, Hideaki; Tajima, Tomoyuki; Nishina, Yuta; Kurashige, Wataru; Negishi, Yuichi; Takaguchi, Yutaka

    2017-03-06

    Single-walled carbon nanotubes (SWCNTs) are potentially strong optical absorbers with tunable absorption bands depending on their chiral indices (n, m). Their application for solar energy conversion is difficult because of the large binding energy (>100 meV) of electron-hole pairs, known as excitons, produced by optical absorption. Recent development of photovoltaic devices based on SWCNTs as light-absorbing components have shown that the creation of heterojunctions by pairing chirality-controlled SWCNTs with C60 is the key for high power conversion efficiency. In contrast to thin film devices, photocatalytic reactions in a dispersion/solution system triggered by the photoexcitation of SWCNTs have never been reported due to the difficulty of the construction of a well-ordered surface on SWCNTs. Here, we show a clear-cut example of a SWCNT photocatalyst producing H2 from water. Self-organization of a fullerodendron on the SWCNT core affords water-dispersible coaxial nanowires possessing SWCNT/C60 heterojunctions, of which a dendron shell can act as support of a co-catalyst for H2 evolution. Because the band offset between the LUMO levels of (8, 3)SWCNT and C60 satisfactorily exceeds the exciton binding energy to allow efficient exciton dissociation, the (8, 3)SWCNT/fullerodendron coaxial photocatalyst shows H2-evolving activity (QY = 0.015) upon 680-nm illumination, which is E22 absorption of (8, 3) SWCNT.

  7. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    DOE PAGES

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; ...

    2016-02-26

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase seperated regions. The ability to simultanousely track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of- the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiatedmore » at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, which is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. Lastly, the direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.« less

  8. Linking photochemistry in the gas and solution phase: S-H bond fission in p-methylthiophenol following UV photoexcitation.

    PubMed

    Oliver, Thomas A A; Zhang, Yuyuan; Ashfold, Michael N R; Bradforth, Stephen E

    2011-01-01

    Gas-phase H (Rydberg) atom photofragment translational spectroscopy and solution-phase femtosecond-pump dispersed-probe transient absorption techniques are applied to explore the excited state dynamics of p-methylthiophenol connecting the short time reactive dynamics in the two phases. The molecule is excited at a range of UV wavelengths from 286 to 193 nm. The experiments clearly demonstrate that photoexcitation results in S-H bond fission--both in the gas phase and in ethanol solution-and that the resulting p-methythiophenoxyl radical fragments are formed with significant vibrational excitation. In the gas phase, the recoil anisotropy of the H atom and the vibrational energy disposal in the p-MePhS radical products formed at the longer excitation wavelengths reveal the operation of two excited state dissociation mechanisms. The prompt excited state dissociation motif appears to map into the condensed phase also. In both phases, radicals are produced in both their ground and first excited electronic states; characteristic signatures for both sets of radical products are already apparent in the condensed phase studies after 50 fs. No evidence is seen for either solute ionisation or proton coupled electron transfer--two alternate mechanisms that have been proposed for similar heteroaromatics in solution. Therefore, at least for prompt S-H bond fissions, the direct observation of the dissociation process in solution confirms that the gas phase photofragmentation studies indeed provide important insights into the early time dynamics that transfer to the condensed phase.

  9. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    PubMed Central

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J.; Jung, Il Woong; Walko, Donald A.; Dufresne, Eric M.; Jeong, Jaewoo; Samant, Mahesh G.; Parkin, Stuart S. P.; Freeland, John W.; Evans, Paul G.; Wen, Haidan

    2016-01-01

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems. PMID:26915398

  10. SWCNT Photocatalyst for Hydrogen Production from Water upon Photoexcitation of (8, 3) SWCNT at 680-nm Light

    NASA Astrophysics Data System (ADS)

    Murakami, Noritake; Tango, Yuto; Miyake, Hideaki; Tajima, Tomoyuki; Nishina, Yuta; Kurashige, Wataru; Negishi, Yuichi; Takaguchi, Yutaka

    2017-03-01

    Single-walled carbon nanotubes (SWCNTs) are potentially strong optical absorbers with tunable absorption bands depending on their chiral indices (n, m). Their application for solar energy conversion is difficult because of the large binding energy (>100 meV) of electron-hole pairs, known as excitons, produced by optical absorption. Recent development of photovoltaic devices based on SWCNTs as light-absorbing components have shown that the creation of heterojunctions by pairing chirality-controlled SWCNTs with C60 is the key for high power conversion efficiency. In contrast to thin film devices, photocatalytic reactions in a dispersion/solution system triggered by the photoexcitation of SWCNTs have never been reported due to the difficulty of the construction of a well-ordered surface on SWCNTs. Here, we show a clear-cut example of a SWCNT photocatalyst producing H2 from water. Self-organization of a fullerodendron on the SWCNT core affords water-dispersible coaxial nanowires possessing SWCNT/C60 heterojunctions, of which a dendron shell can act as support of a co-catalyst for H2 evolution. Because the band offset between the LUMO levels of (8, 3)SWCNT and C60 satisfactorily exceeds the exciton binding energy to allow efficient exciton dissociation, the (8, 3)SWCNT/fullerodendron coaxial photocatalyst shows H2-evolving activity (QY = 0.015) upon 680-nm illumination, which is E22 absorption of (8, 3) SWCNT.

  11. An electron spin polarization study of the interaction of photoexcited triplet molecules with mono- and polynitroxyl stable free radicals

    SciTech Connect

    Turro, N.J.; Khudyakov, I.V.; Bossmann, S.H. ); Dwyer, D.W. )

    1993-02-11

    Time-resolved electron spin resonance (TR ESR) has been used to investigate the chemically induced dynamic electron polarization (CIDEP) generated by the interaction of stable free radicals with the triplet states of benzophenone, benzil, and 2-acetylnaphthalene. The stable radicals were mono-, di-, tri-, and tetranitroxyl free radicals possessing the 2,2,6,6-tetramethylpiperidine-N-oxyl moiety. All of the stable radical systems investigated were found to be emissively polarized by interaction with the triplet states, and the phase of polarization was independent of the sign of zero-field splitting (D) of the interacting triple molecule. Possible and likely mechanisms of polarization transfer (creation) resulting from the interaction of photoexcited triplet molecules with nitroxyls in the strong electron exchange are discussed. The emissive CIDEP of nitroxyls observed in the interactions with triplet benzil, which has D > 0, provides strong support for the operation of the radical-triplet pair mechanism. Within the time scale of TR ESR experiments ([approximately]10[sup [minus]7]--10[sup [minus]6] s) no significant variation in the shape of the CIDEP spectra of the nitroxyls was observed, either in viscous media or in micelles. It is concluded that intramolecular spin exchange (or conformational change) of polynitroyls occurs much faster than the time resolution of the experiment. 24 refs., 6 figs., 1 tab.

  12. Spatially Resolved Photoexcited Charge-Carrier Dynamics in Phase-Engineered Monolayer MoS2

    SciTech Connect

    Yamaguchi, Hisato; Blancon, Jean-Christophe; Kappera, Rajesh; Lei, Sidong; Najmaei, Sina; Mangum, Benjamin D.; Gupta, Gautam; Ajayan, Pulickel M.; Lou, Jun; Chhowalla, Manish; Crochet, Jared J.; Mohite, Aditya D.

    2014-12-18

    A fundamental understanding of the intrinsic optoelectronic properties of atomically thin transition metal dichalcogenides (TMDs) is crucial for its integration into high performance semiconductor devices. We investigate the transport properties of chemical vapor deposition (CVD) grown monolayer molybdenum disulfide (MoS2) under photo-excitation using correlated scanning photocurrent microscopy and photoluminescence imaging. We examined the effect of local phase transformation underneath the metal electrodes on the generation of photocurrent across the channel length with diffraction-limited spatial resolution. While maximum photocurrent generation occurs at the Schottky contacts of semiconducting (2H-phase) MoS2, after the metallic phase transformation (1T-phase), the photocurrent peak is observed towards the center of the device channel, suggesting a strong reduction of native Schottky barriers. Analysis using the bias and position dependence of the photocurrent indicates that the Schottky barrier heights are few meV for 1T- and ~200 meV for 2H-contacted devices. We also demonstrate that a reduction of native Schottky barriers in a 1T device enhances the photo responsivity by more than one order of magnitude, a crucial parameter in achieving high performance optoelectronic devices. The obtained results pave a pathway for the fundamental understanding of intrinsic optoelectronic properties of atomically thin TMDs where Ohmic contacts are necessary for achieving high efficiency devices with low power consumption.

  13. Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy

    PubMed Central

    Santomauro, Fabio G.; Grilj, Jakob; Mewes, Lars; Nedelcu, Georgian; Yakunin, Sergii; Rossi, Thomas; Capano, Gloria; Al Haddad, André; Budarz, James; Kinschel, Dominik; Ferreira, Dario S.; Rossi, Giacomo; Gutierrez Tovar, Mario; Grolimund, Daniel; Samson, Valerie; Nachtegaal, Maarten; Smolentsev, Grigory; Kovalenko, Maksym V.; Chergui, Majed

    2016-01-01

    We report on an element-selective study of the fate of charge carriers in photoexcited inorganic CsPbBr3 and CsPb(ClBr)3 perovskite nanocrystals in toluene solutions using time-resolved X-ray absorption spectroscopy with 80 ps time resolution. Probing the Br K-edge, the Pb L3-edge, and the Cs L2-edge, we find that holes in the valence band are localized at Br atoms, forming small polarons, while electrons appear as delocalized in the conduction band. No signature of either electronic or structural changes is observed at the Cs L2-edge. The results at the Br and Pb edges suggest the existence of a weakly localized exciton, while the absence of signatures at the Cs edge indicates that the Cs+ cation plays no role in the charge transport, at least beyond 80 ps. This first, time-resolved element-specific study of perovskites helps understand the rather modest charge carrier mobilities in these materials. PMID:28083541

  14. Manipulation of an Innate Escape Response in Drosophila: Photoexcitation of acj6 Neurons Induces the Escape Response

    PubMed Central

    Manoli, Devanand S.; Zhang, Feng; Deisseroth, Karl; Baker, Bruce S.; Scott, Matthew P.

    2009-01-01

    Background The genetic analysis of behavior in Drosophila melanogaster has linked genes controlling neuronal connectivity and physiology to specific neuronal circuits underlying a variety of innate behaviors. We investigated the circuitry underlying the adult startle response, using photoexcitation of neurons that produce the abnormal chemosensory jump 6 (acj6) transcription factor. This transcription factor has previously been shown to play a role in neuronal pathfinding and neurotransmitter modality, but the role of acj6 neurons in the adult startle response was largely unknown. Principal Findings We show that the activity of these neurons is necessary for a wild-type startle response and that excitation is sufficient to generate a synthetic escape response. Further, we show that this synthetic response is still sensitive to the dose of acj6 suggesting that that acj6 mutation alters neuronal activity as well as connectivity and neurotransmitter production. Results/Significance These results extend the understanding of the role of acj6 and of the adult startle response in general. They also demonstrate the usefulness of activity-dependent characterization of neuronal circuits underlying innate behaviors in Drosophila, and the utility of integrating genetic analysis into modern circuit analysis techniques. PMID:19340304

  15. (2)H-decoupling-accelerated (1)H spin diffusion in dynamic nuclear polarization with photoexcited triplet electrons.

    PubMed

    Negoro, M; Nakayama, K; Tateishi, K; Kagawa, A; Takeda, K; Kitagawa, M

    2010-10-21

    In dynamic nuclear polarization (DNP) experiments applied to organic solids for creating nonequilibrium, high (1)H spin polarization, an efficient buildup of (1)H polarization is attained by partially deuterating the material of interest with an appropriate (1)H concentration. In such a dilute (1)H spin system, it is shown that the (1)H spin diffusion rate and thereby the buildup efficiency of (1)H polarization can further be enhanced by continually applying radiofrequency irradiation for deuterium decoupling during the DNP process. As experimentally confirmed in this work, the electron spin polarization of the photoexcited triplet state is mainly transferred only to those (1)H spins, which are in the vicinity of the electron spins, and (1)H spin diffusion transports the localized (1)H polarization over the whole sample volume. The (1)H spin diffusion coefficients are estimated from DNP repetition interval dependence of the initial buildup rate of (1)H polarization, and the result indicates that the spin diffusion coefficient is enhanced by a factor of 2 compared to that without (2)H decoupling.

  16. A photoexcited broadband switchable metamaterial absorber with polarization-insensitive and wide-angle absorption for terahertz waves

    NASA Astrophysics Data System (ADS)

    Cheng, Yongzhi; Gong, Rongzhou; Cheng, Zhengze

    2016-02-01

    We present a design and numerical study of a polarization-insensitive and wide-angle photoexcited broadband switchable metamaterial absorber (MMA) in the terahertz (THz) regime. The switchable MMA comprises a periodic array of dielectric substrate sandwiched with metallic four-splits-ring resonator (FSRR) structure and continuous metallic film. Filling the gap between the SRRs with a photoconductive semiconductor (silicon, Si), leading to easy modification of its electromagnetic (EM) response through a pump beam. The conductivity of photoconductive Si pads filled in the gap of SRRs can be tuned efficiently by external pump power. This results in the modulation of absorption magnitude with a modulation depth of 62.2%, and a broadband switch of absorption peak frequencies varying from 0.82 to 0.51 THz. Further numerical simulations demonstrate that the switchable MMA has the merit of polarization-insensitive and wide-angle absorption. The realization of broadband redshift tunable MMA offers opportunities to mature semiconductor technologies and potential applications in active THz modulator and switcher.

  17. Localized holes and delocalized electrons in photoexcited inorganic perovskites: Watching each atomic actor by picosecond X-ray absorption spectroscopy.

    PubMed

    Santomauro, Fabio G; Grilj, Jakob; Mewes, Lars; Nedelcu, Georgian; Yakunin, Sergii; Rossi, Thomas; Capano, Gloria; Al Haddad, André; Budarz, James; Kinschel, Dominik; Ferreira, Dario S; Rossi, Giacomo; Gutierrez Tovar, Mario; Grolimund, Daniel; Samson, Valerie; Nachtegaal, Maarten; Smolentsev, Grigory; Kovalenko, Maksym V; Chergui, Majed

    2017-07-01

    We report on an element-selective study of the fate of charge carriers in photoexcited inorganic CsPbBr3 and CsPb(ClBr)3 perovskite nanocrystals in toluene solutions using time-resolved X-ray absorption spectroscopy with 80 ps time resolution. Probing the Br K-edge, the Pb L3-edge, and the Cs L2-edge, we find that holes in the valence band are localized at Br atoms, forming small polarons, while electrons appear as delocalized in the conduction band. No signature of either electronic or structural changes is observed at the Cs L2-edge. The results at the Br and Pb edges suggest the existence of a weakly localized exciton, while the absence of signatures at the Cs edge indicates that the Cs(+) cation plays no role in the charge transport, at least beyond 80 ps. This first, time-resolved element-specific study of perovskites helps understand the rather modest charge carrier mobilities in these materials.

  18. Time Evolution of Charge Carriers & Phonons after Photo-Excitation by an Ultra-Short Light Pulse in Bulk Germanium

    NASA Astrophysics Data System (ADS)

    Fahy, Stephen; Murphy-Armando, Felipe; Trigo, Mariano; Savic, Ivana; Murray, Eamonn; Reis, David

    We have calculated the time-evolution of carriers and generated phonons in Ge after ultrafast photo-excitation above the direct band-gap. The relevant electron-phonon and anharmonic phonon scattering rates are obtained from first-principles electronic structure calculations. Measurements of the x-ray diffuse scattering after excitation near the L point in the Brillouin zone find a relatively slow (5 ps, compared to the typical electron-phonon energy relaxation of the Gamma-L phonon) increase of the phonon population. We find this is due to emission caused by the scattering of electrons between the Delta and L valleys, after the initial depopulation of the Gamma valley. The relative slowness of this process is due to a combination of causes: (i) the finite time for the initial depopulation of the conduction Gamma valley; (ii) the associated electron-phonon coupling is relatively weaker (compared to Gamma-L, Gamma-Delta and Delta-Delta couplings) ; (iii) the TA associated phonon has a long lifetime and (iv) the depopulation of the Delta valley suppresses the phonon emission. Supported by Science Foundation Ireland, Grant 12/1A/1601.

  19. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy.

    PubMed

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J; Jung, Il Woong; Walko, Donald A; Dufresne, Eric M; Jeong, Jaewoo; Samant, Mahesh G; Parkin, Stuart S P; Freeland, John W; Evans, Paul G; Wen, Haidan

    2016-02-26

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

  20. Photoexcited Nuclear Dynamics with Ab Initio Electronic Structure Theory: Is TD-DFT Ready For the Challenge?

    NASA Astrophysics Data System (ADS)

    Subotnik, Joseph

    In this talk, I will give a broad overview of our work in nonadiabatic dynamics, i.e. the dynamics of strongly coupled nuclear-electronic motion whereby the relaxation of a photo-excited electron leads to the heating up of phonons. I will briefly discuss how to model such nuclear motion beyond mean field theory. Armed with the proper framework, I will then focus on how to calculate one flavor of electron-phonon couplings, known as derivative couplings in the chemical literature. Derivative couplings are the matrix elements that couple adiabatic electronic states within the Born-Oppenheimer treatment, and I will show that these matrix elements show spurious poles using formal (frequency-independent) time-dependent density functional theory. To correct this TD-DFT failure, a simple approximation will be proposed and evaluated. Finally, time permitting, I will show some ab initio calculations whereby one can use TD-DFT derivative couplings to study electronic relaxation through a conical intersection.

  1. Photoexcitation and charge-transfer-to-solvent relaxation dynamics of the I(-)(CH3CN) complex.

    PubMed

    Mak, Chun C; Timerghazin, Qadir K; Peslherbe, Gilles H

    2013-08-15

    Photoexcitation of iodide-acetonitrile clusters, I(-)(CH3CN)n, to the charge-transfer-to-solvent (CTTS) state and subsequent cluster relaxation could result in the possible formation of cluster analogues of the bulk solvated electron. In this work, the relaxation process of the CTTS excited iodide-acetonitrile binary complex, [I(-)(CH3CN)]*, is investigated using rigorous ab initio quantum chemistry calculations and direct-dynamics simulations to gain insight into the role and motion of iodine and acetonitrile in the relaxation of CTTS excited I(-)(CH3CN)n. Computed potential energy curves and profiles of the excited electron vertical detachment energy for [I(-)(CH3CN)]* along the iodine-acetonitrile distance coordinate reveal for the first time significant dispersion effects between iodine and the excited electron, which can have a significant stabilizing effect on the latter. Results of direct-dynamics simulations demonstrate that [I(-)(CH3CN)]* undergoes dissociation to iodine and acetonitrile fragments, resulting in decreased stability of the excited electron. The present work provides strong evidence of solvent translational motion and iodine ejection as key aspects of the early time relaxation of CTTS excited I(-)(CH3CN)n that can also have a substantial impact on the subsequent electron solvation processes and further demonstrates that intricate details of the relaxation process of CTTS excited iodide-polar solvent molecule clusters make it heavily solvent-dependent.

  2. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    NASA Astrophysics Data System (ADS)

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J.; Jung, Il Woong; Walko, Donald A.; Dufresne, Eric M.; Jeong, Jaewoo; Samant, Mahesh G.; Parkin, Stuart S. P.; Freeland, John W.; Evans, Paul G.; Wen, Haidan

    2016-02-01

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase separated regions. The ability to simultaneously track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of-the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, and is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. The direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

  3. Probing the photoexcited states of rhodium corroles by time-resolved Q-band EPR. Observation of strong spin-orbit coupling effects.

    PubMed

    Rozenshtein, V; Wagnert, L; Berg, A; Stavitski, E; Berthold, T; Kothe, G; Saltsman, I; Gross, Z; Levanon, H

    2008-06-19

    The photoexcited states of two 5,10,15-tris(pentafluorophenyl)corroles (tpfc), hosting Rh(III) in their core, namely Rh(pyr)(PPh 3)(tpfc) and Rh(PPh 3)(tpfc), have been studied by time-resolved electron paramagnetic resonance (TREPR) combined with pulsed laser excitation. Using the transient nutation technique, the spin polarized spectra are assigned to photoexcited triplet states. The spectral widths observed for the two Rh(III) corroles crucially depend on the axial ligands at the Rh(III) metal ion. In case of Rh(PPh 3)(tpfc), the TREPR spectra are found to extend over 200 mT, which exceeds the spectral width of non-transition-metal corroles by more than a factor of 3. Moreover, the EPR lines of the Rh(III) corroles are less symmetric than those of the non-transition-metal corrroles. The peculiarities in the TREPR spectra of the Rh(III) corroles can be rationalized in terms of strong spin-orbit coupling (SOC) associated with the transition-metal character of the Rh(III) ion. It is assumed that SOC in the photoexcited Rh(III) corroles effectively admixes metal centered (3)dd-states to the corrole centered (3)pipi*-states detected in the TREPR experiments. This admixture leads to an increased zero-field splitting and a large g-tensor anisotropy as manifested by the excited Rh(III) corroles.

  4. Experimental and theoretical study of hydroxyquinolines: hydroxyl group position dependent dipole moment and charge-separation in the photoexcited state leading to fluorescence.

    PubMed

    Mehata, Mohan Singh; Singh, Ajay K; Sinha, Ravindra Kumar

    2016-11-17

    Optical absorption and fluorescence (FL) spectra of 2-, 6-, 7-, 8-hydroxyquinolines (2-,6-,7- and 8-HQs) have been measured at room temperature in the wide range of solvents of different polarities, dielectric constant and refractive index. The ground state dipole moment (µ g) and excited state dipole moment (µ e) of 2-, 6-, 7- and 8-HQs were obtained using solvatochromic shift (SS) methods and microscopic solvent polarity parameters (MSPP). Change in the dipole moment (Δµ) between the ground and photo-excited states was estimated from SS and MSPP methods. DFT and TDDFT based theoretical calculations were performed for the ground and excited states dipole moments, and for vertical transitions. A significant enhancement in the excited state dipole moment was observed following photo-excitation. The large value of Δµ clearly indicates to the charge-separation in the photo-excited states, which in turn depends on the position of the hydroxyl group in the ring.

