WorldWideScience

Sample records for fast electron transfer

  1. Vibrational control of electron-transfer reactions: a feasibility study for the fast coherent transfer regime.

    Science.gov (United States)

    Antoniou, P; Ma, Z; Zhang, P; Beratan, D N; Skourtis, S S

    2015-12-14

    Molecular vibrations and electron-vibrational interactions are central to the control of biomolecular electron and energy-transfer rates. The vibrational control of molecular electron-transfer reactions by infrared pulses may enable the precise probing of electronic-vibrational interactions and of their roles in determining electron-transfer mechanisms. This type of electron-transfer rate control is advantageous because it does not alter the electronic state of the molecular electron-transfer system or irreversibly change its molecular structure. For bridge-mediated electron-transfer reactions, infrared (vibrational) excitation of the bridge linking the electron donor to the electron acceptor was suggested as being capable of influencing the electron-transfer rate by modulating the bridge-mediated donor-to-acceptor electronic coupling. This kind of electron-transfer experiment has been realized, demonstrating that bridge-mediated electron-transfer rates can be changed by exciting vibrational modes of the bridge. Here, we use simple models and ab initio computations to explore the physical constraints on one's ability to vibrationally perturb electron-transfer rates using infrared excitation. These constraints stem from the nature of molecular vibrational spectra, the strengths of the electron-vibrational coupling, and the interaction between molecular vibrations and infrared radiation. With these constraints in mind, we suggest parameter regimes and molecular architectures that may enhance the vibrational control of electron transfer for fast coherent electron-transfer reactions.

  2. Evidences from electron momentum spectroscopy for ultra-fast charge transfers and structural reorganizations in a floppy molecule: Ethanol

    Energy Technology Data Exchange (ETDEWEB)

    Deleuze, Michael S; Hajgato, Balazs; Morini, Filippo, E-mail: michael.deleuze@uhasselt.b [Theoretical Chemistry, Department SBG, Hasselt University, Agoralaan Gebouw D, B-3590 Diepenbeek (Belgium)

    2009-11-01

    Calculations of electron momentum distributions employing advanced Dyson orbital theories and statistical thermodynamics beyond the RRHO approximation fail to quantitatively reproduce the outermost momentum profile inferred from experiments on ethanol employing high resolution Electron Momentum Spectroscopy [1]. Study of the influence of nuclear dynamics in the initial ground state and final ionized state indicates that this discrepancy between theory and experiment reflects a charge transfer occurring during an ultra-fast dissociation of the ethanol radical cation into a methyl radical and H{sub 2}C=O-H{sup +}.

  3. Electron transfer in proteins

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1991-01-01

    Electron migration between and within proteins is one of the most prevalent forms of biological energy conversion processes. Electron transfer reactions take place between active centers such as transition metal ions or organic cofactors over considerable distances at fast rates and with remarkable...... specificity. The electron transfer is attained through weak electronic interaction between the active sites, so that considerable research efforts are centered on resolving the factors that control the rates of long-distance electron transfer reactions in proteins. These factors include (in addition......-containing proteins. These proteins serve almost exclusively in electron transfer reactions, and as it turns out, their metal coordination sites are endowed with properties uniquely optimized for their function....

  4. Fast electron transfer through a single molecule natively structured redox protein

    DEFF Research Database (Denmark)

    Della Pia, Eduardo Antonio; Chi, Qijin; Macdonald, J. Emyr;

    2012-01-01

    a gold surface and a platinum–iridium STM tip. Two different orientations of the linkers were examined: a long-axis configuration (SH-LA) and a short-axis configuration (SH-SA). In each case, the molecular conductance could be ‘gated’ through electrochemical control of the heme redox state. Reproducible...... and remarkably high conductance was observed in this relatively complex electron transfer system, with single-molecule conductance values peaking around 18 nS and 12 nS for the SH-SA and SH-LA cytochrome b562 molecules near zero electrochemical overpotential. This strongly points to the important role...

  5. Chapter 4 Electron transfer in respiratory complexes resolved by an ultra-fast freeze-quench approach.

    Science.gov (United States)

    Belevich, Nikolai P; Verkhovskaya, Marina L; Verkhovsky, Michael I

    2009-01-01

    The investigation of the molecular mechanism of the respiratory chain complexes requires determination of the time-dependent evolution of the catalytic cycle intermediates. The ultra-fast freeze-quench approach makes possible trapping such intermediates with consequent analysis of their chemical structure by means of different physical spectroscopic methods (e.g., EPR, optic, and Mössbauer spectroscopies). This chapter presents the description of a setup that allows stopping the enzymatic reaction in the time range from 100 microsec to tens of msec. The construction and production technology of