  5. Experimental and theoretical study of hydroxyquinolines: hydroxyl group position dependent dipole moment and charge-separation in the photoexcited state leading to fluorescence

    NASA Astrophysics Data System (ADS)

    Singh Mehata, Mohan; Singh, Ajay K.; Sinha, Ravindra Kumar

    2016-12-01

    Optical absorption and fluorescence (FL) spectra of 2-, 6-, 7-, 8-hydroxyquinolines (2-,6-,7- and 8-HQs) have been measured at room temperature in the wide range of solvents of different polarities, dielectric constant and refractive index. The ground state dipole moment (µ g) and excited state dipole moment (µ e) of 2-, 6-, 7- and 8-HQs were obtained using solvatochromic shift (SS) methods and microscopic solvent polarity parameters (MSPP). Change in the dipole moment (Δµ) between the ground and photo-excited states was estimated from SS and MSPP methods. DFT and TDDFT based theoretical calculations were performed for the ground and excited states dipole moments, and for vertical transitions. A significant enhancement in the excited state dipole moment was observed following photo-excitation. The large value of Δµ clearly indicates to the charge-separation in the photo-excited states, which in turn depends on the position of the hydroxyl group in the ring.

  6. Tuning Hole and Electron Transfer from Photo-excited CdSe Quantum Dot to Phenol Derivatives: Effect of Electron Donating and Withdrawing Moiety.

    PubMed

    Ghosh, Hirendra Nath; Debnath, Tushar; Sebastian, Deepa; Maiti, Sourav

    2017-03-27

    Charge transfer processes from photo-excited CdSe QDs to phenol derivatives with electron donating (4-methoxy) and electron withdrawing (4-nitro) moiety have been demonstrated by using steady state and time-resolved emission and femto-second transient absorption spectroscopy. Steady state and time-resolved emission studies suggest that in presence of both 4-nitro phenol (4NP) and 4-methoxy phenol (4MP) CdSe QDs luminescence gets quenched. Stern-Volmer analysis suggests both static and dynamic mechanisms are active for both the QD/phenol composites. Cyclic volatmetric analysis recommends that photo-excited CdSe QDs can donate electron to 4NP and hole to 4MP. To reconfirm both electron and hole transfer mechanism CdSe/CdS quasi type-II and CdSe/CdTe type-II core-shell NC were synthesized and the photoluminescence quenching were monitored in absence and in presence of both 4NP and 4MP where systematically hole and electron transfer were restricted. Our studies suggest that indeed electron and hole transfer take place from photo-excited CdSe to 4NP and 4MP respectively. To monitor the charge transfer dynamics in both the systems in early time scale, we have employed femtosecond transient absorption (TA) spectroscopic techniques. Both electron and hole transfer and charge recombination dynamics have been discussed and effect of electron donating and withdrawing group has been demonstrated.

  7. Prediction of core level binding energies in density functional theory: Rigorous definition of initial and final state contributions and implications on the physical meaning of Kohn-Sham energies.

    PubMed

    Pueyo Bellafont, Noèlia; Bagus, Paul S; Illas, Francesc

    2015-06-07

    A systematic study of the N(1s) core level binding energies (BE's) in a broad series of molecules is presented employing Hartree-Fock (HF) and the B3LYP, PBE0, and LC-BPBE density functional theory (DFT) based methods with a near HF basis set. The results show that all these methods give reasonably accurate BE's with B3LYP being slightly better than HF but with both PBE0 and LCBPBE being poorer than HF. A rigorous and general decomposition of core level binding energy values into initial and final state contributions to the BE's is proposed that can be used within either HF or DFT methods. The results show that Koopmans' theorem does not hold for the Kohn-Sham eigenvalues. Consequently, Kohn-Sham orbital energies of core orbitals do not provide estimates of the initial state contribution to core level BE's; hence, they cannot be used to decompose initial and final state contributions to BE's. However, when the initial state contribution to DFT BE's is properly defined, the decompositions of initial and final state contributions given by DFT, with several different functionals, are very similar to those obtained with HF. Furthermore, it is shown that the differences of Kohn-Sham orbital energies taken with respect to a common reference do follow the trend of the properly calculated initial state contributions. These conclusions are especially important for condensed phase systems where our results validate the use of band structure calculations to determine initial state contributions to BE shifts.

  8. Deep vein thrombosis - discharge

    MedlinePlus

    ... this page: //medlineplus.gov/ency/patientinstructions/000027.htm Deep vein thrombosis - discharge To use the sharing features ... page, please enable JavaScript. You were treated for deep vein thrombosis ( DVT ). This is a condition in ...

  9. Taoism and Deep Ecology.

    ERIC Educational Resources Information Center

    Sylvan, Richard; Bennett, David

    1988-01-01

    Contrasted are the philosophies of Deep Ecology and ancient Chinese. Discusses the cosmology, morality, lifestyle, views of power, politics, and environmental philosophies of each. Concludes that Deep Ecology could gain much from Taoism. (CW)

  10. Taoism and Deep Ecology.

    ERIC Educational Resources Information Center

    Sylvan, Richard; Bennett, David

    1988-01-01

    Contrasted are the philosophies of Deep Ecology and ancient Chinese. Discusses the cosmology, morality, lifestyle, views of power, politics, and environmental philosophies of each. Concludes that Deep Ecology could gain much from Taoism. (CW)

  11. Mechanism of photoexcited precession of magnetization in (Ga,Mn)As on the basis of time-resolved spectroscopy

    NASA Astrophysics Data System (ADS)

    Matsuda, T.; Munekata, H.

    2016-02-01

    In order to investigate the mechanism of photoexcited precession of magnetization in ferromagnetic G a1 -xM nxAs , magneto-optical (MO) and differential reflectivity (Δ R /R ; DR) temporal profiles are studied at relatively long (picosecond to nanosecond) and ultrashort (1 ps or less) time scales for samples with different Mn content (x =0.01 -0.11 ) . As to the oscillatory MO profiles observed in the long time scale, simulation based on the Landau-Lifshitz-Gilbert equation combined with two different MO effects confirms photoinducement of the perpendicular anisotropy component Δ Heff ,⊥ . As for the profiles observed in the ultrashort time scale, they are consistently explained in terms of the dynamics of photogenerated carriers, but not by the sudden reduction in magnetization (the ultrafast demagnetization). In light of these experimental results and analyses, a mechanism that accounts for the photoinduced Δ Heff ,⊥ is addressed: namely, photoionizationlike excitation of M n2 + , M n2 ++h ν →M n2 +,*=M n3++e- . That such excitation tips magnetic anisotropy toward the out-of-plane direction through the inducement of orbital angular momentum and the gradient ∂ (M n2 +,* )/∂ z is discussed. The validity of the proposed mechanism is examined by estimating the efficiency of excitation on the basis of the Lambert-Beer law and the experimental Δ Heff ,⊥ values, through which an efficiency of 1-10 ppm with a nominal optical cross section of around 5 ×10-12m2 is obtained.

  12. Deep Space Telecommunications

    NASA Technical Reports Server (NTRS)

    Kuiper, T. B. H.; Resch, G. M.

    2000-01-01

    The increasing load on NASA's deep Space Network, the new capabilities for deep space missions inherent in a next-generation radio telescope, and the potential of new telescope technology for reducing construction and operation costs suggest a natural marriage between radio astronomy and deep space telecommunications in developing advanced radio telescope concepts.

  13. Deep Web video

    SciTech Connect

    None Available

    2009-06-01

    To make the web work better for science, OSTI has developed state-of-the-art technologies and services including a deep web search capability. The deep web includes content in searchable databases available to web users but not accessible by popular search engines, such as Google. This video provides an introduction to the deep web search engine.

  14. Deep Web video

    ScienceCinema

    None Available

    2016-07-12

    To make the web work better for science, OSTI has developed state-of-the-art technologies and services including a deep web search capability. The deep web includes content in searchable databases available to web users but not accessible by popular search engines, such as Google. This video provides an introduction to the deep web search engine.

  15. Probing the Electronic Structure of a Photoexcited Solar Cell Dye with Transient X-ray Absorption Spectroscopy

    SciTech Connect

    Van Kuiken, Benjamin E.; Huse, Nils; Cho, Hana; Strader, Matthew L.; Lynch, Michael S.; Schoenlein, Robert W.; Khalil, Munira

    2012-06-21

    This study uses transient X-ray absorption (XA) spectroscopy and timedependent density functional theory (TD-DFT) to directly visualize the charge density around the metal atom and the surrounding ligands following an ultrafast metal-to-ligand charge-transfer (MLCT) process in the widely used RuII solar cell dye, Ru(dcbpy)2(NCS)2 (termed N3). We measure the Ru L-edge XA spectra of the singlet ground (1A1) and the transient triplet (3MLCT) excited state of N34 and perform TD-DFT calculations of 2p core-level excitations, which identify a unique spectral signature of the electron density on the NCS ligands. We find that the Ru 2p, Ru eg, and NCS orbitals are stabilized by 2.0, 1.0, and 0.6 eV, respectively, in the transient 3MLCT state of the dye. These results highlight the role of the NCS ligands in governing the oxidation state of the Ru center.

  16. The photoexcitation of crystalline ice and amorphous solid water: A molecular dynamics study of outcomes at 11 K and 125 K

    SciTech Connect

    Crouse, J.; Loock, H.-P. Cann, N. M.

    2015-07-21

    Photoexcitation of crystalline ice Ih and amorphous solid water at 7-9 eV is examined using molecular dynamics simulations and a fully flexible water model. The probabilities of photofragment desorption, trapping, and recombination are examined for crystalline ice at 11 K and at 125 K and for amorphous solid water at 11 K. For 11 K crystalline ice, a fully rigid water model is also employed for comparison. The kinetic energy of desorbed H atoms and the distance travelled by trapped fragments are correlated to the location and the local environment of the photoexcited water molecule. In all cases, H atom desorption is found to be the most likely outcome in the top bilayer while trapping of all photofragments is most probable deeper in the solid where the likelihood for recombination of the fragments into H{sub 2}O molecules also rises. Trajectory analysis indicates that the local hydrogen bonding network in amorphous solid water is more easily distorted by a photodissociation event compared to crystalline ice. Also, simulations indicate that desorption of OH radicals and H{sub 2}O molecules are more probable in amorphous solid water. The kinetic energy distributions for desorbed H atoms show a peak at high energy in crystalline ice, arising from photoexcited water molecules in the top monolayer. This peak is less pronounced in amorphous solid water. H atoms that are trapped may be displaced by up to ∼10 water cages, but migrate on average 3 water cages. Trapped OH fragments tend to stay near the original solvent cage.

  17. Photoexcitations in Polyacetylene.

    DTIC Science & Technology

    1981-11-11

    recombination luminescence; (CH) X interband absorption edge; excitation energies ; Stokes shift; temperature 0....dependence; isomerization; phototransport...turns on sharply for excitation S energies greater than 2.k5e ; irLivin., as S;takes shift of 0.15eV. Studies of the temperature Ulependence kT 7K) -ci...Philadelphia, PA 19104 INov ~e!f M 81 Reproduction in whole or in part is permitted for any purpose of the United States Government Approved for public

  18. Identification of Deep Earthquakes

    DTIC Science & Technology

    2010-09-01

    develop a ground truth dataset of earthquakes at both normal crustal depths and earthquakes from subduction zones , below the overlying crust. Many...deep earthquakes (depths between about 50 and 300 km). These deep earthquakes are known to occur in the Asia-India continental collision zone ...and/or NIL, as these stations are within a few hundred km of the zone where deep earthquakes are known to occur. To date we have selected about 300

  19. The deep space network

    NASA Technical Reports Server (NTRS)

    1975-01-01

    Summaries are given of Deep Space Network progress in flight project support, tracking and data acquisition research and technology, network engineering, hardware and software implementation, and operations.

  20. The deep space network

    NASA Technical Reports Server (NTRS)

    1977-01-01

    Presented is Deep Space Network (DSN) progress in flight project support, tracking and data acquisition (TDA) research and technology, network engineering, hardware and software implementation, and operations.

  1. Deep Space Communication

    NASA Technical Reports Server (NTRS)

    Manshadi, Farzin

    2012-01-01

    ITU defines deep space as the volume of Space at distances from the Earth equal to, or greater than, 2 106 km. Deep Space Spacecraft have to travel tens of millions of km from Earth to reach the nearest object in deep space. Spacecraft mass and power are precious. Large ground-based antennas and very high power transmitters are needed to overcome large space loss and spacecraft's small antennas and low power transmitters. Navigation is complex and highly dependent on measurements from the Earth. Every deep space mission is unique and therefore very costly to develop.

  2. A deep reef in deep trouble

    USGS Publications Warehouse

    Menza, Charles; Kendall, M.; Rogers, C.; Miller, J.

    2007-01-01

    The well-documented degradation of shallower reefs which are often closer to land and more vulnerable to pollution, sewage and other human-related stressors has led to the suggestion that deeper, more remote offshore reefs could possibly serve as sources of coral and fish larvae to replenish the shallower reefs. Yet, the distribution, status, and ecological roles of deep (>30 m) Caribbean reefs are not well known. In this report, an observation of a deep reef which has undergone a recent extensive loss of coral cover is presented. In stark contrast to the typical pattern of coral loss in shallow reefs, the deeper corals were most affected. This report is the first description of such a pattern of coral loss on a deep reef.

  3. Radiative and nonradiative recombination of photoexcited excitons in multi-shell-coated CdSe/CdS/ZnS quantum dots

    NASA Astrophysics Data System (ADS)

    Fu, Y.; Ågren, H.; Kowalewski, J. M.; Brismar, H.; Wu, J.; Yue, Y.; Dai, N.; Thylén, L.

    2009-05-01

    Colloidal quantum dots (QDs) have been widely studied for nanophotonics and bioimaging applications for which the lifetime of their fluorescence is of critical importance. We report experimental and theoretical characterizations of dynamic optical properties of multi-shell-coated CdSe/CdS/ZnS QDs. Quantum-mechanical studies of fundamental optical excitations and Monte Carlo simulations of energy relaxation mechanisms indicate that the excitonic states are densely compacted in the QDs and are easily photoexcited by the laser pulse in the presence of nonradiative electron-phonon interactions. For spherical QDs, the decay time of spontaneous radiative emission of individual photoexcited excitonic states with zero angular momenta is found to be only tens of picoseconds. In our multi-shell QDs, high-energy excitonic states of nonzero angular momenta have to go through a number of nonradiative electron-phonon interaction steps in order to relax to zero-angular-momentum excitonic states for radiative emission, resulting in an effective fluorescence peak at about 2 ns in the photoncount-time relationship. This explains the measured long average fluorescence lifetime of 3.6 ns. Such a long lifetime facilitates the applications of colloidal QDs in areas such as QD-based solar cells, bioimaging and metamaterials.

  4. Effects of interface states on photoexcited carriers in ZnO/Zn(2)SnO(4) type-II radial heterostructure nanowires.

    PubMed

    Cheng, Baochang; Wu, Guohong; Ouyang, Zhiyong; Su, Xiaohui; Xiao, Yanhe; Lei, Shuijin

    2014-03-26

    Type-II band alignment of heterostructure contributes to spatially separate electrons and holes leading to an increase in minority carrier lifetime, which has much more advantages in photocatalytic activities and photovoltaic device applications. Here, Zn2SnO4-sheathed ZnO radial heterostructure nanowires were constructed to investigate systematically interfacial charge separation. The lattice mismatch between ZnO and Zn2SnO4 induces interface states to exist at their heterointerface. At low pump fluence, photoexcited charges are localized within the ZnO core rather than separated due to the large interface barrier. Correspondingly, only ZnO-related bandedge ultraviolet (UV) and green emissions are dominated in photoluminescence spectra. At high pump fluence, however, impurities are ionized and electrons trapped in interface states are excited, resulting in a decrease in interface barrier, which makes photogenerated charges efficiently separated at their heterointerface by direct tunneling, and, consequently, an additional blue-violet emission, attributed to the heterointerface recombination of electrons in Zn2SnO4 conduction band (CB) and holes in ZnO valence band. Additionally, the heterointerface can separate effectively photoexcited carriers and form a photovoltaic effect. Our results provide the localization/separation condition of photogenerated charges for the type-II band alignment of core/shell heterostructure, which should be very useful for the realization of underpinned mechanism of the developed optoelectronic devices.

  5. Characterization of a deep-level compensation ratio through picosecond four-wave mixing on a transient reflection grating

    NASA Astrophysics Data System (ADS)

    Kadys, A.; Delaye, Ph; Roosen, G.; Jarasiunas, K.

    2007-09-01

    We demonstrate a novel application of a time-resolved four-wave mixing technique for the determination of a deep-level compensation ratio in a semi-insulating crystal. The approach is based on photoexcitation of carriers from deep impurity levels, formation of a space-charge electric field in deep traps, and monitoring dynamics of photorefractive, free- carrier and absorption gratings by light diffraction. The analysis of anisotropic diffraction features on the reflection grating provided requirements for crystal orientation in order to discriminate contribution of amplitude grating from the photorefractive phase grating, both being related to deep-trap occupation. Contributions of these optical nonlinearities were studied experimentally in (0 0 1)-oriented GaAs wafers by using a transient reflection grating configuration with a very small grating period (150 nm). Comparison of the reflection grating picosecond kinetics and its diffraction efficiency with modeling curves allowed us to ascribe the slow decay component to amplitude grating in recharged deep traps and determine their compensation ratio. The proposed technique allowed the determination of the compensation ratio of a deep EL2 donor, equal to 0.6 ± 0.05 in the given GaAs crystal.

  6. The deep space network

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The progress is reported of Deep Space Network (DSN) research in the following areas: (1) flight project support, (2) spacecraft/ground communications, (3) station control and operations technology, (4) network control and processing, and (5) deep space stations. A description of the DSN functions and facilities is included.

  7. Deep Impact Spots Quarry

    NASA Technical Reports Server (NTRS)

    2005-01-01

    Sixty-nine days before it gets up-close-and-personal with a comet, NASA's Deep Impact spacecraft successfully photographed its quarry, comet Tempel 1, at a distance of 39.7 million miles. The image, taken on April 25, 2005, is the first of many comet portraits Deep Impact will take leading up to its historic comet encounter on July 4.

  8. The Deep Space Network

    NASA Technical Reports Server (NTRS)

    1979-01-01

    Deep Space Network progress in flight project support, tracking and data acquisition, research and technology, network engineering, hardware and software implementation, and operations is cited. Topics covered include: tracking and ground based navigation; spacecraft/ground communication; station control and operations technology; ground communications; and deep space stations.

  9. Deep sea waste disposal

    SciTech Connect

    Kester, D.R.; Burt, W.V.; Capuzzo, J.M.; Park, P.K.; Ketchum, B.W.; Duedall, I.W.

    1985-01-01

    The book presents papers on the marine disposal of wastes. Topics considered include incineration at sea, the modelling and biological effects of industrial wastes, microbial studies of ocean dumping, deep-sea mining wastes, the chemical analysis of ferromanganese nodules, and economic aspects of deep-sea disposal.

  10. Hubble Deep Fields

    NASA Astrophysics Data System (ADS)

    Ferguson, H.; Murdin, P.

    2000-11-01

    The Hubble Deep Fields are two small areas of the sky that were carefully selected for deep observations by the HUBBLE SPACE TELESCOPE (HST). They represent the deepest optical observations to date and reveal galaxies as faint as V=30, 4 billion times fainter than can be seen with the unaided eye....

  11. Deep Space (Space Technology)

    NASA Astrophysics Data System (ADS)

    Murdin, P.

    2002-04-01

    Series of NASA technology demonstration missions under NASA's New Millennium programme. DEEP SPACE 1 (launched October 1998) carries 12 advanced technologies, including autonomous navigation and ion propulsion. It may be directed to encounter near-Earth asteroid 1992 KD and two comets. Deep Space 2 (launched January 1999) comprises two small surface penetrators, part of the failed Mars Polar Land...

  12. Deep-diving dinosaurs

    NASA Astrophysics Data System (ADS)

    Hayman, John

    2012-08-01

    Dysbaric bone necrosis demonstrated in ichthyosaurs may be the result of prolonged deep diving rather than rapid ascent to escape predators. The bone lesions show structural and anatomical similarity to those that may occur in human divers and in the deep diving sperm whale, Physeter macrocephalus.

  13. [Deep neck infections].

    PubMed

    Nowak, Katarzyna; Szyfter, Witold

    2006-01-01

    Deep neck infection is relatively rare but potentially life threatening complication of common oropharyngeal infections. This retrospective study was aimed at analyzing the occurrence of complications, diagnostic methods and proper management of deep neck infection. A review was conducted in 32 cases who were diagnosed as having deep neck infection from 1995 to 2005. The causes of deep neck infections were tonsillitis (16 cases), tooth diseases (6 cases), paratonsillar abscess (4 cases), parotitis (1 case), pussy lymphonodes after tonsillectomy (2 cases), pussy congenital neck cyst (1 case), chronic otitis media (1 case), parotitis (1 case), foreign body of the esophagus (1 case). All the puss bacterial cultivation were positive. All the patients were treated by different ways of chirurgical drainage and use of large dosage of antibiotics. Deep neck infection should be suspected in patients with long lasting fever and painful swelling of the neck and treatment should begin quick as possible.

  14. New achievements on relaxation dynamics of atoms and molecules photoexcited in the tender x-ray domain at synchrotron SOLEIL

    NASA Astrophysics Data System (ADS)

    Piancastelli, M. N.; Guillemin, R.; Marchenko, T.; Journel, L.; Travnikova, O.; Marin, T.; Goldsztejn, G.; Cunha de Miranda, B.; Ismail, I.; Simon, M.

    2017-02-01

    The so-called ‘tender’ x-ray domain, from 2 to 13 keV, has recently become available for atomic and molecular studies at the French synchrotron SOLEIL with state-of-the-art photon and electron energy resolution. We investigated a wealth of new phenomena by means of photoelectron and Auger spectroscopy and electron–ion coincidence techniques. The list includes recoil due to the photoelectron’s momentum, ultrafast nuclear motion on the femto- and sub-femtosecond time scale, double-core-hole studies, electron recapture effects, exotic Auger decay pathways, deep-edge molecular-frame photoelectron angular distribution studies, and core-hole localization/delocalization phenomena for deep-core vacancies. We demonstrate that the newly accessible extended photon energy range does not simply allow studying more systems with deeper core edges, but opens a totally new horizon in what concerns electron and nuclear dynamics of deep-core-excited and core-ionized isolated species.

  15. Deep learning in bioinformatics.

    PubMed

    Min, Seonwoo; Lee, Byunghan; Yoon, Sungroh

    2016-07-29

    In the era of big data, transformation of biomedical big data into valuable knowledge has been one of the most important challenges in bioinformatics. Deep learning has advanced rapidly since the early 2000s and now demonstrates state-of-the-art performance in various fields. Accordingly, application of deep learning in bioinformatics to gain insight from data has been emphasized in both academia and industry. Here, we review deep learning in bioinformatics, presenting examples of current research. To provide a useful and comprehensive perspective, we categorize research both by the bioinformatics domain (i.e. omics, biomedical imaging, biomedical signal processing) and deep learning architecture (i.e. deep neural networks, convolutional neural networks, recurrent neural networks, emergent architectures) and present brief descriptions of each study. Additionally, we discuss theoretical and practical issues of deep learning in bioinformatics and suggest future research directions. We believe that this review will provide valuable insights and serve as a starting point for researchers to apply deep learning approaches in their bioinformatics studies.

  16. Deep Moonquakes: Remaining Problems

    NASA Technical Reports Server (NTRS)

    Nakamura, Y.

    2004-01-01

    We have recently reexamined more than 9000 United States previously unidentified seismic events catalogued during the Apollo landing missions and positively identified for the first time about 30 deep moonquake nests on the far side of the Moon. Although only a few of them are currently locatable, the relative arrival times among stations for the rest and presence or absence of seismic signals at particular stations suggest that either (a) the region within about $40\\deg$ of the antipode is aseismic or (b) the deep interior of the Moon severely attenuates or deflects seismic waves. Aside from the obvious question of how to distinguish between such hypothetical models, this effort raised several more general questions concerning the use of deep moonquake signals to infer the structure and dynamics of the deep interior of the Moon. Among more important ones are: (1) How reliable are the seismic arrival picks from which to compute the seismic velocity variations in the Moon? (2) How do the possible lateral variations in seismic velocity affect the computed radial variation in seismic velocity at depth? (3) Can we tell more about the distribution and mechanism of deep moonquakes from the newly expanded database of identified deep moonquakes? Questions (1) and (2) are especially important because the inferred deep internal structure of the Moon depends critically on their answers. Answering these questions may demand additional data collected on future lunar missions, but some may be resolved with further examination of the existing data.

  17. Deep subsurface microbial processes

    USGS Publications Warehouse

    Lovley, D.R.; Chapelle, F.H.

    1995-01-01

    Information on the microbiology of the deep subsurface is necessary in order to understand the factors controlling the rate and extent of the microbially catalyzed redox reactions that influence the geophysical properties of these environments. Furthermore, there is an increasing threat that deep aquifers, an important drinking water resource, may be contaminated by man's activities, and there is a need to predict the extent to which microbial activity may remediate such contamination. Metabolically active microorganisms can be recovered from a diversity of deep subsurface environments. The available evidence suggests that these microorganisms are responsible for catalyzing the oxidation of organic matter coupled to a variety of electron acceptors just as microorganisms do in surface sediments, but at much slower rates. The technical difficulties in aseptically sampling deep subsurface sediments and the fact that microbial processes in laboratory incubations of deep subsurface material often do not mimic in situ processes frequently necessitate that microbial activity in the deep subsurface be inferred through nonmicrobiological analyses of ground water. These approaches include measurements of dissolved H2, which can predict the predominant microbially catalyzed redox reactions in aquifers, as well as geochemical and groundwater flow modeling, which can be used to estimate the rates of microbial processes. Microorganisms recovered from the deep subsurface have the potential to affect the fate of toxic organics and inorganic contaminants in groundwater. Microbial activity also greatly influences 1 the chemistry of many pristine groundwaters and contributes to such phenomena as porosity development in carbonate aquifers, accumulation of undesirably high concentrations of dissolved iron, and production of methane and hydrogen sulfide. Although the last decade has seen a dramatic increase in interest in deep subsurface microbiology, in comparison with the study of

  18. A study of angle-resolved photoemission extended fine structure as applied to the Ni 3p, Cu 3s, and Cu 3p core levels of the respective clean (111) surfaces

    SciTech Connect

    Huff, W.R.A.; Moler, E.J.; Kellar, S.A.

    1997-04-01

    The first non-s initial state angle-resolved photoemission extended fine structure (ARPEFS) study of clean surfaces for the purpose of further understanding the technique is reported. The surface structure sensitivity of ARPEFS applied to clean surfaces and to arbitrary initial states is studied using normal photoemission data taken from the Ni 3p core levels of a Ni(111) single crystal and the Cu 3s and the Cu 3p core-levels of a Cu(111) single crystal. The Fourier transforms of these clean surface data are dominated by backscattering. Unlike the s initial state data, the p initial state data show a peak in the Fourier transform corresponding to in-plane scattering from the six nearest-neighbors to the emitter. Evidence was seen for single-scattering events from in the same plane as the emitters and double-scattering events. Using a newly developed, multiple-scattering calculation program, ARPEFS data from clean surfaces and from p initial states can be modeled to high precision. Although there are many layers of emitters when measuring photoemission from a clean surface, test calculations show that the ARPEFS signal is dominated by photoemission from atoms in the first two crystal layers. Thus, ARPEFS applied to clean surfaces is sensitive to surface reconstruction. The known contraction of the first two Cu(111) layers is confirmed. The best-fit calculation for clean Ni(111) indicates an expansion of the first two layers. To better understand the ARPEFS technique, the authors studied s and non-s initial state photoemission from clean metal surfaces.

  19. Photo-excitation of adenine cation radical [A•+] in the near UV-vis region produces sugar radicals in Adenosine and in its nucleotides

    PubMed Central

    Adhikary, Amitava; Khanduri, Deepti; Kumar, Anil; Sevilla, Michael D.

    2011-01-01

    In this study, we report the formation of ribose sugar radicals in high yields (85 – 100%) via photo-excitation of adenine cation radical (A•+) in Ado and its ribonucleotides. Photo-excitation of A•+ at low temperatures in homogenous aqueous glassy samples of Ado, 2′-AMP, 3′-AMP and 5′-AMP forms sugar radicals predominantly at C5′- and also at C3′-sites. The C5′• and C3′• sugar radicals were identified employing Ado deuterated at specific carbon sites: C1′, C2′, and at C5′. Phosphate substitution is found to deactivate sugar radical formation at the site of substitution. Thus, in 5′-AMP, C3′• is observed to be the main radical formed via photo-excitation at ca. 143 K whereas in 3′-AMP, C5′• is the only species found. These results were supported by results obtained employing 5′-AMP with specific deuteration at C5′-site (i.e., 5′,5′-D,D-5′-AMP). Moreover, contrary to the C5′• observed in 3′-dAMP, we find that C5′• in 3′-AMP shows a clear pH dependent conformational change as evidenced by a large increase in the C4′ β–hyperfine coupling on increasing the pH from 6 to 9. Calculations performed employing DFT (B3LYP/6-31G*) for C5′• in 3′-AMP show that the two conformations of C5′• result from strong hydrogen bond formation between the O5′-H and the 3′-phosphate dianion at higher pHs. Employing time-dependent density functional theory [TD-DFT, B3LYP/6-31G(d)] we show that in the excited state, the hole transfers to the sugar moiety and has significant hole localization at the C5′-site in a number of allowed transitions. This hole localization is proposed to lead to the formation of the neutral C5′-radical (C5′•) via deprotonation. PMID:19367991

  20. The deep space network

    NASA Technical Reports Server (NTRS)

    1979-01-01

    Progress is reported in flight project support, tracking and data acquisition research and technology, network engineering, hardware and software implementation, and operations. The functions and facilities of the Deep Space Network are emphasized.

  1. The deep space network

    NASA Technical Reports Server (NTRS)

    1979-01-01

    A report is given of the Deep Space Networks progress in (1) flight project support, (2) tracking and data acquisition research and technology, (3) network engineering, (4) hardware and software implementation, and (5) operations.

  2. The Deep Space Network

    NASA Technical Reports Server (NTRS)

    1979-01-01

    Progress on the Deep Space Network (DSN) supporting research and technology, advanced development, engineering and implementation, and DSN operations is presented. The functions and facilities of the DSN are described.

  3. Deep Vein Thrombosis (DVT)

    MedlinePlus

    ... helps reduce the chances that your blood will pool and clot. You should wear these stockings during ... Make lifestyle changes. Lose weight and quit smoking. Obesity and smoking increase your risk of deep vein ...

  4. The Deep Space Network

    NASA Technical Reports Server (NTRS)

    1977-01-01

    The various systems and subsystems are discussed for the Deep Space Network (DSN). A description of the DSN is presented along with mission support, program planning, facility engineering, implementation and operations.

  5. The deep space network

    NASA Technical Reports Server (NTRS)

    1977-01-01

    A Deep Space Network progress report is presented dealing with in flight project support, tracking and data acquisition research and technology, network engineering, hardware and software implementation, and operations.

  6. The deep space network

    NASA Technical Reports Server (NTRS)

    1980-01-01

    The functions and facilities of the Deep Space Network are considered. Progress in flight project support, tracking and data acquisition research and technology, network engineering, hardware and software implementation, and operations is reported.

  7. Deep Impact Spots Quarry

    NASA Image and Video Library

    2005-04-27

    Taken on April 25, 2005, sixty-nine days before it gets up-close-and-personal with a comet, NASA Deep Impact spacecraft successfully photographed its quarry, comet Tempel 1, at a distance of 39.7 million miles.

  8. The deep space network

    NASA Technical Reports Server (NTRS)

    1977-01-01

    The facilities, programming system, and monitor and control system for the deep space network are described. Ongoing planetary and interplanetary flight projects are reviewed, along with tracking and ground-based navigation, communications, and network and facility engineering.

  9. Deep Vein Thrombosis

    MedlinePlus

    ... vein swells, the condition is called thrombophlebitis. A deep vein thrombosis can break loose and cause a serious problem in the lung, called a pulmonary embolism. Sitting still for a long time can make ...

  10. Nurturing Deep Connections.

    ERIC Educational Resources Information Center

    Kessler, Rachael

    2002-01-01

    Argues that the missing ingredient in school reform is soul, that is, deep connections among students, teachers, and administrators. Discusses five principles of leadership with soul: Personalize, pacing, permission, protection, and paradox. (PKP)

  11. The deep space network

    NASA Technical Reports Server (NTRS)

    1975-01-01

    The objectives, functions, and organization of the Deep Space Network are summarized along with deep space station, ground communication, and network operations control capabilities. Mission support of ongoing planetary/interplanetary flight projects is discussed with emphasis on Viking orbiter radio frequency compatibility tests, the Pioneer Venus orbiter mission, and Helios-1 mission status and operations. Progress is also reported in tracking and data acquisition research and technology, network engineering, hardware and software implementation, and operations.

  12. The Deep Space Network

    NASA Technical Reports Server (NTRS)

    1974-01-01

    The objectives, functions, and organization, of the Deep Space Network are summarized. Deep Space stations, ground communications, and network operations control capabilities are described. The network is designed for two-way communications with unmanned spacecraft traveling approximately 1600 km from earth to the farthest planets in the solar system. It has provided tracking and data acquisition support for the following projects: Ranger, Surveyor, Mariner, Pioneer, Apollo, Helios, Viking, and the Lunar Orbiter.

  13. Exploration for deep coal

    SciTech Connect

    2008-12-15

    The most important factor in safe mining is the quality of the roof. The article explains how the Rosebud Mining Co. conducts drilling and exploration in 11 deep coal mine throughout Pennsylvania and Ohio. Rosebud uses two Atlas Copco CS10 core drilling rigs mounted on 4-wheel drive trucks. The article first appeared in Atlas Copco's in-house magazine, Deep Hole Driller. 3 photos.

  14. Diagnosing Deep Venous Thrombosis

    PubMed Central

    Doyle, D. Lynn

    1992-01-01

    Patients often present with unexplained lower limb pain and swelling. It is important to exclude deep venous thrombosis in the diagnosis because of the threat of sudden death. Simple clinical diagnosis is unacceptable, and noninvasive tests should be used initially. Serial testing detects proximal extension of isolated calf thrombi. Multiple diagnostic modalities are employed to diagnose a new deep venous thrombosis in patients with postphlebitic syndrome. PMID:21221369

  15. Polarization analysis of fluorescence probing the alignment of Xe+ ions in the resonant Auger decay of the Xe* 4d-15/26p photoexcited state

    NASA Astrophysics Data System (ADS)

    Meyer, M.; Marquette, A.; Grum-Grzhimailo, A. N.; Kleiman, U.; Lohmann, B.

    2001-08-01

    Xe II fluorescence, following the resonant Auger decay of the Xe* 4d-15/26p photoexcited state, has been measured in the wavelength region 400 nm <=λ (fluo) <=610 nm by means of dispersed fluorescence spectroscopy, and the degree of linear polarization of the emitted light has been analyzed. From these data, the alignment of the ionic 5p46p states produced by the Auger decay has been determined by taking into account the depolarization of the radiatively decaying Xe II multiplet due to cascade population and hyperfine interactions. Calculations of the alignment are performed in a multiconfigurational Dirac-Fock approach and compared with the experiment. Good agreement between experiment and theory has been obtained for almost all fine-structure components of the Xe II 5p46p multiplet, providing reliable alignment parameters of the ionic states produced upon resonant Auger decay.

  16. New insight into the potential energy landscape and relaxation pathways of photoexcited aniline from CASSCF and XMCQDPT2 electronic structure calculations.

    PubMed

    Sala, Matthieu; Kirkby, Oliver M; Guérin, Stéphane; Fielding, Helen H

    2014-02-21

    There have been a number of recent experimental investigations of the nonadiabatic relaxation dynamics of aniline following excitation to the first three singlet excited states, 1(1)ππ*, 1(1)π3s/πσ* and 2(1)ππ*. Motivated by differences between the interpretations of experimental observations, we have employed CASSCF and XMCQDPT2 calculations to explore the potential energy landscape and relaxation pathways of photoexcited aniline. We find a new prefulvene-like MECI connecting the 1(1)ππ* state with the GS in which the carbon-atom carrying the amino group is distorted out-of-plane. This suggests that excitation above the 1(1)π3s/πσ* vertical excitation energy could be followed by electronic relaxation from the 1(1)ππ* state to the ground-electronic state through this MECI. We find a MECI connecting the 1(1)π3s/πσ* and 1(1)ππ* states close to the local minimum on 1(1)π3s/πσ* which suggests that photoexcitation to the 1(1)π3s/πσ* state could be followed by relaxation to the 1(1)ππ* state and to the dissociative component of the 1(1)π3s/πσ* state. We also find evidence for a new pathway from the 2(1)ππ* state to the ground electronic state that is likely to pass through a three-state conical intersection involving the 2(1)ππ*, 1(1)π3s/πσ* and 1(1)ππ* states.

  17. Real-time propagation time-dependent density functional theory study on the ring-opening transformation of the photoexcited crystalline benzene

    NASA Astrophysics Data System (ADS)

    Tateyama, Yoshitaka; Oyama, Norihisa; Ohno, Takahisa; Miyamoto, Yoshiyuki

    2006-03-01

    Mechanism of the ring-opening transformation in the photoexcited crystalline benzene is investigated on the femtosecond scale by a computational method based on the real-time propagation (RTP) time-dependent density functional theory (TDDFT). The excited-state dynamics of the benzene molecule is also examined not only for the distinction between the intrinsic properties of molecule and the intermolecular interaction but for the first validation using the vibration frequencies for the RTP-TDDFT approach. It is found that the vibration frequencies of the excited and ground states in the molecule are well reproduced. This demonstrates that the present method of time evolution using the Suzuki-Trotter-type split operator technique starting with the Franck-Condon state approximated by the occupation change of the Kohn-Sham orbitals is adequately accurate. For the crystalline benzene, we carried out the RTP-TDDFT simulations for two typical pressures. At both pressures, large swing of the C-H bonds and subsequent twist of the carbon ring occurs, leading to tetrahedral (sp3-like) C-H bonding. The ν4 and ν16 out-of-plane vibration modes of the benzene molecule are found mostly responsible for these motions, which is different from the mechanism proposed for the thermal ring-opening transformation occurring at higher pressure. Comparing the results between different pressures, we conclude that a certain increase of the intermolecular interaction is necessary to make seeds of the ring opening (e.g., radical site formation and breaking of the molecular character) even with the photoexcitation, while the hydrogen migration to fix them requires more free volume, which is consistent with the experimental observation that the transformation substantially proceeds on the decompression.

  18. Deep ocean environmental biotechnology

    PubMed

    Deming

    1998-06-01

    Major recent advances in deep-sea biotechnology have come in the form of continuing discoveries of novel microorganisms, unexpected genetic diversity, and new natural products of potential relevance to human health or environmental bioremediation. Continuing explorations of submarine hydrothermal vent environments have yielded new hyperthermophiles (maximal growth at 90 degreesC or greater) and more evidence that elevated hydrostatic pressure stabilizes cells and enzymes at high temperature. Vent samples have also yielded new mesophiles (optimal growth near 30 degreesC) that produce heparin-like exopolysaccharides or express extraordinary tolerance (removal by precipitation) of heavy metals. From the cold deep sea have come new findings of unexpected microbial diversity and the promise of industrially useful enzymes or secondary metabolites. New classes of predictive models are emerging to guide future exploration of microbial diversity in the deep ocean.

  19. Deep dysgraphia in Turkish.

    PubMed

    Raman, Ilhan; Weekes, Brendan Stuart

    2005-01-01

    Deep dysgraphic patients make semantic errors when writing to dictation and they cannot write nonwords. Extant reports of deep dysgraphia come from languages with relatively opaque orthographies. Turkish is a transparent orthography because the bidirectional mappings between phonology and orthography are completely predictable. We report BRB, a biscriptal Turkish-English speaker who has acquired dysgraphia characterised by semantic errors as well as effects of grammatical class and imageability on writing in Turkish. Nonword spelling is abolished. A similar pattern of errors is observed in English. BRB is the first report of acquired dysgraphia in a truly transparent writing system. We argue that deep dysgraphia results from damage to the mappings that are common to both languages between word meanings and orthographic representations.

  20. The deep penetrating nevus.

    PubMed

    Strazzula, Lauren; Senna, Maryanne Makredes; Yasuda, Mariko; Belazarian, Leah

    2014-12-01

    The deep penetrating nevus (DPN), also known as the plexiform spindle cell nevus, is a pigmented lesion that commonly arises on the head and neck in the first few decades of life. Histopathologically, the DPN is wedge-shaped and contains melanocytes that exhibit deep infiltration into the dermis. Given these features, DPN may clinically and histopathologically mimic malignant melanoma, sparking confusion about the appropriate evaluation and management of these lesions. The goal of this review is to summarize the clinical and histopathological features of DPN and to discuss diagnostic and treatment strategies for dermatologists.

  1. DEEP UNDERGROUND NEUTRINO EXPERIMENT

    SciTech Connect

    Wilson, Robert J.

    2016-03-03

    The Deep Underground Neutrino Experiment (DUNE) collaboration will perform an experiment centered on accelerator-based long-baseline neutrino studies along with nucleon decay and topics in neutrino astrophysics. It will consist of a modular 40-kt (fiducial) mass liquid argon TPC detector located deep underground at the Sanford Underground Research Facility in South Dakota and a high-resolution near detector at Fermilab in Illinois. This conguration provides a 1300-km baseline in a megawatt-scale neutrino beam provided by the Fermilab- hosted international Long-Baseline Neutrino Facility.

  2. Deep space laser communications

    NASA Astrophysics Data System (ADS)

    Biswas, Abhijit; Kovalik, Joseph M.; Srinivasan, Meera; Shaw, Matthew; Piazzolla, Sabino; Wright, Malcolm W.; Farr, William H.

    2016-03-01

    A number of laser communication link demonstrations from near Earth distances extending out to lunar ranges have been remarkably successful, demonstrating the augmented channel capacity that is accessible with the use of lasers for communications. The next hurdle on the path to extending laser communication and its benefits throughout the solar system and beyond is to demonstrate deep-space laser communication links. In this paper, concepts and technology development being advanced at the Jet Propulsion Laboratory (JPL) in order to enable deep-space link demonstrations to ranges of approximately 3 AU in the next decade, will be discussed.

  3. Calculating core-level excitations and X-ray absorption spectra of medium-sized closed-shell molecules with the algebraic-diagrammatic construction scheme for the polarization propagator.

    PubMed

    Wenzel, Jan; Wormit, Michael; Dreuw, Andreas

    2014-10-05

    Core-level excitations are generated by absorption of high-energy radiation such as X-rays. To describe these energetically high-lying excited states theoretically, we have implemented a variant of the algebraic-diagrammatic construction scheme of second-order ADC(2) by applying the core-valence separation (CVS) approximation to the ADC(2) working equations. Besides excitation energies, the CVS-ADC(2) method also provides access to properties of core-excited states, thereby allowing for the calculation of X-ray absorption spectra. To demonstrate the potential of our implementation of CVS-ADC(2), we have chosen medium-sized molecules as examples that have either biological importance or find application in organic electronics. The calculated results of CVS-ADC(2) are compared with standard TD-DFT/B3LYP values and experimental data. In particular, the extended variant, CVS-ADC(2)-x, provides the most accurate results, and the agreement between the calculated values and experiment is remarkable.

  4. Core-level electronic structure of solid-phase glycine, glycyl-glycine, diglycyl-glycine, and polyglycine: X-ray photoemission analysis and Hartree-Fock calculations of their zwitterions.

    PubMed

    Chatterjee, Avisek; Zhao, Liyan; Zhang, Lei; Pradhan, Debabrata; Zhou, Xiaojing; Leung, K T

    2008-09-14

    X-ray photoelectron spectroscopy (XPS) has been used to investigate the core-level electronic structures of glycine (G) and its peptides, including glycyl-glycine (GG), diglycyl-glycine (GGG), and polyglycine (poly-G), in their powder forms. Increasing the number of G units in the peptides does not change the locations of the respective C 1s, N 1s, and O 1s features corresponding to different functional groups: -COO(-), -NH(3)(+), >CH(2), and -CONH-. The electronic structures of the zwitterions of these molecules have been calculated as isolated molecules and as molecules in an aqueous environment under the periodic boundary conditions by quantum-mechanical and molecular mechanics methods. In the case of glycine zwitterion, the binding energies of the C 1s, N 1s, and O 1s XPS features are found to be in reasonable accord with the respective orbital energies obtained by Hartree-Fock self-consistent-field calculations, within the context of Koopmans' approximation. However, considerably worse agreement in the binding energies is found for the larger zwitterions (with the specific conformations considered in this work), indicating the need for higher-level calculations. The present work shows that optimizing the zwitterion in an aqueous environment under the periodic boundary conditions by molecular mechanics could be a very cost-effective approach for calculating the electronic structures of large, complex biomolecular systems.

  5. Extreme Deep Space Communications

    NASA Technical Reports Server (NTRS)

    Deutsch, Leslie J.; Edwards, Charles D.; Lesh, James R.

    1996-01-01

    Recent work in deep space telecommunication systems has been performed in support of NASA's Mission to the Solar System planning activity. The results show that high bandwidth communications (higher thatn 1 Mbps) are feasible with communication infrastructure investments at targets of high exploration activity. These targets include Mars, Jupiter, and Neptune. Infrastructure improvements must also be made at Earth.

  6. Reading Knee-Deep

    ERIC Educational Resources Information Center

    Jewett, Pamela

    2007-01-01

    Freire told his audience at a seminar at the University of Massachusetts, "You need to read knee-deep in texts, for deeper than surface meanings, and you need to know the words to be able to do it" (quoted in Cleary, 2003). In a children's literature class, fifteen teachers and I traveled along a path that moved us toward reading…

  7. Deep Space Test Bed

    NASA Technical Reports Server (NTRS)

    Milton, Martha E.

    2005-01-01

    This viewgraph presentation describes the Deep Space Test Bed (DSTB), a balloon-borne device which can expose multiple payloads to the interplanetary Galactic Cosmic Ray environment on high altitude polar balloon flights. The DSTB is carried by National Scientific Balloon Facility (NSBF) Long Duration Balloons on polar flights so that its balloon-borne experiments can avoid geomagnetic cut-offs.

  8. The Deep Space Network

    NASA Technical Reports Server (NTRS)

    1975-01-01

    Work accomplished on the Deep Space Network (DSN) was described, including the following topics: supporting research and technology, advanced development and engineering, system implementation, and DSN operations pertaining to mission-independent or multiple-mission development as well as to support of flight projects.

  9. Teaching for Deep Learning

    ERIC Educational Resources Information Center

    Smith, Tracy Wilson; Colby, Susan A.

    2007-01-01

    The authors have been engaged in research focused on students' depth of learning as well as teachers' efforts to foster deep learning. Findings from a study examining the teaching practices and student learning outcomes of sixty-four teachers in seventeen different states (Smith et al. 2005) indicated that most of the learning in these classrooms…

  10. Reading Knee-Deep

    ERIC Educational Resources Information Center

    Jewett, Pamela

    2007-01-01

    Freire told his audience at a seminar at the University of Massachusetts, "You need to read knee-deep in texts, for deeper than surface meanings, and you need to know the words to be able to do it" (quoted in Cleary, 2003). In a children's literature class, fifteen teachers and I traveled along a path that moved us toward reading…

  11. Groth Deep Image

    NASA Image and Video Library

    2003-07-25

    This ultraviolet color blowup of the Groth Deep Image was taken by NASA Galaxy Evolution Explorer on June 22 and June 23, 2003. Many hundreds of galaxies are detected in this portion of the image. NASA astronomers believe the faint red galaxies are 6 billion light years away. http://photojournal.jpl.nasa.gov/catalog/PIA04625

  12. The Deep Space Network

    NASA Technical Reports Server (NTRS)

    1988-01-01

    The Deep Space Network (DSN) is the largest and most sensitive scientific telecommunications and radio navigation network in the world. Its principal responsibilities are to support unmanned interplanetary spacecraft missions and to support radio and radar astronomy observations in the exploration of the solar system and the universe. The DSN facilities and capabilities as of January 1988 are described.

  13. Deep Learning Is Difficult.

    ERIC Educational Resources Information Center

    Sandberg, Jacobijn; Barnard, Yvonne

    1997-01-01

    Explanations for poor learning include inadequate subject matter, students, and approach, but this article argues that the information processing needed for deep learning is hampered when students can not spontaneously engage in cognitive activities fostering such learning. Describes three studies in which high school students learned about the…

  14. [Deep vein thrombosis prophylaxis.

    PubMed

    Sandoval-Chagoya, Gloria Alejandra; Laniado-Laborín, Rafael

    2013-01-01

    Background: despite the proven effectiveness of preventive therapy for deep vein thrombosis, a significant proportion of patients at risk for thromboembolism do not receive prophylaxis during hospitalization. Our objective was to determine the adherence to thrombosis prophylaxis guidelines in a general hospital as a quality control strategy. Methods: a random audit of clinical charts was conducted at the Tijuana General Hospital, Baja California, Mexico, to determine the degree of adherence to deep vein thrombosis prophylaxis guidelines. The instrument used was the Caprini's checklist for thrombosis risk assessment in adult patients. Results: the sample included 300 patient charts; 182 (60.7 %) were surgical patients and 118 were medical patients. Forty six patients (15.3 %) received deep vein thrombosis pharmacologic prophylaxis; 27.1 % of medical patients received deep vein thrombosis prophylaxis versus 8.3 % of surgical patients (p < 0.0001). Conclusions: our results show that adherence to DVT prophylaxis at our hospital is extremely low. Only 15.3 % of our patients at risk received treatment, and even patients with very high risk received treatment in less than 25 % of the cases. We have implemented strategies to increase compliance with clinical guidelines.

  15. Teaching for Deep Learning

    ERIC Educational Resources Information Center

    Smith, Tracy Wilson; Colby, Susan A.

    2007-01-01

    The authors have been engaged in research focused on students' depth of learning as well as teachers' efforts to foster deep learning. Findings from a study examining the teaching practices and student learning outcomes of sixty-four teachers in seventeen different states (Smith et al. 2005) indicated that most of the learning in these classrooms…

  16. Dynamical mechanism of charge separation by photoexcited generation of proton-electron pairs in organic molecular systems. A nonadiabatic electron wavepacket dynamics study

    NASA Astrophysics Data System (ADS)

    Yamamoto, Kentaro; Takatsuka, Kazuo

    2016-08-01

    In this perspective article, we review, along with presenting new results, a series of our theoretical analyses on the excited-state mechanism of charge separation (proton-electron pair creation) relevant to the photoinduced water-splitting reaction (2H2O → 4H+ + 4e- + O2) in organic and biological systems, which quite often includes Mn clusters in various molecular configurations. The present mechanism is conceived to be universal in the triggering process of the photoexcited water splitting dynamics. In other words, any Mn-based catalytic charge separation is quite likely to be initiated according to this mechanism. As computationally tractable yet realistic models, we examine a series of systems generally expressed as X-Mn-OH2⋯A, where X = (OH, Ca(OH)3) and A = (N-methylformamidine, guanidine, imidazole or ammonia cluster) in terms of the theory of nonadiabatic electron wavepacket dynamics. We first find both an electron and a proton are simultaneously transferred to the acceptors through conical intersections upon photoexcitation. In this mechanism, the electron takes different pathways from that of the proton and reaches the densely lying Rydberg-like states of the acceptors in the end, thereby inducing charge separation. Therefore the presence of the Rydberg-like diffused unoccupied states as an electron acceptor is critical for this reaction to proceed. We also have found another crucial nonadiabatic process that deteriorates the efficiency of charge separation by rendering the created pair of proton and electron back to the originally donor site through the states of d-d band originated from Mn atom. Repetition of this process gradually annihilates the created pair of proton and electron in a way different from the usual charge recombination process. We address this dynamics by means of our proposed path-branching representation. The dynamical roles of a doped Ca atom are also uncovered, which are relevant to controlling the pathways of electron

  17. Weak Donor-Acceptor Interaction and Interface Polarization Define Photoexcitation Dynamics in the MoS2/TiO2 Composite: Time-Domain Ab Initio Simulation.

    PubMed

    Wei, Yaqing; Li, Linqiu; Fang, Weihai; Long, Run; Prezhdo, Oleg V

    2017-07-12

    To realize the full potential of transition metal dichalcogenides interfaced with bulk semiconductors for solar energy applications, fast photoinduced charge separation, and slow electron-hole recombination are needed. Using a combination of time-domain density functional theory with nonadiabatic molecular dynamics, we demonstrate that the key features of the electron transfer (ET), energy relaxation and electron-hole recombination in a MoS2-TiO2 system are governed by the weak van der Waals interfacial interaction and interface polarization. Electric fields formed at the interface allow charge separation to happen already during the photoexcitation process. Those electrons that still reside inside MoS2, transfer into TiO2 slowly and by the nonadiabatic mechanism, due to weak donor-acceptor coupling. The ET time depends on excitation energy, because the TiO2 state density grows with energy, increasing the nonadiabatic transfer rate, and because MoS2 sulfur atoms start to contribute to the photoexcited state at higher energies, increasing the coupling. The ET is slower than electron-phonon energy relaxation because the donor-acceptor coupling is weak, rationalizing the experimentally observed injection of primarily hot electrons. The weak van der Waals MoS2-TiO2 interaction ensures a long-lived charge separated state and a short electron-hole coherence time. The injection is promoted primarily by phonons within the 200-800 cm(-1) range. Higher frequency modes are particularly important for the electron-hole recombinations, because they are able to accept large amounts of electronic energy. The predicted time scales for the forward and backward ET, and energy relaxation can be measured by time-resolved spectroscopies. The reported simulations generate a detailed time-domain atomistic description of the complex interplay of the charge and energy transfer processes at the MoS2/TiO2 interface that are of fundamental importance to photovoltaic and photocatalytic

  18. Direct Observation of Charge-Transfer-to-Solvent Reactions: Femtosecond Studies of the Photoexcited Alkali Metal Anion Sodide (Na-)

    NASA Astrophysics Data System (ADS)

    Schwartz, Benjamin

    2000-03-01

    Charge-transfer-to-solvent (CTTS) transitions have been the subject of a great deal of interest recently because they represent the simplest possible charge transfer reaction: the CTTS electron transfer from an atomic ion to a cavity in the surrounding solvent involves only electronic degrees of freedom. Most of the work in this area, both experimental and theoretical, has focused on aqueous halides. Experimentally, however, halides are a poor choice for studying the CTTS phenomenon because the relevant spectroscopic transitions are deep in the UV and because the charge transfer dynamics can be monitored only indirectly through the appearance of the solvated electron. In this talk, we show that these difficulties can be overcome by taking advantage of the CTTS transitions in solutions of alkali metal anions, in particular, the near-IR CTTS band of sodide (Na ) in tetrahydrofuran (THF). Using femtosecond pump-probe techniques, we have been able to spectroscopically separate and identify transient absorption contributions not only from the solvated electron, but also from the bleaching dynamics of the Na ground state and from the absorption of the neutral sodium atom. Perhaps most importantly, we also have been able to directly observe the decay of the Na * excited CTTS state, providing the first direct measure of the electron transfer rate for any CTTS system. Taken together, the data at a variety of pump and probe wavelengths provide a direct test for several kinetic models of the CTTS process. The model which best fits the data assumes a delayed ejection of the electron from the CTTS excited state in 700 fs. Once ejected, a fraction of the electrons recombine with the neutral sodium parent atom on a 1.3 ps time scale. The fraction of electrons that recombine depends sensitively on the choice of excitation wavelength, suggesting multiple pathways for charge transfer. All the results are compared to previous studies of both CTTS dynamics and alkali metal solutions

  19. Deep Ecology and Ultimate Premises.

    ERIC Educational Resources Information Center

    Naess, Arne

    1988-01-01

    Presented is support for the basic tenets of the Deep Ecology Movement. Answers several criticisms concerning mysticism, nuclear war, and destiny. Provides a platform and two models for the philosophy of Deep Ecology. (CW)

  20. The Making of Deep Impact

    NASA Image and Video Library

    2006-10-19

    This image shows NASA Deep Impact spacecraft being built at Ball Aerospace & Technologies Corporation, Boulder, Colo. on July 2, 2005. The spacecraft impactor was released from Deep Impact flyby spacecraft.

  1. Deduction of the chemical state and the electronic structure of Nd{sub 2}Fe{sub 14}B compound from X-ray photoelectron spectroscopy core-level and valence-band spectra

    SciTech Connect

    Wang, Jing; Liang, Le; Zhang, Lanting E-mail: lmsun@sjtu.edu.cn; Sun, Limin E-mail: lmsun@sjtu.edu.cn; Hirano, Shinichi

    2014-10-28

    Characterization of chemical state and electronic structure of the technologically important Nd{sub 2}Fe{sub 14}B compound is attractive for understanding the physical nature of its excellent magnetic properties. X-ray photoelectron spectroscopy (XPS) study of such rare-earth compound is important and also challenging due to the easy oxidation of surface and small photoelectron cross-sections of rare-earth 4f electrons and B 2p electrons, etc. Here, we reported an investigation based on XPS spectra of Nd{sub 2}Fe{sub 14}B compound as a function of Ar ion sputtering time. The chemical state of Fe and that of B in Nd{sub 2}Fe{sub 14}B compound can be clearly determined to be 0 and −3, respectively. The Nd in Nd{sub 2}Fe{sub 14}B compound is found to have the chemical state of close to +3 instead of +3 as compared with the Nd in Nd{sub 2}O{sub 3}. In addition, by comparing the valence-band spectrum of Nd{sub 2}Fe{sub 14}B compound to that of the pure Fe, the contributions from Nd, Fe, and B to the valence-band structure of Nd{sub 2}Fe{sub 14}B compound is made more clear. The B 2p states and B 2s states are identified to be at ∼11.2 eV and ∼24.6 eV, respectively, which is reported for the first time. The contribution from Nd 4f states can be identified both in XPS core-level spectrum and XPS valence-band spectrum. Although Nd 4f states partially hybridize with Fe 3d states, Nd 4f states are mainly localized in Nd{sub 2}Fe{sub 14}B compound.

  2. I. Excitonic Phase Diagram in Silicon: Evidence for Two Condensed Phases. I. Motion of Photoexcited Carriers in GALLIUM-ARSENIDE/ALUMINUM(X)GALLIUM(1-X)ARSENIDE Multiple Quantum Wells-Anomalous Confinement at High Densities.

    NASA Astrophysics Data System (ADS)

    Smith, Leigh Morris

    This thesis describes work on the thermodynamics and transport properties of photoexcited carriers in bulk and two-dimensional semiconductors. Two major topics are addressed. I. Photoluminescence experiments of excitons in unstressed silicon are presented which indicate the existence of a new non-degenerate condensed phase of plasma. This new liquid has a density one-tenth that of the ground state electron-hole liquid and is observed both above and below the liquid-gas critical point (~24.5K). A new phase diagram of excitons in silicon is presented which includes these two condensed plasmas. Consistent with the Gibbs phase rule, a triple point at 18.5 K is inferred from the luminescence data as the only temperature where the exciton gas, condensed plasma (CP) and electron-hole liquid (EHL) coexist. The low density condensed plasma persists up to a second critical point at 45 +/- 5K, above which the photoexcited carriers are observed to continuously decay into a partially ionized excitonic gas. II. We have measured the in-plane motion of photoexcited carriers in semiconductor quantum wells with 5 μm spatial and 10 ps temporal resolution and have discovered several surprising results. The effective diffusivity of the carriers at densities below n = 2 times 10^{11}cm ^{-2} is found to depend upon excitation level, possibly indicating defect-limited diffusion or phonon-wind effects. Above this density the spatial profiles exhibit two distinct components with widely differing diffusivities. This remarkable behavior may be understood with consideration of the interactions of non-equilibrium phonons with the photoexcited carriers. We postulate that the slowly diffusing component represents carriers which are "thermally confined" to a phonon hot spot, while the rapidly moving component is driven by the flux of non-equilibrium phonons away from the excitation region.

  3. Direct observation of charge-transfer-to-solvent (CTTS) reactions: Ultrafast dynamics of the photoexcited alkali metal anion sodide (Na-)

    NASA Astrophysics Data System (ADS)

    Barthel, Erik R.; Martini, Ignacio B.; Schwartz, Benjamin J.

    2000-06-01

    Charge-transfer-to-solvent (CTTS) transitions have been the subject of a great deal of interest recently because they represent the simplest possible charge transfer reaction: The CTTS electron transfer from an atomic ion to a cavity in the surrounding solvent involves only electronic degrees of freedom. Most of the work in this area, both experimental and theoretical, has focused on aqueous halides. Experimentally, however, halides make a challenging choice for studying the CTTS phenomenon because the relevant spectroscopic transitions are deep in the UV and because the charge-transfer dynamics can be monitored only indirectly through the appearance of the solvated electron. In this paper, we show that these difficulties can be overcome by taking advantage of the CTTS transitions in solutions of alkali metal anions, in particular, the near-IR CTTS band of sodide (Na-) in tetrahydrofuran (THF). Using femtosecond pump-probe techniques, we have been able to spectroscopically separate and identify transient absorption contributions not only from the solvated electron, but also from the bleaching dynamics of the Na- ground state and from the absorption of the neutral sodium atom. Perhaps most importantly, we also have been able to directly observe the decay of the Na-* excited CTTS state, providing the first direct measure of the electron transfer rate for any CTTS system. Taken together, the data at a variety of pump and probe wavelengths provide a direct test for several kinetic models of the CTTS process. The model which best fits the data assumes a delayed ejection of the electron from the CTTS excited state in ˜700 fs. Once ejected, a fraction of the electrons, which remain localized in the vicinity of the neutral sodium parent atom, recombine on a ˜1.5-ps time scale. The fraction of electrons that recombine depends sensitively on the choice of excitation wavelength, suggesting multiple pathways for charge transfer. The spectrum of the neutral sodium atom, which

  4. Project DEEP STEAM

    NASA Astrophysics Data System (ADS)

    Aeschliman, D. P.; Clay, R. G.; Donaldson, A. B.; Eisenhawer, S. W.; Fox, R. L.; Johnson, D. R.; Mulac, A. J.

    1982-01-01

    The objective of Project DEEP STEAM is to develop the technology to economically produce heavy oils from deep reservoirs. The tasks included in this project are the development of thermally efficient delivery systems and downhole steam generation systems. During the period January 1-March 31, 1981, effort has continued on a low pressure combustion downhole generator (Rocketdyne), and on two high pressure designs (Foster-Miller Associates, Sandia National Laboratories). The Sandia design was prepared for deployment in the Wilmington Field at Long Beach, California. Progress continued on the Min-Stress II packer concept at L'Garde, Inc., and on the extruded metal packer at Foster-Miller. Initial bare string field data are reported on the insulated tubular test at Lloydminster, Saskatchewan, Canada.

  5. Deep depth undex simulator

    SciTech Connect

    Higginbotham, R. R.; Malakhoff, A.

    1985-01-29

    A deep depth underwater simulator is illustrated for determining the dual effects of nuclear type underwater explosion shockwaves and hydrostatic pressures on a test vessel while simulating, hydrostatically, that the test vessel is located at deep depths. The test vessel is positioned within a specially designed pressure vessel followed by pressurizing a fluid contained between the test and pressure vessels. The pressure vessel, with the test vessel suspended therein, is then placed in a body of water at a relatively shallow depth, and an explosive charge is detonated at a predetermined distance from the pressure vessel. The resulting shockwave is transmitted through the pressure vessel wall so that the shockwave impinging on the test vessel is representative of nuclear type explosive shockwaves transmitted to an underwater structure at great depths.

  6. Butterfly deformation modes in a photoexcited pyrazolate-bridged Pt complex measured by time-resolved x-ray scattering in solution

    SciTech Connect

    Haldrup, Kristoffer; Dohn, Asmus O.; Shelby, Megan L.; Mara, Michael W.; Stickrath, Andrew B.; Harpham, Michael R.; Huang, Jier; Zhang, Xiaoyi; Moller, Klaus B.; Chakraborty, Arnab; Castellano, Felix N.; Tiede, David M.; Chen, Lin X.

    2016-08-27

    Pyrazolate-bridged di-nuclear Pt complexes represent a series of molecules with tunable absorption and emission properties that can be directly modulated by structural factors, such as the Pt-Pt distance. However, direct experimental information regarding the structure of the emissive triplet excited state has remained scarce. Using time-resolved wide angle X-ray scattering (WAXS), the molecular structure of the triplet excited state for one of the complexes [Pt(ppy)(μ-tBu2pz)]2 was obtained in a dilute (0.5 mM) toluene solution utilizing the monochromatic X-ray beamline 11IDD of the Advanced Photon Source. The excited state structural analysis was carried out based on the results from both transient WAXS measurements and DFT calculations to shed light on the primary structural changes, in particular the Pt-Pt distance and ligand rotation taking place following the photo-excitation of [Pt(ppy)(μ-tBu2pz)]2 in toluene solution. We find that in the triplet excited state a pronounced contraction along the Pt-Pt axis has taken place accompanied by rotational motions of ppy ligands toward one another. Our results suggest that the contraction is larger than what has previously been reported, but are in good agreement with recent theoretical efforts and suggest the ppy moieties as targets for rational synthesis aimed at tuning the excited-state structure and properties

  7. Butterfly deformation modes in a photoexcited pyrazolate-bridged Pt complex measured by time-resolved x-ray scattering in solution

    DOE PAGES

    Haldrup, Kristoffer; Dohn, Asmus O.; Shelby, Megan L.; ...

    2016-08-27

    Pyrazolate-bridged di-nuclear Pt complexes represent a series of molecules with tunable absorption and emission properties that can be directly modulated by structural factors, such as the Pt-Pt distance. However, direct experimental information regarding the structure of the emissive triplet excited state has remained scarce. Using time-resolved wide angle X-ray scattering (WAXS), the molecular structure of the triplet excited state for one of the complexes [Pt(ppy)(μ-tBu2pz)]2 was obtained in a dilute (0.5 mM) toluene solution utilizing the monochromatic X-ray beamline 11IDD of the Advanced Photon Source. The excited state structural analysis was carried out based on the results from both transientmore » WAXS measurements and DFT calculations to shed light on the primary structural changes, in particular the Pt-Pt distance and ligand rotation taking place following the photo-excitation of [Pt(ppy)(μ-tBu2pz)]2 in toluene solution. We find that in the triplet excited state a pronounced contraction along the Pt-Pt axis has taken place accompanied by rotational motions of ppy ligands toward one another. Our results suggest that the contraction is larger than what has previously been reported, but are in good agreement with recent theoretical efforts and suggest the ppy moieties as targets for rational synthesis aimed at tuning the excited-state structure and properties« less

  8. Photoexcited calphostin C selectively destroys nuclear lamin B1 in neoplastic human and rat cells - a novel mechanism of action of a photodynamic tumor therapy agent.

    PubMed

    Chiarini, Anna; Whitfield, James F; Pacchiana, Raffaella; Armato, Ubaldo; Dal Pra, Ilaria

    2008-09-01

    Lamin B1, a major component of the nuclear lamina, anchors the nucleus to the cytoskeletal cage, and controls nuclear orientation, chromosome positioning and, alongside several enzymes, fundamental nuclear functions. Exposing polyomavirus-transformed rat pyF111 fibroblasts and human cervical carcinoma (HCC) C4-I cells for 30 min to photoexcited perylenequinone calphostin C, i.e. Cal C(phiE), an established reactive oxygen species (ROS)-generator and protein kinase C (PKC) inhibitor, caused the cells to selectively oxidize and then totally destroy their nuclear lamin B1 by only 60 min after starting the treatment, i.e. when apoptotic caspases' activities had not yet increased. However, while the oxidized lamin B1 was being destroyed, lamins A/C, the lamin A-associated nuclear envelope protein emerin, and the nucleoplasmic protein cyclin E were neither oxidized nor destroyed. The oxidized lamin B was ubiquitinated and demolished in the proteasome probably by an enhanced peptidyl-glutaminase-like activity. Hence, the Cal C(phiE)-induced rapid and selective lamin B1 oxidation and proteasomal destruction ahead of the activation of apoptotic caspases was by itself a most severe molecular lesion impairing vital nuclear functions. Conversely, Cal C directly added to the cells kept in the dark damaged neither nuclear lamin B1 nor cell viability. Thus, our findings reveal a novel cell-damaging mechanism of a photodynamic tumor therapeutic agent.

  9. Mesoscopic structural phase progression in photo-excited VO2 revealed by time-resolved x-ray diffraction microscopy

    SciTech Connect

    Zhu, Yi; Cai, Zhonghou; Chen, Pice; Zhang, Qingteng; Highland, Matthew J.; Jung, II Woong; Walko, Donald A.; Dufresne, Eric M.; Jaewoo, Jeong; Samant, Mahesh G.; Parkin, Stuart S. P.; Freeland, John W.; Evans, Paul G.; Wen, Haidan

    2016-02-26

    Dynamical phase separation during a solid-solid phase transition poses a challenge for understanding the fundamental processes in correlated materials. Critical information underlying a phase transition, such as localized phase competition, is difficult to reveal by measurements that are spatially averaged over many phase seperated regions. The ability to simultanousely track the spatial and temporal evolution of such systems is essential to understanding mesoscopic processes during a phase transition. Using state-of- the-art time-resolved hard x-ray diffraction microscopy, we directly visualize the structural phase progression in a VO2 film upon photoexcitation. Following a homogenous in-plane optical excitation, the phase transformation is initiated at discrete sites and completed by the growth of one lattice structure into the other, instead of a simultaneous isotropic lattice symmetry change. The time-dependent x-ray diffraction spatial maps show that the in-plane phase progression in laser-superheated VO2 is via a displacive lattice transformation as a result of relaxation from an excited monoclinic phase into a rutile phase. The speed of the phase front progression is quantitatively measured, which is faster than the process driven by in-plane thermal diffusion but slower than the sound speed in VO2. Lastly, the direct visualization of localized structural changes in the time domain opens a new avenue to study mesoscopic processes in driven systems.

  10. Glass-like recovery of antiferromagnetic spin ordering in a photo-excited manganite Pr0.7Ca0.3MnO3

    SciTech Connect

    Zhou, S. Y.; Langner, M. C.; Zhu, Y.; Chuang, Y. -D.; Rini, M.; Glover, T. E.; Hertlein, M. P.; Gonzalez, A.G. Cruz; Tahir, N.; Tomioka, Y.; Tokura, Y.; Hussain, Z.; Schoenlein, R. W.

    2014-01-16

    Electronic orderings of charges, orbitals and spins are observed in many strongly correlated electron materials, and revealing their dynamics is a critical step toward understanding the underlying physics of important emergent phenomena. Here we use time-resolved resonant soft x-ray scattering spectroscopy to probe the dynamics of antiferromagnetic spin ordering in the manganite Pr0:7Ca0:3MnO3 following ultrafast photo-exitation. Our studies reveal a glass-like recovery of the spin ordering and a crossover in the dimensionality of the restoring interaction from quasi-1D at low pump fluence to 3D at high pump fluence. This behavior arises from the metastable state created by photo-excitation, a state characterized by spin disordered metallic droplets within the larger charge- and spin-ordered insulating domains. Comparison with time-resolved resistivity measurements suggests that the collapse of spin ordering is correlated with the insulator-to-metal transition, but the recovery of the insulating phase does not depend on the re-establishment of the spin ordering.

  11. Spatio-spectral characteristics of ultra-broadband THz emission from two-colour photoexcited gas plasmas and their impact for nonlinear spectroscopy

    NASA Astrophysics Data System (ADS)

    Blank, V.; Thomson, M. D.; Roskos, H. G.

    2013-07-01

    We present a characterization of the combined spatial and spectral properties of the terahertz (THz) and mid-infrared emission from gas plasmas generated and driven by two-colour femtosecond optical pulses. For its use in nonlinear spectroscopy, the impact of the relatively complex spatial profile for both broadband (∼ 10 THz) and ultra-broadband (> 100 THz) emission needs to be considered, in particular for experiments based on z-scan techniques. Here we apply spatially resolved measurements based on both field autocorrelation and sum-frequency (up-conversion) detection. Based on these results, we present simulations of the ultra-broadband profile during its passage through a focal region. In addition to the inherent features of the emission profile due to the generation mechanism in the plasma filament, we also analyse the role of the semconductor (silicon) wafer typically placed after the plasma to discard the optical pump beams, whose photoexcitation also can play a role in the resultant THz profile.

  12. Rationalizing long-lived photo-excited carriers in photocatalyst (La5Ti2CuS5O7) in terms of one-dimensional carrier transport

    NASA Astrophysics Data System (ADS)

    Suzuki, Yohichi; Singh, Rupashree Balia; Matsuzaki, Hiroyuki; Furube, Akihiro; Ma, Guijun; Hisatomi, Takashi; Domen, Kazunari; Seki, Kazuhiko

    2016-09-01

    The semiconductor La5Ti2CuS5O7 (LTC) is a potential photocatalyst capable of operating under visible light irradiation and behaves both as a photocathode and anode when embedded onto metal layers. Time-resolved diffuse reflectance (TRDR) measurements were carried out on LTC powder and LTC deposited on Au as the back contact using the particle-transfer method. Results of TRDR measurements of powdered LTC indicated the existence of long-lived photo-excited carriers, and suggested the existence of a mechanism for preventing carrier loss in LTC. Prior research has reported that LTC has a rod-shaped crystal structure and that electrons and holes are transported through different, spatially separated channels. Based on this, we introduced a one-dimensional carrier transport model. By analyzing TRDR data, we extracted material parameters such as the diffusion coefficient of LTC. Theoretical results indicated that a micron-sized LTC particle would be preferable if carriers trapped at the top-surface do contribute to photocatalytic gas generation.

  13. Glass-like recovery of antiferromagnetic spin ordering in a photo-excited manganite Pr0.7Ca0.3MnO3

    NASA Astrophysics Data System (ADS)

    Zhou, S. Y.; Langner, M. C.; Zhu, Y.; Chuang, Y.-D.; Rini, M.; Glover, T. E.; Hertlein, M. P.; Gonzalez, A. G. Cruz; Tahir, N.; Tomioka, Y.; Tokura, Y.; Hussain, Z.; Schoenlein, R. W.

    2014-02-01

    Electronic orderings of charges, orbitals and spins are observed in many strongly correlated electron materials, and revealing their dynamics is a critical step toward undertsanding the underlying physics of important emergent phenomena. Here we use time-resolved resonant soft x-ray scattering spectroscopy to probe the dynamics of antiferromagnetic spin ordering in the manganite Pr0.7Ca0.3MnO3 following ultrafast photo-exitation. Our studies reveal a glass-like recovery of the spin ordering and a crossover in the dimensionality of the restoring interaction from quasi-1D at low pump fluence to 3D at high pump fluence. This behavior arises from the metastable state created by photo-excitation, a state characterized by spin disordered metallic droplets within the larger charge- and spin-ordered insulating domains. Comparison with time-resolved resistivity measurements suggests that the collapse of spin ordering is correlated with the insulator-to-metal transition, but the recovery of the insulating phase does not depend on the re-establishment of the spin ordering.

  14. Glass-like recovery of antiferromagnetic spin ordering in a photo-excited manganite Pr₀.₇Ca₀.₃MnO₃.

    PubMed

    Zhou, S Y; Langner, M C; Zhu, Y; Chuang, Y-D; Rini, M; Glover, T E; Hertlein, M P; Gonzalez, A G Cruz; Tahir, N; Tomioka, Y; Tokura, Y; Hussain, Z; Schoenlein, R W

    2014-02-13

    Electronic orderings of charges, orbitals and spins are observed in many strongly correlated electron materials, and revealing their dynamics is a critical step toward undertsanding the underlying physics of important emergent phenomena. Here we use time-resolved resonant soft x-ray scattering spectroscopy to probe the dynamics of antiferromagnetic spin ordering in the manganite Pr₀.₇Ca₀.₃MnO₃ following ultrafast photo-exitation. Our studies reveal a glass-like recovery of the spin ordering and a crossover in the dimensionality of the restoring interaction from quasi-1D at low pump fluence to 3D at high pump fluence. This behavior arises from the metastable state created by photo-excitation, a state characterized by spin disordered metallic droplets within the larger charge- and spin-ordered insulating domains. Comparison with time-resolved resistivity measurements suggests that the collapse of spin ordering is correlated with the insulator-to-metal transition, but the recovery of the insulating phase does not depend on the re-establishment of the spin ordering.

  15. Glass-like recovery of antiferromagnetic spin ordering in a photo-excited manganite Pr0.7Ca0.3MnO3

    PubMed Central

    Zhou, S. Y.; Langner, M. C.; Zhu, Y.; Chuang, Y.-D.; Rini, M.; Glover, T. E.; Hertlein, M. P.; Gonzalez, A. G. Cruz; Tahir, N.; Tomioka, Y.; Tokura, Y.; Hussain, Z.; Schoenlein, R. W.

    2014-01-01

    Electronic orderings of charges, orbitals and spins are observed in many strongly correlated electron materials, and revealing their dynamics is a critical step toward undertsanding the underlying physics of important emergent phenomena. Here we use time-resolved resonant soft x-ray scattering spectroscopy to probe the dynamics of antiferromagnetic spin ordering in the manganite Pr0.7Ca0.3MnO3 following ultrafast photo-exitation. Our studies reveal a glass-like recovery of the spin ordering and a crossover in the dimensionality of the restoring interaction from quasi-1D at low pump fluence to 3D at high pump fluence. This behavior arises from the metastable state created by photo-excitation, a state characterized by spin disordered metallic droplets within the larger charge- and spin-ordered insulating domains. Comparison with time-resolved resistivity measurements suggests that the collapse of spin ordering is correlated with the insulator-to-metal transition, but the recovery of the insulating phase does not depend on the re-establishment of the spin ordering. PMID:24522173

  16. The structure and electronic state of photoexcited fullerene linked with a nitroxide radical based on an analysis of a two-dimensional electron paramagnetic resonance nutation spectrum

    NASA Astrophysics Data System (ADS)

    Mizuochi, Norikazu; Ohba, Yasunori; Yamauchi, Seigo

    1999-08-01

    An electron paramagnetic resonance (EPR) study of 3,4-fulleropyrrolidine-2-spiro-4'[2',2',6',6'-tetramethyl]piperidine-1'-oxyl (1) was performed on the photoexcited quartet state in toluene glass. The spectrum of the |S,Ms>=|3/2,±3/2>⇔|3/2,±1/2> transitions was observed selectively by using a two-dimensional (2D) nutation method and analyzed with a spectral simulation in a randomly oriented system. A position of the nitroxide moiety was determined with respect to the zero-field splitting (zfs) axes of excited triplet fullerene (3C60) by taking into account of the dipolar-dipolar interaction between the radical and 3C60, the hyperfine coupling, the anisotropic g-value of the nitroxide radical, and the zfs of the 3C60 moiety. It was found that none of the zfs axes of the 3C60 moiety coincide with the local C2 axis of the molecule which is defined by the position of addition. A symmetry of the electronic structure in 3C60 is discussed on the basis of the result.

  17. Selective Stabilization of the Spin States of a Magnetically Anisotropic Dysprosium Ion Induced by Photo-Excitation of the Associated Cyclic π-Conjugated System.

    PubMed

    Fukuda, Takamitsu; Ozawa, Hideaki; Sakaguchi, Yutaro; Kizaki, Kazuro; Kobayashi, Toshiya; Fuyuhiro, Akira; Ishikawa, Naoto

    2017-09-08

    The presence of a new electronic interaction, which couples a 4f-electronic system with a total angular momentum J and a photo-excited cyclic π-conjugated system with an orbital angular momentum L, in the bis(phthalocyaninato)dysprosium single molecule magnet (Pc2Dy-) is reported. Two π-π* excited states in the visible spectral region of Pc2Dy-, which are denoted here as QL and QH, showed significantly different temperature and field dependences of the magnetic circular dichroism (MCD) A-term intensity. This phenomenon indicates not only the presence of the "J-L" interaction but also that the interaction generates two different preferred orientations of the J-L pair, either parallel (in the QH band) or anti-parallel (in the QL band), depending on the excitation energy. We have succeeded in construction of a theoretical model that reproduces the temperature and field dependences, and quantitatively evaluated the J-L interaction. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Conductivity and magnetoresistance of La0.7Ce0.3MnO3-δ thin films under photoexcitation

    NASA Astrophysics Data System (ADS)

    Thiessen, A.; Beyreuther, E.; Werner, R.; Kleiner, R.; Koelle, D.; Eng, L. M.

    2015-01-01

    La0.7Ce0.3MnO3 thin films of different thicknesses, degrees of CeO2-phase segregation and oxygen deficiency, grown on SrTiO3 single crystal substrates, were comparatively investigated with respect to both their spectral and temperature-dependent photoconductivity (PC) and their magnetoresistance (MR) behaviour under photoexcitation. While as-grown films were insensitive to optical excitation, oxygen reduction appeared to be an effective way to decrease the film resistance, but the film thickness was found to play a minor role. However, from the evaluation of the spectral behaviour of the PC and the comparison of the MR of the LCeMO/substrate-samples with a bare substrate under illumination we find that the photoconductivity data reflects not only contributions from (i) photogenerated charge carriers in the film and (ii) carriers injected from the photoconductive substrate (as concluded from earlier works), but also (iii) a decisive parallel photoconduction in the SrTiO3 substrate. Furthermore—also by analyzing the MR characteristics—the unexpected occurence of a strong electroresistive effect in the sample with the highest degree of CeO2 segregation and oxygen deficiency could be attributed to the electroresistance of the SrTiO3 substrate as well. The results suggest a critical reconsideration and possibly a reinterpretation of several previous photoconductivity and electroresistance investigations of manganite thin films on SrTiO3.

  19. 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.

  20. Deep Water Ocean Acoustics

    DTIC Science & Technology

    2016-12-22

    Final Report 3. DATES COVERED (From - To) 7/1/15 to 12/22/16 4. TITLE AND SUBTITLE Deep Water Ocean Acoustics 5a. CONTRACT NUMBER...NUMBER Ocean Acoustical Services and Instrumentation Systems, Inc. 5 Militia Drive, Ste. 104 Lexington, MA 02421-4706...FR-14C0172- Ocean Acoustics- 123116 9. SPONSORING / MONITORING AGENCY NAME(S) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S ACRONYM(S) Office of Naval

  1. Deep Water Ocean Acoustics

    DTIC Science & Technology

    2016-10-07

    OASIS, INC. 1 Report No. QSR-14C0172- Ocean Acoustics-093016 Quarterly Progress Report Technical and Financial Deep Water Ocean Acoustics...Award No.: N00014-14-C-0172 Report No. QSR-14C0172- Ocean Acoustics-093016 Prepared for: Office of Naval Research For the period: July 1, 2016...to September 30, 2016 Submitted by: Principal Investigator/Author: Kevin Heaney Ocean Acoustical Services and Instrumentation Systems, Inc. 5

  2. Deep Water Ocean Acoustics

    DTIC Science & Technology

    2016-08-03

    OASIS, INC. 1 Report No. QSR-14C0172- Ocean Acoustics-063016 Quarterly Progress Report Technical and Financial Deep Water Ocean Acoustics...Award No.: N00014-14-C-0172 Report No. QSR-14C0172- Ocean Acoustics-063016 Prepared for: Office of Naval Research For the period: April 1...2016 to June 30, 2016 Submitted by: Principal Investigator/Author: Kevin Heaney Ocean Acoustical Services and Instrumentation Systems, Inc. 5

  3. Deep Water Ocean Acoustics

    DTIC Science & Technology

    2016-04-30

    OASIS, INC. 1 Report No. QSR-14C0172- Ocean Acoustics-043016 Quarterly Progress Report Technical and Financial Deep Water Ocean Acoustics...Award No.: N00014-14-C-0172 Report No. QSR-14C0172- Ocean Acoustics-093015 Prepared for: Office of Naval Research For the period: January 1...2016 to March 31, 2015 Submitted by: Principal Investigator/Author: Kevin Heaney Ocean Acoustical Services and Instrumentation Systems, Inc. 5

  4. Deep Water Ocean Acoustics

    DTIC Science & Technology

    2015-07-17

    under-ice scattering , bathymetric diffraction and the application of the ocean acoustic Parabolic Equation to infrasound. 2. Tasks a. Task 1...QSR-14C0172-Ocean Acoustics -063015 Figure 10. Estimated reflection coefficient as a function of frequency by taking the difference of downgoing and...OASIS, INC. 1 Report No. QSR-14C0172-Ocean Acoustics -063015 Quarterly Progress Report Technical and Financial Deep Water Ocean Acoustics

  5. Deep Imaging Survey

    NASA Image and Video Library

    2003-07-25

    This is the first Deep Imaging Survey image taken by NASA Galaxy Evolution Explorer. On June 22 and 23, 2003, the spacecraft obtained this near ultraviolet image of the Groth region by adding multiple orbits for a total exposure time of 14,000 seconds. Tens of thousands of objects can be identified in this picture. http://photojournal.jpl.nasa.gov/catalog/PIA04627

  6. Deep-water archeology.

    PubMed

    Bascom, W

    1971-10-15

    There is reason to believe that some old wooden ships on the deep-sea floor have survived for thousands of years without much change. They will not be covered with much sediment, and it will be possible to find them using new searching techniques. These are embodied in the system of the Alcoa Seaprobe, which is also equipped to identify and raise old ships.

  7. Deep-Sarsa

    NASA Astrophysics Data System (ADS)

    Andrecut, M.; Ali, M. K.

    In this paper we discuss the application of reinforcement learning algorithms to the problem of autonomous robot navigation. We show that the autonomous navigation using the standard delayed reinforcement learning algorithms is an ill posed problem and we present a more efficient algorithm for which the convergence speed is greatly improved. The proposed algorithm (Deep-Sarsa) is based on a combination between the Depth-First Search (a graph searching algorithm) and Sarsa (a delayed reinforcement learning algorithm).

  8. Deep Brain Stimulation

    PubMed Central

    Chen, X.L.; Xiong, Y.Y.; Xu, G.L.; Liu, X.F.

    2013-01-01

    Deep brain stimulation (DBS) has provided remarkable therapeutic benefits for people with a variety of neurological disorders. Despite the uncertainty of the precise mechanisms underlying its efficacy, DBS is clinically effective in improving motor function of essential tremor, Parkinson's disease and primary dystonia and in relieving obsessive-compulsive disorder. Recently, this surgical technique has continued to expand to other numerous neurological diseases with encouraging results. This review highlighted the current and potential future clinical applications of DBS. PMID:25187779

  9. Understanding deep convolutional networks

    PubMed Central

    Mallat, Stéphane

    2016-01-01

    Deep convolutional networks provide state-of-the-art classifications and regressions results over many high-dimensional problems. We review their architecture, which scatters data with a cascade of linear filter weights and nonlinearities. A mathematical framework is introduced to analyse their properties. Computations of invariants involve multiscale contractions with wavelets, the linearization of hierarchical symmetries and sparse separations. Applications are discussed. PMID:26953183

  10. Deep Water Formation

    NASA Technical Reports Server (NTRS)

    Killworth, P. D.

    1984-01-01

    Some simple arguments on plumes of dense water and filling boxes were given. What determines the time for a large-scale environment to be modified by the injection of dense water at its edge is the mass flux, not the buoyancy flux. However, it is the denser buoyancy flux, when there are several competing plumes (e.g., the Mediterranean outflow versus the Denmark Strait outflow) that determines which plume will provide the bottom water for that ocean basin. It was noted that the obvious laboratory experiment (rotate a pie-shaped annulus, and heat/cool it on the surface) had never been performed. Thus, to some extent our belief that deep convection is somehow automatic at high latitudes to close off some ill-defined meridional circulation has never been tested. A summary of deep convection was given. The two fundamental formation mechanisms were shown. Of the two, it is open-ocean convection which forms the water which supplies the Denmark Strait overflow -- in all likelihood, as formation in the Greenland Sea remains stubbornly unobserved. But it is the slope convection which finally creates North Atlantic deep water, following the Denmark Strait overspill.

  11. Thymine dimer repair by electron transfer from photo-excited 2',3',5'-tri-O-acetyl-8-oxo-7,8-dihydroguanosine or 2',3',5'-tri-O-acetyl-ribosyluric acid - a theoretical study

    NASA Astrophysics Data System (ADS)

    Marchaj, Marzena; Sieradzan, Iwona; Anusiewicz, Iwona; Skurski, Piotr; Simons, Jack

    2013-07-01

    Electronic structure calculations are combined with published experimental data from another laboratory to interpret trends in the rates of thymine dimer repair induced by photo-exciting the title molecules or their deprotonated derivatives. Opening of the thymine dimer's cyclobutane ring is believed to be initiated by electron transfer from the photo-excited molecule and to then pass over thermally accessible energy barriers. Therefore, the repair rates are determined by rates of accessing activation barriers connecting the photo-excited state to the electron-transferred state. These barriers are shown to depend on the electronic excitation energy and electron-binding energy of the donor and the electron affinity of the thymine dimer acceptor. For neutral donors, the barriers also depend on the distance between the donor and the thymine dimer through a screened Coulomb interaction between the donor cation and acceptor anion. For the deprotonated (anionic) donors, this Coulomb-derived distance dependence is absent. For both neutral and anionic donors, the range for electron transfer is spatially limited by the strength of the electronic couplings. The model put forth here rationalizes why anionic donors can be expected to perform better than neutrals and offers a framework for designing electron transfer agents optimal for a given electron acceptor.

  12. Imagining Deep Time (Invited)

    NASA Astrophysics Data System (ADS)

    Talasek, J.

    2013-12-01

    Imagining Deep Time '...the mind seemed to grow giddy by looking so far into the abyss of time.' John Playfair (1748 -1819), scientist and mathematician "Man cannot afford to conceive of nature and exclude himself." Emmit Gowin, photographer 'A person would have to take themselves out of the human context to begin to think in terms of geologic time. They would have to think like a rock.' Terry Falke, photographer The term Deep Time refers to the vastness of the geological time scale. First conceived in the 18th century, the development of this perspective on time has been pieced together like a jigsaw puzzle of information and observations drawn from the study of the earth's structure and discovered fossilized flora and fauna. Deep time may possibly be the greatest contribution made by the discipline of geology forever impacting our perception of earth and our relationship to it. How do we grasp such vast concepts as deep time which relates to the origins of the earth or cosmic time which relates to the origins of the universe - concepts that exist far beyond the realm of human experience? Further more how do we communicate this? The ability to visualize is a powerful tool of discovery and communication for the scientist and it is part and parcel of the work of visual artists. The scientific process provides evidence yet it is imagination on the part of the scientists and artists alike that is needed to interpret that information. This exhibition represents an area where both rational and intuitive thinking come together to explore this question of how we relate to the vastness of time. The answer suggested by the combination of art work assembled here suggests that we do so through a combination of visual metaphors (cycles, circles, arrows, trajectories) and visual evidence (rock formations, strata, fossils of fauna and flora) while being mediated through various technologies. One provides factual and empirical evidence while the other provides a way of grasping

  13. Dissociation of deep-core-excited CH{sub 3}Cl

    SciTech Connect

    Hansen, D.L.; Martin, R.; Vanderford, B.

    1997-04-01

    Using x-rays from B.L. 9.3.1, a space-focused time-of-flight (TOF) was used to study photofragmentation of CH{sub 3}Cl following excitation in the neighborhood of the Cl K-shell threshold ({approximately} 2.8 keV). Multi-ion coincidence measurements were used to search for selective dissociation of specific bonds in the molecule. Such selectivity has been observed for excitation near outer-core-level thresholds (e.g., Cl 2p), but this is the first study in deep core levels, where very-short core-hole lifetimes and Auger cascade effects may influence fragmentation. Both high-resolution time-of-flight spectroscopy and multi-coincidence photoelectron-photoion-photoion (PE-PIPICO), as well as photoelectron-photoion-photoion-photoion (PE3PICO) measurements were performed. Dramatic changes in the line shapes for different fragment ions are observed as a function of the excitation energy, and are attributed to selective dissociation of the CH{sub 3}Cl molecule along the C-Cl bond. In addition, pronounced angular distributions of the ejected ions are observed on resonance.

  14. The deep subterranean biosphere

    NASA Astrophysics Data System (ADS)

    Pedersen, Karsten

    1993-08-01

    The main purpose with this review is to summarise present research on the microbiology of deep subterranean environments, deeper than 50-100 m. Included are mainly studies where drilling, excavation, core sampling and ground water sampling have been made for research. Studies done in environments penetrated for commercial purposes, such as water wells, mining, oil recovery etc., have been dismissed because of the obvious risk for contamination during the penetration. Different measures that can be applied to reduce the risk of microbial contamination of sampled specimens by the access operations are discussed. The requirement for reliable estimations of the present microbial biomass, its activity and diversity in subterranean ecosystems, is fundamental. An array of different methods to achieve this goal are presented. The depth limit for subterranean life is suggested to be set by temperature, provided there is energy available for microbial life. If so, it should be possible to enrich thermophilic bacteria from deep hot ground waters which also has been done. There are only a few sites where the subterranean microbiology has been studied in multidisiplinary programs including chemistry and geology. The two most extensively published sites are the sediments of the Atlantic coastal plain of South Carolina, USA, studied in a subsurface program, initiated and sponsored by the U.S. Department of Energy, and crystalline bed-rock in Sweden studied in a program concerning the safety of future underground repositories for nuclear waste. This review presents an array of independent reports suggesting that microbial life is widespread at depth in the crust of earth—the deep subterranean biosphere. The obvious consequences is that microbes may be involved in many subterranean geochemical processes, such as diagenesis, weathering, precipitation, and in oxidation or reduction reactions of metals, carbon, nitrogen and sulfur—just as they are in most terranean environments.

  15. Deep shadow occulter

    NASA Technical Reports Server (NTRS)

    Cash, Webster (Inventor)

    2010-01-01

    Methods and apparatus are disclosed for occulting light. The occulter shape suppresses diffraction at any given size or angle and is practical to build because it can be made binary to avoid scatter. Binary structures may be fully opaque or fully transmitting at specific points. The diffraction suppression is spectrally broad so that it may be used with incoherent white light. An occulter may also include substantially opaque inner portion and an at least partially transparent outer portion. Such occulters may be used on the ground to create a deep shadow in a short distance, or may be used in space to suppress starlight and reveal exoplanets.

  16. Deep Space Positioning System

    NASA Technical Reports Server (NTRS)

    Vaughan, Andrew T. (Inventor); Riedel, Joseph E. (Inventor)

    2016-01-01

    A single, compact, lower power deep space positioning system (DPS) configured to determine a location of a spacecraft anywhere in the solar system, and provide state information relative to Earth, Sun, or any remote object. For example, the DPS includes a first camera and, possibly, a second camera configured to capture a plurality of navigation images to determine a state of a spacecraft in a solar system. The second camera is located behind, or adjacent to, a secondary reflector of a first camera in a body of a telescope.

  17. Groth Deep Locations Image

    NASA Image and Video Library

    2003-07-25

    NASA's Galaxy Evolution Explorer photographed this ultraviolet color blowup of the Groth Deep Image on June 22 and June 23, 2003. Hundreds of galaxies are detected in this portion of the image, and the faint red galaxies are believed to be 6 billion light years away. The white boxes show the location of these distant galaxies, of which more than a 100 can be detected in this image. NASA astronomers expect to detect 10,000 such galaxies after extrapolating to the full image at a deeper exposure level. http://photojournal.jpl.nasa.gov/catalog/PIA04626

  18. Fluorescence Excitation Function Produced Through Photoexcitation of the Rydberg States b, cn, and o3 of N2 in the 80-100 nm Region

    NASA Astrophysics Data System (ADS)

    Wu, R. C.; Judge, D. L.; Singh, T. S.; Mu, X. L.; Nee, J. B.; Chiang, S. Y.; Fung, H. S.

    2006-12-01

    Fluorescence excitation functions produced through photoexcitation of N2 using synchrotron radiation in the spectral region between 80 and 100 nm have been studied. Two broadband detectors were employed to simultaneously monitor fluorescence in the 115-320 nm and 300-700 nm region, respectively. The peaks in the VUV Fluorescence excitation functions are found to correspond to excitation of absorption transitions from the ground electronic state to the Rydberg states of b, cn (with n= 4-9), and o3 of N2. The relative fluorescence production cross sections for the observed peaks are determined. No fluorescence has been produced through excitation of the most dominating absorption features of the b-X transition except the (1,0), (5,0), and (6,0) bands, in excellent agreement with the recent lifetime measurements [1] and theoretical calculations [2]. In addition, fluorescence peaks correlate with the long vibrational progression of the c4 (v = 0-7) has also been observed. Weak fluorescence excitation peaks are also found to correlate with the excitation of the (1,0), (2,0), and (3,0) bands of the o3 VX transition. The present results provide important information for further unraveling of complicated and intriguing interactions among the excited electronic states of N2. Furthermore, solar photon excitation of N2 leading to the production of c4(0) may provide useful data required for evaluation and analysis of dayglow models of the c4(0) issue of the Earth's atmosphere [3]. Detailed results will be presented. This research is based on work supported by NSF grant ATM-0096761. [1] Sprengers, J. P., W. Ubachs, and K. G. H. Baldwin, J. Chem. Phys., 122, 144301 (2005). [2] Lewis, B. R., S. T. Gibson, W. Zhang, H. Lefebvre-Brion, and J.-M. Robbe, J. Chem. Phys., 122, 144302 (2005). [3] e.g., Meier, R. R., Space Sci. Rev., 58, 1 (1991).

  19. Deep drawing of uranium metal

    SciTech Connect

    Jackson, R J; Lundberg, M R

    1987-01-19

    A procedure was developed to fabricate uranium forming blanks with high ''draw-ability'' so that cup shapes could be easily and uniformly deep drawn. The overall procedure involved a posttreatment to develop optimum mechanical and structural properties in the deep-drawn cups. The fabrication sequence is casting high-purity logs, pucking cast logs, cross-rolling pucks to forming blanks, annealing and outgassing forming blanks, cold deep drawing to hemispherical shapes, and stress relieving, outgassing, and annealing deep-drawn parts to restore ductility and impart dimensional stability. The fabrication development and the resulting fabrication procedure are discussed in detail. The mechanical properties and microstructural properties are discussed.

  20. Deep learning for image classification

    NASA Astrophysics Data System (ADS)

    McCoppin, Ryan; Rizki, Mateen

    2014-06-01

    This paper provides an overview of deep learning and introduces the several subfields of deep learning including a specific tutorial of convolutional neural networks. Traditional methods for learning image features are compared to deep learning techniques. In addition, we present our preliminary classification results, our basic implementation of a convolutional restricted Boltzmann machine on the Mixed National Institute of Standards and Technology database (MNIST), and we explain how to use deep learning networks to assist in our development of a robust gender classification system.

  1. Groth Deep Locations Image

    NASA Technical Reports Server (NTRS)

    2003-01-01

    NASA's Galaxy Evolution Explorer photographed this ultraviolet color blowup of the Groth Deep Image on June 22 and June 23, 2003. Hundreds of galaxies are detected in this portion of the image, and the faint red galaxies are believed to be 6 billion light years away. The white boxes show the location of these distant galaxies, of which more than a 100 can be detected in this image. NASA astronomers expect to detect 10,000 such galaxies after extrapolating to the full image at a deeper exposure level.

    The Galaxy Evolution Explorer mission is led by the California Institute of Technology, which is also responsible for the science operations and data analysis. NASA's Jet Propulsion Laboratory, Pasadena, Calif., a division of Caltech, manages the mission and built the science instrument. The mission was developed under NASA's Explorers Program, managed by the Goddard Space Flight Center, Greenbelt, Md. The mission's international partners include South Korea and France.

  2. Deep Brain Stimulation

    PubMed Central

    Lyketsos, Constantine G.; Pendergrass, Jo Cara; Lozano, Andres M.

    2012-01-01

    Recent studies have identified an association between memory deficits and defects of the integrated neuronal cortical areas known collectively as the default mode network. It is conceivable that the amyloid deposition or other molecular abnormalities seen in patients with Alzheimer’s disease may interfere with this network and disrupt neuronal circuits beyond the localized brain areas. Therefore, Alzheimer’s disease may be both a degenerative disease and a broader system-level disorder affecting integrated neuronal pathways involved in memory. In this paper, we describe the rationale and provide some evidence to support the study of deep brain stimulation of the hippocampal fornix as a novel treatment to improve neuronal circuitry within these integrated networks and thereby sustain memory function in early Alzheimer’s disease. PMID:23346514

  3. Neptune's deep atmosphere revealed

    SciTech Connect

    de Pater, I. ); Atreya, S.K. ); Romani, P.N.

    1989-08-01

    The brightness temperature of Uranus at 20 cm is 260 {plus minus} 10K, while for Neptune it is 318 {plus minus} 16K. Since NH{sub 3} is the dominant absorber at this wavelength the authors have modeled the microwave spectra of Neptune based upon an assumed deep gaseous mixing ratio of NH{sub 3} and subsequent loss into clouds. The difference between the two brightness temperatures implies that the NH{sub 3} mixing ratio below the level of cloud formation on Neptune compared to Uranus is lower by nearly 2 order of magnitude. An alternative explanation is that the 20 cm radiation from Neptune is a combination of thermal plus synchrotron emission as proposed by de Pater and Goertz (1989).

  4. Deep, zonal subequatorial currents.

    PubMed

    Talley, L D; Johnson, G C

    1994-02-25

    Large-scale, westward-extending tongues of warm (Pacific) and cold (Atlantic) water are found between 2000 and 3000 meters both north and south of the equator in the Pacific and Atlantic oceans. They are centered at 5 degrees to 8 degrees north and 10 degrees to 15 degrees south (Pacific) and 5 degrees to 8 degrees north and 15 degrees to 20 degrees south (Atlantic). They are separated in both oceans by a contrasting eastward-extending tongue, centered at about 1 degrees to 2 degrees south, in agreement with previous helium isotope observations (Pacific). Thus, the indicated deep tropical westward flows north and south of the equator and eastward flow near the equator may result from more general forcing than the hydrothermal forcing previously hypothesized.

  5. Method of deep drilling

    SciTech Connect

    Colgate, S. A.

    1984-11-20

    Deep drilling is facilitated by the following steps practiced separately or in any combination: Periodically and sequentially fracturing zones adjacent the bottom of the bore hole with a thixotropic fastsetting fluid that is accepted into the fracture to overstress the zone, such fracturing and injection being periodic as a function of the progression of the drill. Casing the bore hole with ductile, pre-annealed casing sections, each of which is run down through the previously set casing and swaged in situ to a diameter large enough to allow the next section to run down through it. Drilling the bore hole using a drill string of a low density alloy and a high density drilling mud so that the drill string is partially floated.

  6. Method of deep drilling

    DOEpatents

    Colgate, Stirling A.

    1984-01-01

    Deep drilling is facilitated by the following steps practiced separately or in any combination: (1) Periodically and sequentially fracturing zones adjacent the bottom of the bore hole with a thixotropic fastsetting fluid that is accepted into the fracture to overstress the zone, such fracturing and injection being periodic as a function of the progression of the drill. (2) Casing the bore hole with ductile, pre-annealed casing sections, each of which is run down through the previously set casing and swaged in situ to a diameter large enough to allow the next section to run down through it. (3) Drilling the bore hole using a drill string of a low density alloy and a high density drilling mud so that the drill string is partially floated.

  7. Deep frequency modulation interferometry.

    PubMed

    Gerberding, Oliver

    2015-06-01

    Laser interferometry with pm/Hz precision and multi-fringe dynamic range at low frequencies is a core technology to measure the motion of various objects (test masses) in space and ground based experiments for gravitational wave detection and geodesy. Even though available interferometer schemes are well understood, their construction remains complex, often involving, for example, the need to build quasi-monolithic optical benches with dozens of components. In recent years techniques have been investigated that aim to reduce this complexity by combining phase modulation techniques with sophisticated digital readout algorithms. This article presents a new scheme that uses strong laser frequency modulations in combination with the deep phase modulation readout algorithm to construct simpler and easily scalable interferometers.

  8. Deep 6-DOF Tracking.

    PubMed

    Garon, Mathieu; Lalonde, Jean-Francois

    2017-11-01

    We present a temporal 6-DOF tracking method which leverages deep learning to achieve state-of-the-art performance on challenging datasets of real world capture. Our method is both more accurate and more robust to occlusions than the existing best performing approaches while maintaining real-time performance. To assess its efficacy, we evaluate our approach on several challenging RGBD sequences of real objects in a variety of conditions. Notably, we systematically evaluate robustness to occlusions through a series of sequences where the object to be tracked is increasingly occluded. Finally, our approach is purely data-driven and does not require any hand-designed features: robust tracking is automatically learned from data.

  9. Toward a comprehensive understanding of solid-state core-level XPS linewidths: Experimental and theoretical studies on the Si2p and O1s linewidths in silicates

    NASA Astrophysics Data System (ADS)

    Bancroft, G. M.; Nesbitt, H. W.; Ho, R.; Shaw, D. M.; Tse, J. S.; Biesinger, M. C.

    2009-08-01

    High resolution X-ray Photoelectron Spectroscopy (XPS) core-level Si2p and O1s spectra of the nonconductors α-SiO2 (quartz) at 120 and 300 K and vitreous SiO2 at 300 K were obtained with a Kratos Axis Ultra XPS instrument (instrumental resolution of <0.4eV ) which incorporates a unique charge compensation system that minimizes differential charge broadening on nonconductors. The Si2p and O1s linewidths at 300 K ( ˜1.1 and ˜1.2eV , respectively) are similar for all silicates (and similar to previous thin film SiO2 spectra obtained previously), showing that differential charging does not contribute significantly to our spectra. At 120 K, there is a small decrease (0.04 eV) in the Si2p linewidth of α-SiO2 , but no measurable decrease in O1s linewidth. The O1s lines are generally and distinctly asymmetric. We consider all possible sources of line broadening and show that final state vibrational broadening (FSVB) and phonon broadening are the major causes of the broad and asymmetric lines. Previous high resolution gas phase XPS studies have identified large FSVB contributions to the Si2p spectra of SiCl4 , SiF4 , and Si(OCH3)4 molecules, and this vibrational structure leads total Si2p3/2 linewidths of up to ˜0.5eV , even with individual peak linewidths of <0.1eV . The Si atom of Si(OCH3)4 is an excellent analog for Si in crystalline SiO2 because the Si-O bond lengths and symmetric stretch frequencies are similar in both compounds. Similar vibrational contributions to the Si2p and O1s spectra of solid silicates are anticipated if the Si2p and O1s core-hole states produce similar changes to the Si-O bond length in both phases. To investigate the possibility, Car-Parrinello molecular dynamics calculations were performed and show that changes to Si-O bond lengths between ion and ground states (Δr) for both Si2p and O1s hole states are similar for both crystalline SiO2 and gaseous Si(OCH3)4 . Δr are -0.04Å for Si2p and ˜+0.05Å for O1s in both compounds. Indeed, the

  10. Modeling ocean deep convection

    NASA Astrophysics Data System (ADS)

    Canuto, V. M.; Howard, A.; Hogan, P.; Cheng, Y.; Dubovikov, M. S.; Montenegro, L. M.

    The goal of this study is to assess models for Deep Convection with special emphasis on their use in coarse resolution ocean general circulation models. A model for deep convection must contain both vertical transport and lateral advection by mesoscale eddies generated by baroclinic instabilities. The first process operates mostly in the initial phases while the second dominates the final stages. Here, the emphasis is on models for vertical mixing. When mesoscales are not resolved, they are treated with the Gent and McWilliams parameterization. The model results are tested against the measurements of Lavender, Davis and Owens, 2002 (LDO) in the Labrador Sea. Specifically, we shall inquire whether the models are able to reproduce the region of " deepest convection," which we shall refer to as DC (mixed layer depths 800-1300 m). The region where it was measured by Lavender et al. (2002) will be referred to as the LDO region. The main results of this study can be summarized as follows. 3° × 3° resolution. A GFDL-type OGCM with the GISS vertical mixing model predicts DC in the LDO region where the vertical heat diffusivity is found to be 10 m 2 s -1, a value that is quite close to the one suggested by heuristic studies. No parameter was changed from the original GISS model. However, the GISS model also predicts some DC in a region to the east of the LDO region. 3° × 3° resolution. A GFDL-type OGCM with the KPP model (everything else being the same) does not predict DC in the LDO region where the vertical heat diffusivity is found to be 0.5 × 10 -4 m 2 s -1 which is the background value. The KPP model yields DC only to the east of the LDO region. 1° × 1° resolution. In this case, a MY2.5 mixing scheme predicts DC in the LDO region. However, it also predicts DC to the west, north and south of it, where it is not observed. The behavior of the KPP and MY models are somewhat anti-symmetric. The MY models yield too low a mixing in stably stratified flows since they

  11. Deep space network energy program

    NASA Technical Reports Server (NTRS)

    Friesema, S. E.

    1980-01-01

    If the Deep Space Network is to exist in a cost effective and reliable manner in the next decade, the problems presented by international energy cost increases and energy availability must be addressed. The Deep Space Network Energy Program was established to implement solutions compatible with the ongoing development of the total network.

  12. Context and Deep Learning Design

    ERIC Educational Resources Information Center

    Boyle, Tom; Ravenscroft, Andrew

    2012-01-01

    Conceptual clarification is essential if we are to establish a stable and deep discipline of technology enhanced learning. The technology is alluring; this can distract from deep design in a surface rush to exploit the affordances of the new technology. We need a basis for design, and a conceptual unit of organization, that are applicable across…

  13. Context and Deep Learning Design

    ERIC Educational Resources Information Center

    Boyle, Tom; Ravenscroft, Andrew

    2012-01-01

    Conceptual clarification is essential if we are to establish a stable and deep discipline of technology enhanced learning. The technology is alluring; this can distract from deep design in a surface rush to exploit the affordances of the new technology. We need a basis for design, and a conceptual unit of organization, that are applicable across…

  14. Deep Ecology: Beyond Mere Environmentalism.

    ERIC Educational Resources Information Center

    Weber, Suzanne

    1994-01-01

    Outlines the principles of deep ecology, a movement that questions the societal values that have resulted in damage to the earth's life-supporting biosphere. In contrast to shallow reform, deep ecology encourages individuals to examine their values and relationship to nature to address the environmental crisis. (LP)

  15. The Capodimonte Deep Field

    NASA Astrophysics Data System (ADS)

    2001-04-01

    A Window towards the Distant Universe Summary The Osservatorio Astronomico Capodimonte Deep Field (OACDF) is a multi-colour imaging survey project that is opening a new window towards the distant universe. It is conducted with the ESO Wide Field Imager (WFI) , a 67-million pixel advanced camera attached to the MPG/ESO 2.2-m telescope at the La Silla Observatory (Chile). As a pilot project at the Osservatorio Astronomico di Capodimonte (OAC) [1], the OACDF aims at providing a large photometric database for deep extragalactic studies, with important by-products for galactic and planetary research. Moreover, it also serves to gather experience in the proper and efficient handling of very large data sets, preparing for the arrival of the VLT Survey Telescope (VST) with the 1 x 1 degree 2 OmegaCam facility. PR Photo 15a/01 : Colour composite of the OACDF2 field . PR Photo 15b/01 : Interacting galaxies in the OACDF2 field. PR Photo 15c/01 : Spiral galaxy and nebulous object in the OACDF2 field. PR Photo 15d/01 : A galaxy cluster in the OACDF2 field. PR Photo 15e/01 : Another galaxy cluster in the OACDF2 field. PR Photo 15f/01 : An elliptical galaxy in the OACDF2 field. The Capodimonte Deep Field ESO PR Photo 15a/01 ESO PR Photo 15a/01 [Preview - JPEG: 400 x 426 pix - 73k] [Normal - JPEG: 800 x 851 pix - 736k] [Hi-Res - JPEG: 3000 x 3190 pix - 7.3M] Caption : This three-colour image of about 1/4 of the Capodimonte Deep Field (OACDF) was obtained with the Wide-Field Imager (WFI) on the MPG/ESO 2.2-m telescope at the la Silla Observatory. It covers "OACDF Subfield no. 2 (OACDF2)" with an area of about 35 x 32 arcmin 2 (about the size of the full moon), and it is one of the "deepest" wide-field images ever obtained. Technical information about this photo is available below. With the comparatively few large telescopes available in the world, it is not possible to study the Universe to its outmost limits in all directions. Instead, astronomers try to obtain the most detailed

  16. Deep sulfur cycle

    NASA Astrophysics Data System (ADS)

    Shimizu, N.; Mandeville, C. W.

    2009-12-01

    Geochemical cycle of sulfur in near-surface reservoirs has been a subject of intense studies for decades. It has been shown that sulfur isotopic compositions of sedimentary sulfides and sulfates record interactions of the atmosphere, hydrosphere, biosphere and lithosphere, with δ34S of sedimentary sulfides continuously decreasing from 0‰ toward present-day values of ~-30 to -40‰ over the Phanerozoic (e.g., Canfield, 2004). It has also been shown that microbial reduction of the present-day seawater sulfate (δ34S=+21‰) results in large shifts in isotopic compositions of secondary pyrites in altered oceanic crust (to δ34S=-70‰: Rouxel et al., 2009). How much of these near surface isotopic variations survive during deep geochemical cycle of sulfur interacting with the mantle infinite reservoir with δ34S=0‰? Could extent of their survival be used as a tracer of processes and dynamics involved in deep geochemical cycle? As a first step toward answering these questions, δ34S was determined in-situ using a Cameca IMS 1280 ion microprobe at Woods Hole Oceanographic Institution in materials representing various domains of deep geochemical cycle. They include pyrites in altered MORB as potential subducting materials and pyrites in UHP eclogites as samples that have experienced subduction zone processes, and mantle-derived melts are represented by olivine-hosted melt inclusions in MORB and those in IAB, and undegassed submarine OIB glasses. Salient features of the results include: (1) pyrites in altered MORB (with O. Rouxel; from ODP site 801 and ODP Hole 1301B) range from -70 to +19‰, (2) pyrites in UHP eclogites from the Western Gneiss Region, Norway (with B. Hacker and A. Kylander-Clark) show a limited overall range from -3.4 to + 2.8‰ among five samples, with one of them covering almost the entire range, indicating limited scale lengths of isotopic equilibration during subduction, (3) olivine-hosted melt inclusions in arc basalts from Galunggung (-2

  17. Deep Space Test Bed

    NASA Technical Reports Server (NTRS)

    Milton, Martha E.; Christl, Mark

    2004-01-01

    The DSTB Facility provides a new capability for the National Aeronautics and Space Administration s (NASA s) Space Radiation Shielding Project (SRSP). The objective of the DSTB is to provide a platform to conduct radiation shielding investigations in an environment more similar to deep space than most Low Earth orbits or is achievable at a particle accelerator. The DSTB provides a means to experimentally test radiation shielding effectiveness of various materials and to test the accuracy of radiation transport code predictions in the deep space cosmic ray environment more frequently and at a lower cost compared to space flight missions. New spectrometers, dosimeters and other techniques may be exercised and verified using the DSTB before space flight. The DSTB will be implemented through NASA s National Scientific Balloon Facility (NSBF) which provides polar balloon flights that lift science payloads to high altitude (120,000 A. (36.58km)) to escape much of the shielding effects of the Earth s atmosphere and magnetosphere. Polar flights are conducted through NSBF in coordination with the United States Polar Program. The DSTB will be launched on a Long Duration Balloon (LDB) from McMurdo, Antarctica (77.86 degrees south latitude) for circumpolar flights, nominally 20 days, traveling to the west and typically bounded between 73 to 82 degrees south latitude. Float altitudes for these balloons with payload are 115,000 to 130,000 feet (35.05 to 39.62km). The DSTB will be able to accommodate up to 20 investigations per flight. Annual flight opportunities are planned starting in December 2005. Balloon campaigns in Antarctica occur in December and January during the Austral summer. Since a key goal of the DSTB facility is to efficiently serve the varied needs of the radiation shielding community; it must be designed with a flexible architecture. By implementing the DSTB facility with NASA s balloon program, which operates under reduced formalities compared to space flight

  18. Deep Learning the Universe

    NASA Astrophysics Data System (ADS)

    Singh, Shiwangi; Bard, Deborah

    2017-01-01

    Weak gravitational lensing is an effective tool to map the structure of matter in the universe, and has been used for more than ten years as a probe of the nature of dark energy. Beyond the well-established two-point summary statistics, attention is now turning to methods that use the full statistical information available in the lensing observables, through analysis of the reconstructed shear field. This offers an opportunity to take advantage of powerful deep learning methods for image analysis. We present two early studies that demonstrate that deep learning can be used to characterise features in weak lensing convergence maps, and to identify the underlying cosmological model that produced them.We developed an unsupervised Denoising Convolutional Autoencoder model in order to learn an abstract representation directly from our data. This model uses a convolution-deconvolution architecture, which is fed with input data (corrupted with binomial noise to prevent over-fitting). Our model effectively trains itself to minimize the mean-squared error between the input and the output using gradient descent, resulting in a model which, theoretically, is broad enough to tackle other similarly structured problems. Using this model we were able to successfully reconstruct simulated convergence maps and identify the structures in them. We also determined which structures had the highest “importance” - i.e. which structures were most typical of the data. We note that the structures that had the highest importance in our reconstruction were around high mass concentrations, but were highly non-Gaussian.We also developed a supervised Convolutional Neural Network (CNN) for classification of weak lensing convergence maps from two different simulated theoretical models. The CNN uses a softmax classifier which minimizes a binary cross-entropy loss between the estimated distribution and true distribution. In other words, given an unseen convergence map the trained CNN determines

  19. Etude experimentale de la photoexcitation des colorants de type anthracene, azobenzene et thioindigo dans des matrices de cristaux liquides nematiques et smectiques

    NASA Astrophysics Data System (ADS)

    Saad, Bendaoud

    Nous avons étudié le comportement de différents colorants (tétracène et azobenzènes AZD3, DR1 et D2) dans des matrices de cristaux liquides (E7 et 5CB). Les résultats obtenus ont montré que la réorientation optique des molécules de cristaux liquides se produit à des intensités extrêmement faibles (~1 μW/cm 2). Nous avons attribué cet effet à l'interaction entre les molécules des colorants photoexcitées et celles des cristaux liquides hôtes. Ces interactions se produisent lorsque les molécules dichroïques exçitées transitent entre des états triplets intermédiaires tout en conduisant à la génération d'un nouveau moment optique géant, responsable de la réorientation des molécules. Le changement de la forme de la molécule du colorant, dû à l'isomérisation Trans-Cis , est à l'origine de la création de ce moment. Ce qui distingue notre réorientation moléculaire de celle obtenue sur d'autres systèmes hôtes-dopants est que les molécules sont repoussées du champ électrique de la lumière. Par ailleurs, cette réorientation est accompagnée d'une diffusion anisotrope des molécules excitées. Nous avons aussi étudié le cristal liquide PhBz rendu ferroélectrique en le dopant par des molécules thioindigos. En exploitant l'augmentation de la polarisation spontanée due à la photoisomérisation du colorant, nous avons pu réaliser un hologramme dynamique contrôlable par un champ optique assisté par une tension statique.

  20. Spin Polarization of Rb and Cs np ^{2}P_{3/2} (n=5, 6) Atoms by Circularly Polarized Photoexcitation of a Transient Diatomic Molecule.

    PubMed

    Mironov, A E; Hewitt, J D; Eden, J G

    2017-03-17

    We report the selective population of Rb or Cs np ^{2}P_{3/2} (n=5, 6; F=4, 5) hyperfine states by the photodissociation of a transient, alkali-rare gas diatomic molecule. Circularly polarized (σ^{-}), amplified spontaneous emission (ASE) on the D_{2} line of Rb or Cs (780.0 and 852.1 nm, respectively) is generated when Rb-Xe or Cs-Xe ground state collision pairs are photoexcited by a σ^{+}-polarized optical field having a wavelength within the D_{2} blue satellite continuum, associated with the B^{2}Σ_{1/2}^{+}←X^{2}Σ_{1/2}^{+} (free←free) transition of the diatomic molecule. The degree of spin polarization of Cs (6p ^{2}P_{3/2}), specifically, is found to be dependent on the interatomic distance (R) at which the excited complex is born, a result attributed to the structure of the B^{2}Σ_{1/2}^{+} state. For Cs-Xe atomic pairs, tuning the wavelength of the optical field from 843 to 848 nm varies the degree of circular polarization of the ASE from 63% to almost unity because of the perturbation, in the 5≤R≤6  Å interval, of the ^{2}Σ_{1/2}^{+} potential by a dσ molecular orbital associated with a higher ^{2}Λ electronic state. Monitoring only the Cs 6p ^{2}P_{3/2} spin polarization reveals a previously unobserved interaction of CsXe (B^{2}Σ_{1/2}^{+}) with the lowest vibrational levels of a ^{2}Λ state derived from Cs (5d)+Xe. By inserting a molecular intermediate into the alkali atom excitation mechanism, these experiments realize electronic spin polarization through populating no more than two np ^{2}P_{3/2} hyperfine states, and demonstrate a sensitive spectroscopic probe of R-dependent state-state interactions and their impact on interatomic potentials.

  1. Deep inelastic phenomena

    SciTech Connect

    Prescott, C.Y.

    1980-10-01

    Nucleon structure as seen in the context of deep inelastic scattering is discussed. The lectures begin with consideration of the quark-parton model. The model forms the basis of understanding lepton-nucleon inelastic scattering. As improved data in lepton-nucleon scattering at high energies became available, the quark-parton model failed to explain some crucial features of these data. At approximately the same time a candidate theory of strong interactions based on a SU(3) gauge theory of color was being discussed in the literature, and new ideas on the explanation of inelastic scattering data became popular. A new theory of strong interactions, now called quantum chromodynamics provides a new framework for understanding the data, with a much stronger theoretical foundation, and seems to explain well the features of the data. The lectures conclude with a look at some recent experiments which provide new data at very high energies. These lectures are concerned primarily with charged lepton inelastic scattering and to a lesser extent with neutrino results. Furthermore, due to time and space limitations, topics such as final state hadron studies, and multi-muon production are omitted here. The lectures concentrate on the more central issues: the quark-parton model and concepts of scaling, scale breaking and the ideas of quantum chromodynamics, the Q/sup 2/ dependence of structure function, moments, and the important parameter R.

  2. Operation Deep Sweep

    NASA Astrophysics Data System (ADS)

    Bell, Peter M.

    Fifty scientists and a crew of 18 have embarked on a 64,000 km odyssey to explore the Pacific from pole to pole—the most ambitious program in the history of the marine geology branch of the U.S. Geological Survey (USGS). Called Operation Deep Sweep, the 1-year cruise will search areas above the Arctic Circle, off of Alaska, to McMurdo Sound in Antarctica. The 63-m, 1,300-tonne research vessel Samuel P. Lee sailed from its home port of Redwood City, Calif., to San Francisco to begin the first leg of the lengthy journey.According to USGS officials and the cosponsoring Circum-Pacific Council for Energy and Mineral Resources of the American Association of Petroleum Geologists, the cruise will ultimately involve 150 scientists, some of them representing Germany, France, Australia, and New Zealand. David Howell, branch chief of Pacific Marine Geology for the USGS, said the voyage of the Lee was “the most far reaching and of the longest duration” ever attempted by his unit. He said the cruise would string together a large number of scientific experiments spanning the Pacific. Howell likened the voyage to the Lewis and Clark Expedition of 1803-1806 (which explored Louisiana and the western United States) because “we're going into unknown territory and into regions not studied except in the most cursory manner.”

  3. Deep atomic force microscopy

    SciTech Connect

    Barnard, H.; Drake, B.; Randall, C.; Hansma, P. K.

    2013-12-15

    The Atomic Force Microscope (AFM) possesses several desirable imaging features including the ability to produce height profiles as well as two-dimensional images, in fluid or air, at high resolution. AFM has been used to study a vast selection of samples on the scale of angstroms to micrometers. However, current AFMs cannot access samples with vertical topography of the order of 100 μm or greater. Research efforts have produced AFM scanners capable of vertical motion greater than 100 μm, but commercially available probe tip lengths are still typically less than 10 μm high. Even the longest probe tips are below 100 μm and even at this range are problematic. In this paper, we present a method to hand-fabricate “Deep AFM” probes with tips of the order of 100 μm and longer so that AFM can be used to image samples with large scale vertical topography, such as fractured bone samples.

  4. Conservation of deep pelagic biodiversity.

    PubMed

    Robison, Bruce H

    2009-08-01

    The deep ocean is home to the largest ecosystems on our planet. This vast realm contains what may be the greatest number of animal species, the greatest biomass, and the greatest number of individual organisms in the living world. Humans have explored the deep ocean for about 150 years, and most of what is known is based on studies of the deep seafloor. In contrast, the water column above the deep seabed comprises more than 90% of the living space, yet less than 1% of this biome has been explored. The deep pelagic biota is the largest and least-known major faunal group on Earth despite its obvious importance at the global scale. Pelagic species represent an incomparable reservoir of biodiversity. Although we have yet to discover and describe the majority of these species, the threats to their continued existence are numerous and growing. Conserving deep pelagic biodiversity is a problem of global proportions that has never been addressed comprehensively. The potential effects of these threats include the extensive restructuring of entire ecosystems, changes in the geographical ranges of many species, large-scale elimination of taxa, and a decline in biodiversity at all scales. This review provides an initial framework of threat assessment for confronting the challenge of conserving deep pelagic biodiversity; and it outlines the need for baseline surveys and protected areas as preliminary policy goals.

  5. Deep learning for computational chemistry.

    PubMed

    Goh, Garrett B; Hodas, Nathan O; Vishnu, Abhinav

    2017-06-15

    The rise and fall of artificial neural networks is well documented in the scientific literature of both computer science and computational chemistry. Yet almost two decades later, we are now seeing a resurgence of interest in deep learning, a machine learning algorithm based on multilayer neural networks. Within the last few years, we have seen the transformative impact of deep learning in many domains, particularly in speech recognition and computer vision, to the extent that the majority of expert practitioners in those field are now regularly eschewing prior established models in favor of deep learning models. In this review, we provide an introductory overview into the theory of deep neural networks and their unique properties that distinguish them from traditional machine learning algorithms used in cheminformatics. By providing an overview of the variety of emerging applications of deep neural networks, we highlight its ubiquity and broad applicability to a wide range of challenges in the field, including quantitative structure activity relationship, virtual screening, protein structure prediction, quantum chemistry, materials design, and property prediction. In reviewing the performance of deep neural networks, we observed a consistent outperformance against non-neural networks state-of-the-art models across disparate research topics, and deep neural network-based models often exceeded the "glass ceiling" expectations of their respective tasks. Coupled with the maturity of GPU-accelerated computing for training deep neural networks and the exponential growth of chemical data on which to train these networks on, we anticipate that deep learning algorithms will be a valuable tool for computational chemistry. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  6. Microbial Life in the Deep Subsurface: Deep, Hot and Radioactive

    NASA Technical Reports Server (NTRS)

    DeStefano, Andrea L.; Ford, Jill C.; Winsor, Seana K.; Allen, Carlton C.; Miller, Judith; McNamara, Karen M.; Gibson, Everett K., Jr.

    2000-01-01

    Recent studies, motivated in part by the search for extraterrestrial life, continue to expand the recognized limits of Earth's biosphere. This work explored evidence for life a high-temperature, radioactive environment in the deep subsurface.

  7. Microbial Life in the Deep Subsurface: Deep, Hot and Radioactive

    NASA Technical Reports Server (NTRS)

    DeStefano, Andrea L.; Ford, Jill C.; Winsor, Seana K.; Allen, Carlton C.; Miller, Judith; McNamara, Karen M.; Gibson, Everett K., Jr.

    2000-01-01

    Recent studies, motivated in part by the search for extraterrestrial life, continue to expand the recognized limits of Earth's biosphere. This work explored evidence for life a high-temperature, radioactive environment in the deep subsurface.

  8. Deep Learning in Drug Discovery.

    PubMed

    Gawehn, Erik; Hiss, Jan A; Schneider, Gisbert

    2016-01-01

    Artificial neural networks had their first heyday in molecular informatics and drug discovery approximately two decades ago. Currently, we are witnessing renewed interest in adapting advanced neural network architectures for pharmaceutical research by borrowing from the field of "deep learning". Compared with some of the other life sciences, their application in drug discovery is still limited. Here, we provide an overview of this emerging field of molecular informatics, present the basic concepts of prominent deep learning methods and offer motivation to explore these techniques for their usefulness in computer-assisted drug discovery and design. We specifically emphasize deep neural networks, restricted Boltzmann machine networks and convolutional networks.

  9. Deep UV LEDs

    NASA Astrophysics Data System (ADS)

    Han, Jung; Amano, Hiroshi; Schowalter, Leo

    2014-06-01

    Deep ultraviolet (DUV) photons interact strongly with a broad range of chemical and biological molecules; compact DUV light sources could enable a wide range of applications in chemi/bio-sensing, sterilization, agriculture, and industrial curing. The much shorter wavelength also results in useful characteristics related to optical diffraction (for lithography) and scattering (non-line-of-sight communication). The family of III-N (AlGaInN) compound semiconductors offers a tunable energy gap from infrared to DUV. While InGaN-based blue light emitters have been the primary focus for the obvious application of solid state lighting, there is a growing interest in the development of efficient UV and DUV light-emitting devices. In the past few years we have witnessed an increasing investment from both government and industry sectors to further the state of DUV light-emitting devices. The contributions in Semiconductor Science and Technology 's special issue on DUV devices provide an up-to-date snapshot covering many relevant topics in this field. Given the expected importance of bulk AlN substrate in DUV technology, we are pleased to include a review article by Hartmann et al on the growth of AlN bulk crystal by physical vapour transport. The issue of polarization field within the deep ultraviolet LEDs is examined in the article by Braut et al. Several commercial companies provide useful updates in their development of DUV emitters, including Nichia (Fujioka et al ), Nitride Semiconductors (Muramoto et al ) and Sensor Electronic Technology (Shatalov et al ). We believe these articles will provide an excellent overview of the state of technology. The growth of AlGaN heterostructures by molecular beam epitaxy, in contrast to the common organo-metallic vapour phase epitaxy, is discussed by Ivanov et al. Since hexagonal boron nitride (BN) has received much attention as both a UV and a two-dimensional electronic material, we believe it serves readers well to include the

  10. Jack Dymond's Deep Insights

    NASA Astrophysics Data System (ADS)

    Thomson, R. E.; Delaney, J. R.

    2004-12-01

    Most people do not know that Jack Dymond was a major influence on several aspects of current deep-sea research. Along with Margaret Leinen and Jack, we were part of the first Alvin dive program on the Endeavour hydrothermal field in 1984. Jack was working with Rick, on a sediment-trap study of the overall carbon fluxes in the vicinity of the Endeavour hydrothermal systems in an effort to address a question that Cindy Lee had posed about the overall carbon production from hydrothermal vents. At the time we were recognizing and naming many of the 20- to 40-meter-high sulfide structures in the Endeavour field (Hulk, Grotto, Dante, Dudley, Bastille), Jack commented that it was a shame that the world could not see these magnificent edifices or watch endlessly awesome black smokers. His feeling was that some vent sites should be converted to National Parks to preserve them from invasion by enthusiastic scientists, yet he clearly had the vision that the public should be given a sense of the grandeur involved locally, as well as the vastness of the 70,000-km ridge-crest system running through every ocean. Within a year we started talking about the RIDGE Program, and Jack was an early and enthusiastic participant in the design and development of RIDGE. Jack was among the first to encourage multi-disciplinary research at the hydrothermal vent sites. Recognizing that deep currents are important to vent processes, he urged physical oceanographers to work with the chemists, biologists, and geologists and was personally responsible for Rick becoming interested in studying vents. We, the co-authors of this abstract, became close friends as a result of having been introduced to each other by Jack. Several years ago, we co-authored the first paper ever written on the possible influence of hydrothermal activity on the circulation of the Europan Ocean, a paper that we here dedicate to the memory of Jack. Finally, it was in part because of Jack's conviction that the world should know

  11. DeepPep: Deep proteome inference from peptide profiles

    PubMed Central

    2017-01-01

    Protein inference, the identification of the protein set that is the origin of a given peptide profile, is a fundamental challenge in proteomics. We present DeepPep, a deep-convolutional neural network framework that predicts the protein set from a proteomics mixture, given the sequence universe of possible proteins and a target peptide profile. In its core, DeepPep quantifies the change in probabilistic score of peptide-spectrum matches in the presence or absence of a specific protein, hence selecting as candidate proteins with the largest impact to the peptide profile. Application of the method across datasets argues for its competitive predictive ability (AUC of 0.80±0.18, AUPR of 0.84±0.28) in inferring proteins without need of peptide detectability on which the most competitive methods rely. We find that the convolutional neural network architecture outperforms the traditional artificial neural network architectures without convolution layers in protein inference. We expect that similar deep learning architectures that allow learning nonlinear patterns can be further extended to problems in metagenome profiling and cell type inference. The source code of DeepPep and the benchmark datasets used in this study are available at https://deeppep.github.io/DeepPep/. PMID:28873403

  12. The Deep Space Network, volume 17

    NASA Technical Reports Server (NTRS)

    1973-01-01

    The objectives, functions, and organization of the Deep Space Network are summarized. The Deep Space Instrumentation Facility, the Ground Communications Facility, and the Network Control System are described.

  13. Deep Impact on Its Way

    NASA Image and Video Library

    2005-01-18

    The high speed of NASA Deep Impact spacecraft causes it to appear as a long streak across the sky in the constellation Virgo during the 10-minute exposure time of this photograph taken by Mr. Palomar 200-inch telescope.

  14. Deep Space Telecommunications Systems Engineering

    NASA Technical Reports Server (NTRS)

    Yuen, J. H. (Editor)

    1982-01-01

    Descriptive and analytical information useful for the optimal design, specification, and performance evaluation of deep space telecommunications systems is presented. Telemetry, tracking, and command systems, receiver design, spacecraft antennas, frequency selection, interference, and modulation techniques are addressed.

  15. NEW APPROACHES: Deep inelastic scattering

    NASA Astrophysics Data System (ADS)

    Allday, J.

    1998-01-01

    Feynman diagrams can be used to explain deep inelastic scattering, but it must be remembered that the emission and absorption of a photon are not independent events - the underlying field is important.

  16. What Is Deep Vein Thrombosis?

    MedlinePlus

    ... deep vein of the leg can break off, travel to the lungs, and block blood flow. Rate This Content: NEXT >> Updated: October 28, 2011 Twitter Facebook YouTube Google+ SITE INDEX ACCESSIBILITY PRIVACY STATEMENT FOIA NO FEAR ACT ...

  17. Goldstone Deep Space Communication Complex

    NASA Technical Reports Server (NTRS)

    1990-01-01

    Three 34m (110 ft.) diameter Beam Waveguide antennas located at the Goldstone Deep Space Communications Complex, situated in the Mojave Desert in California. This is one of three complexes which comprise NASA's Deep Space Network (DSN). The DSN provides radio communications for all of NASA's interplanetary spacecraft and is also utilized for radio astronomy and radar observations of the solar system and the universe.

  18. Hot, deep origin of petroleum: deep basin evidence and application

    USGS Publications Warehouse

    Price, Leigh C.

    1978-01-01

    Use of the model of a hot deep origin of oil places rigid constraints on the migration and entrapment of crude oil. Specifically, oil originating from depth migrates vertically up faults and is emplaced in traps at shallower depths. Review of petroleum-producing basins worldwide shows oil occurrence in these basins conforms to the restraints of and therefore supports the hypothesis. Most of the world's oil is found in the very deepest sedimentary basins, and production over or adjacent to the deep basin is cut by or directly updip from faults dipping into the basin deep. Generally the greater the fault throw the greater the reserves. Fault-block highs next to deep sedimentary troughs are the best target areas by the present concept. Traps along major basin-forming faults are quite prospective. The structural style of a basin governs the distribution, types, and amounts of hydrocarbons expected and hence the exploration strategy. Production in delta depocenters (Niger) is in structures cut by or updip from major growth faults, and structures not associated with such faults are barren. Production in block fault basins is on horsts next to deep sedimentary troughs (Sirte, North Sea). In basins whose sediment thickness, structure and geologic history are known to a moderate degree, the main oil occurrences can be specifically predicted by analysis of fault systems and possible hydrocarbon migration routes. Use of the concept permits the identification of significant targets which have either been downgraded or ignored in the past, such as production in or just updip from thrust belts, stratigraphic traps over the deep basin associated with major faulting, production over the basin deep, and regional stratigraphic trapping updip from established production along major fault zones.

  19. Sulfur mass-independent fractionation during photolysis and photoexcitation of SO2 and CS2 and implications to the source reactions for Archean sulfur isotope anomaly

    NASA Astrophysics Data System (ADS)

    Ono, S.; Whitehill, A. R.; Oduro, H. D.

    2012-12-01

    produces large positive anomaly in both Δ33S and Δ36S (up to 100 ‰) even in optically thin conditions, suggesting quantum dynamic origin of the S-MIF. Brown polymer material produced under photolysis and photoexciation of CS2 also yield S-MIF but isotope patterns are different from those of SO2 photochemistry and different from Archean pattern. If SO2 photolysis and photoexcitation are the main source of Archean S-MIF, the different Δ36S/Δ33S values can be linked to the different magnitude of contributions from SO2 photolysis and photoexciation. For example, increased contribution of photoexciation band is expected under a thick organic haze layer that attenuates high energy UV and chemically traps excited state SO2.

  20. FORT UNION DEEP

    SciTech Connect

    Lyle A. Johnson Jr.

    2002-03-01

    Coalbed methane (CBM) is currently the hottest area of energy development in the Rocky Mountain area. The Powder River Basin (PRB) is the largest CBM area in Wyoming and has attracted the majority of the attention because of its high permeability and relatively shallow depth. Other Wyoming coal regions are also being targeted for development, but most of these areas have lower permeability and deeper coal seams. This project consists of the development of a CBM stimulation system for deep coal resources and involves three work areas: (1) Well Placement, (2) Well Stimulation, and (3) Production Monitoring and Evaluation. The focus of this project is the Washakie Basin. Timberline Energy, Inc., the cosponsor, has a project area in southern Carbon County, Wyoming, and northern Moffat County, Colorado. The target coal is found near the top of the lower Fort Union formation. The well for this project, Evans No.1, was drilled to a depth of 2,700 ft. Three coal seams were encountered with sandstone and some interbedded shale between seams. Well logs indicated that the coal seams and the sandstone contained gas. For the testing, the upper seam at 2,000 ft was selected. The well, drilled and completed for this project, produced very little water and only occasional burps of methane. To enhance the well, a mild severity fracture was conducted to fracture the coal seam and not the adjacent sandstone. Fracturing data indicated a fracture half-length of 34 ft, a coal permeability of 0.2226 md, and permeability of 15.3 md. Following fracturing, the gas production rate stabilized at 10 Mscf/day within water production of 18 bpd. The Western Research Institute (WRI) CBM model was used to design a 14-day stimulation cycle followed by a 30-day production period. A maximum injection pressure of 1,200 psig to remain well below the fracture pressure was selected. Model predictions were 20 Mscf/day of air injection for 14 days, a one-day shut-in, then flowback. The predicted flowback

  1. FORT UNION DEEP

    SciTech Connect

    Lyle A. Johnson Jr.

    2002-09-01

    Coalbed methane (CBM) is currently the hottest area of energy development in the Rocky Mountain area. The Powder River Basin (PRB) is the largest CBM area in Wyoming and has attracted the majority of the attention because of its high permeability and relatively shallow depth. Other Wyoming coal regions are also being targeted for development, but most of these areas have lower permeability and deeper coal seams. This project consists of the development of a CBM stimulation system for deep coal resources and involves three work areas: (1) Well Placement, (2) Well Stimulation, and (3) Production Monitoring and Evaluation. The focus of this project is the Washakie Basin. Timberline Energy, Inc., the cosponsor, has a project area in southern Carbon County, Wyoming, and northern Moffat County, Colorado. The target coal is found near the top of the lower Fort Union formation. The well for this project, Evans No.1, was drilled to a depth of 2,700 ft. Three coal seams were encountered with sandstone and some interbedded shale between seams. Well logs indicated that the coal seams and the sandstone contained gas. For the testing, the upper seam at 2,000 ft was selected. The well, drilled and completed for this project, produced very little water and only occasional burps of methane. To enhance the well, a mild severity fracture was conducted to fracture the coal seam and not the adjacent sandstone. Fracturing data indicated a fracture half-length of 34 ft, a coal permeability of 0.2226 md, and permeability of 15.3 md. Following fracturing, the gas production rate stabilized at 10 Mscf/day within water production of 18 bpd. The Western Research Institute (WRI) CBM model was used to design a 14-day stimulation cycle followed by a 30-day production period. A maximum injection pressure of 1,200 psig to remain well below the fracture pressure was selected. Model predictions were 20 Mscf/day of air injection for 14 days, a one-day shut-in, then flowback. The predicted flowback

  2. Making sense of deep sequencing.

    PubMed

    Goldman, D; Domschke, K

    2014-10-01

    This review, the first of an occasional series, tries to make sense of the concepts and uses of deep sequencing of polynucleic acids (DNA and RNA). Deep sequencing, synonymous with next-generation sequencing, high-throughput sequencing and massively parallel sequencing, includes whole genome sequencing but is more often and diversely applied to specific parts of the genome captured in different ways, for example the highly expressed portion of the genome known as the exome and portions of the genome that are epigenetically marked either by DNA methylation, the binding of proteins including histones, or that are in different configurations and thus more or less accessible to enzymes that cleave DNA. Deep sequencing of RNA (RNASeq) reverse-transcribed to complementary DNA is invaluable for measuring RNA expression and detecting changes in RNA structure. Important concepts in deep sequencing include the length and depth of sequence reads, mapping and assembly of reads, sequencing error, haplotypes, and the propensity of deep sequencing, as with other types of 'big data', to generate large numbers of errors, requiring monitoring for methodologic biases and strategies for replication and validation. Deep sequencing yields a unique genetic fingerprint that can be used to identify a person, and a trove of predictors of genetic medical diseases. Deep sequencing to identify epigenetic events including changes in DNA methylation and RNA expression can reveal the history and impact of environmental exposures. Because of the power of sequencing to identify and deliver biomedically significant information about a person and their blood relatives, it creates ethical dilemmas and practical challenges in research and clinical care, for example the decision and procedures to report incidental findings that will increasingly and frequently be discovered.

  3. A Deep ALMA Image of the Hubble Ultra Deep Field

    NASA Astrophysics Data System (ADS)

    Dunlop, J. S.

    2016-12-01

    Although primarily designed as a high-resolution imaging spectrometer at submillimetre/millimetre wavelengths, the Atacama Large Millimeter/submillimeter Array (ALMA) has a vital role to play in producing the key deep, unconfused, submillimetre/millimetre continuum surveys required to bridge the current gap in our understanding of visible and dust-obscured star formation in the young Universe. The first such survey has now been completed, comprising a mosaic of 45 ALMA pointings at a wavelength of 1.3 mm, covering the Hubble Ultra Deep Field (HUDF). This deep, homogeneous ALMA survey, combined with the wealth of existing data in the HUDF, has already provided new clarity on the nature of dusty star-forming galaxies, and the relative evolution of dust-obscured and unobscured star formation over cosmic time.

  4. Deep RNNs for video denoising

    NASA Astrophysics Data System (ADS)

    Chen, Xinyuan; Song, Li; Yang, Xiaokang

    2016-09-01

    Video denoising can be described as the problem of mapping from a specific length of noisy frames to clean one. We propose a deep architecture based on Recurrent Neural Network (RNN) for video denoising. The model learns a patch-based end-to-end mapping between the clean and noisy video sequences. It takes the corrupted video sequences as the input and outputs the clean one. Our deep network, which we refer to as deep Recurrent Neural Networks (deep RNNs or DRNNs), stacks RNN layers where each layer receives the hidden state of the previous layer as input. Experiment shows (i) the recurrent architecture through temporal domain extracts motion information and does favor to video denoising, and (ii) deep architecture have large enough capacity for expressing mapping relation between corrupted videos as input and clean videos as output, furthermore, (iii) the model has generality to learned different mappings from videos corrupted by different types of noise (e.g., Poisson-Gaussian noise). By training on large video databases, we are able to compete with some existing video denoising methods.

  5. Deep Learning and Bayesian Methods

    NASA Astrophysics Data System (ADS)

    Prosper, Harrison B.

    2017-03-01

    A revolution is underway in which deep neural networks are routinely used to solve diffcult problems such as face recognition and natural language understanding. Particle physicists have taken notice and have started to deploy these methods, achieving results that suggest a potentially significant shift in how data might be analyzed in the not too distant future. We discuss a few recent developments in the application of deep neural networks and then indulge in speculation about how such methods might be used to automate certain aspects of data analysis in particle physics. Next, the connection to Bayesian methods is discussed and the paper ends with thoughts on a significant practical issue, namely, how, from a Bayesian perspective, one might optimize the construction of deep neural networks.

  6. Deep space optical communications experiment

    NASA Technical Reports Server (NTRS)

    Kinman, P.; Katz, J.; Gagliardi, R.

    1983-01-01

    An optical communications experiment between a deep space vehicle and an earth terminal is under consideration for later in this decade. The experimental link would be incoherent (direct detection) and would employ two-way cooperative pointing. The deep space optical transceiver would ride piggyback on a spacecraft with an independent scientific objective. Thus, this optical transceiver is being designed for minimum spacecraft impact - specifically, low mass and low power. The choices of laser transmitter, coding/modulation scheme, and pointing mechanization are discussed. A representative telemetry link budget is presented.

  7. Deep Impact Network Experiment (DINET)

    NASA Technical Reports Server (NTRS)

    Burleigh, Scott

    2008-01-01

    DINET is a technology development experiment intended to increase the technical readiness of JPL s implementation of DTN protocols - "ION". The objective is to advance ION in flight and ground SW to TRL 8, with code of sufficient quality that future flight projects can easily use it at low risk. DINET is to be implemented on the Deep Impact flyby spacecraft. DINET operations will be performed in late 2008 during the Deep Impact spacecraft team "stand down" after EPOCH operations and before the start of development for DIXI operations.

  8. Stimulation Technologies for Deep Well Completions

    SciTech Connect

    2003-09-30

    The Department of Energy (DOE) is sponsoring the Deep Trek Program targeted at improving the economics of drilling and completing deep gas wells. Under the DOE program, Pinnacle Technologies is conducting a study to evaluate the stimulation of deep wells. The objective of the project is to assess U.S. deep well drilling & stimulation activity, review rock mechanics & fracture growth in deep, high pressure/temperature wells and evaluate stimulation technology in several key deep plays. An assessment of historical deep gas well drilling activity and forecast of future trends was completed during the first six months of the project; this segment of the project was covered in Technical Project Report No. 1. The second progress report covers the next six months of the project during which efforts were primarily split between summarizing rock mechanics and fracture growth in deep reservoirs and contacting operators about case studies of deep gas well stimulation.

  9. STIMULATION TECHNOLOGIES FOR DEEP WELL COMPLETIONS

    SciTech Connect

    Stephen Wolhart

    2003-06-01

    The Department of Energy (DOE) is sponsoring a Deep Trek Program targeted at improving the economics of drilling and completing deep gas wells. Under the DOE program, Pinnacle Technologies is conducting a project to evaluate the stimulation of deep wells. The objective of the project is to assess U.S. deep well drilling & stimulation activity, review rock mechanics & fracture growth in deep, high pressure/temperature wells and evaluate stimulation technology in several key deep plays. Phase 1 was recently completed and consisted of assessing deep gas well drilling activity (1995-2007) and an industry survey on deep gas well stimulation practices by region. Of the 29,000 oil, gas and dry holes drilled in 2002, about 300 were drilled in the deep well; 25% were dry, 50% were high temperature/high pressure completions and 25% were simply deep completions. South Texas has about 30% of these wells, Oklahoma 20%, Gulf of Mexico Shelf 15% and the Gulf Coast about 15%. The Rockies represent only 2% of deep drilling. Of the 60 operators who drill deep and HTHP wells, the top 20 drill almost 80% of the wells. Six operators drill half the U.S. deep wells. Deep drilling peaked at 425 wells in 1998 and fell to 250 in 1999. Drilling is expected to rise through 2004 after which drilling should cycle down as overall drilling declines.

  10. A strategy to increase the efficiency of the dye-sensitized TiO2 solar cells operated by photoexcitation of dye-to-TiO2 charge-transfer bands.

    PubMed

    Tae, Eunju Lee; Lee, Seung Hwan; Lee, Jae Kwan; Yoo, Su San; Kang, Eun Ju; Yoon, Kyung Byung

    2005-12-01

    Dye-sensitized nanoporous TiO2 solar cells (DSSCs) can be classified into two types, namely, Type-I and Type-II. Type-I DSSCs are the DSSCs in which electrons are injected from the adsorbed dyes by photoexcitation of the dyes followed by electron injection from the excited dyes to TiO2 (pathway A). Type-II DSSCs are the DSSCs in which electrons are injected not only by pathway A but also by direct one-step electron injection from the dyes to TiO2 by photoexcitation of the dye-to-TiO2 charge-transfer (DTCT) bands (pathway B). The DSSCs employing catechol (Cat) or its derivatives as the sensitizers have been the typical examples of Type-II DSSCs. However, their solar energy-to-electricity conversion efficiencies (eta) have never exceeded 0.7%, and the external quantum efficiencies (EQE) at the absorption maximums of the DTCT bands have never exceeded 10%. We found that the attachment of electron-donating compounds such as (pyridin-4-yl)vinyl and (quinolin-4-yl)vinyl, respectively, to Cat (designated as Cat-v-P and Cat-v-Q, respectively) leads to 2- and 2.7-fold increases, respectively, in eta, driven by large increases in short circuit current (Jsc). The EQE increased from 8.5 to 30% at 400 nm upon changing from Cat to Cat-v-P, at which only the DTCT band absorbs. In the case of the Cat-v-Q-sensitized DSSC, even the eta obtained by exciting only the DTCT band was higher than 1%. Interestingly, the illumination of only the DTCT band resulted in the increase of fill factor from 62.6% to 72.3%. This paper provides for the first time an insight into the strategy to increase the eta values of Type-II DSSCs.

  11. C5′- and C3′-sugar radicals produced via photo-excitation of one-electron oxidized adenine in 2′-deoxyadenosine and its derivatives

    PubMed Central

    Adhikary, Amitava; Becker, David; Collins, Sean; Koppen, Jessica; Sevilla, Michael D.

    2006-01-01

    We report that photo-excitation of one-electron-oxidized adenine [A(-H)•] in dAdo and its 2′-deoxyribonucleotides leads to formation of deoxyribose sugar radicals in remarkably high yields. Illumination of A(-H)• in dAdo, 3′-dAMP and 5′-dAMP in aqueous glasses at 143 K leads to 80-100% conversion to sugar radicals at C5′ and C3′. The position of the phosphate in 5′- and 3′-dAMP is observed to deactivate radical formation at the site of substitution. In addition, the pH has a crucial influence on the site of sugar radical formation; e.g. at pH ∼5, photo-excitation of A(-H)• in dAdo at 143 K produces mainly C5′• whereas only C3′• is observed at high pH ∼12. 13C substitution at C5′ in dAdo yields 13C anisotropic couplings of (28, 28, 84) G whose isotropic component 46.7 G identifies formation of the near planar C5′•. A β-13C 16 G isotropic coupling from C3′• is also found. These results are found to be in accord with theoretically calculated 13C couplings at C5′ [DFT, B3LYP, 6-31(G) level] for C5′• and C3′•. Calculations using time-dependent density functional theory [TD-DFT B3LYP, 6-31G(d)] confirm that transitions in the near UV and visible induce hole transfer from the base radical to the sugar group leading to sugar radical formation. PMID:16537838

  12. Deep space telecommunication systems engineering

    NASA Technical Reports Server (NTRS)

    Yuen, J. H. (Editor)

    1983-01-01

    Descriptive and analytical information useful for the optimal design, specification, and performance evaluation of deep space telecommunications systems is presented. Telemetry, tracking, and command systems, receiver design, spacecraft antennas, frequency selection, interference, and modulation techniques are addressed. Previously announced in STAR as N83-22226

  13. Electrochemical Machining Removes Deep Obstructions

    NASA Technical Reports Server (NTRS)

    Catania, Mark J.

    1987-01-01

    Electrochemical machining (ECM) is effective way of removing obstructing material between two deep holes supposed to intersect but do not because of misalignment of drilling tools. ECM makes it possible to rework costly castings otherwise scrapped. Method fast even for tough or hard alloys and complicated three-dimensional shapes.

  14. Digging Deeper: The Deep Web.

    ERIC Educational Resources Information Center

    Turner, Laura

    2001-01-01

    Focuses on the Deep Web, defined as Web content in searchable databases of the type that can be found only by direct query. Discusses the problems of indexing; inability to find information not indexed in the search engine's database; and metasearch engines. Describes 10 sites created to access online databases or directly search them. Lists ways…

  15. Peering Deep into Jupiter Atmosphere

    NASA Image and Video Library

    2013-03-14

    The dark hot spot in this false-color image from NASA Cassini spacecraft is a window deep into Jupiter atmosphere. All around it are layers of higher clouds, with colors indicating which layer of the atmosphere the clouds are in.

  16. Digging Deeper: The Deep Web.

    ERIC Educational Resources Information Center

    Turner, Laura

    2001-01-01

    Focuses on the Deep Web, defined as Web content in searchable databases of the type that can be found only by direct query. Discusses the problems of indexing; inability to find information not indexed in the search engine's database; and metasearch engines. Describes 10 sites created to access online databases or directly search them. Lists ways…

  17. A Deep-Sea Simulation.

    ERIC Educational Resources Information Center

    Montes, Georgia E.

    1997-01-01

    Describes an activity that simulates exploration techniques used in deep-sea explorations and teaches students how this technology can be used to take a closer look inside volcanoes, inspect hazardous waste sites such as nuclear reactors, and explore other environments dangerous to humans. (DDR)

  18. Keeping It Simple and Deep.

    ERIC Educational Resources Information Center

    Strong, Richard; Silver, Harvey; Perini, Matthew

    1999-01-01

    Like today's educators, Japanese haiku poets were caught between standards (like courtly love) and everyday realities. From this tension, they created a remarkable poetic form. Three examples from teachers' professional development work apply simple-and-deep principles to listening tasks, an assessment "deal," and curricular-standards…

  19. Ploughing the deep sea floor.

    PubMed

    Puig, Pere; Canals, Miquel; Company, Joan B; Martín, Jacobo; Amblas, David; Lastras, Galderic; Palanques, Albert

    2012-09-13

    Bottom trawling is a non-selective commercial fishing technique whereby heavy nets and gear are pulled along the sea floor. The direct impact of this technique on fish populations and benthic communities has received much attention, but trawling can also modify the physical properties of seafloor sediments, water–sediment chemical exchanges and sediment fluxes. Most of the studies addressing the physical disturbances of trawl gear on the seabed have been undertaken in coastal and shelf environments, however, where the capacity of trawling to modify the seafloor morphology coexists with high-energy natural processes driving sediment erosion, transport and deposition. Here we show that on upper continental slopes, the reworking of the deep sea floor by trawling gradually modifies the shape of the submarine landscape over large spatial scales. We found that trawling-induced sediment displacement and removal from fishing grounds causes the morphology of the deep sea floor to become smoother over time, reducing its original complexity as shown by high-resolution seafloor relief maps. Our results suggest that in recent decades, following the industrialization of fishing fleets, bottom trawling has become an important driver of deep seascape evolution. Given the global dimension of this type of fishery, we anticipate that the morphology of the upper continental slope in many parts of the world’s oceans could be altered by intensive bottom trawling, producing comparable effects on the deep sea floor to those generated by agricultural ploughing on land.

  20. Electrochemical Machining Removes Deep Obstructions

    NASA Technical Reports Server (NTRS)

    Catania, Mark J.

    1987-01-01

    Electrochemical machining (ECM) is effective way of removing obstructing material between two deep holes supposed to intersect but do not because of misalignment of drilling tools. ECM makes it possible to rework costly castings otherwise scrapped. Method fast even for tough or hard alloys and complicated three-dimensional shapes.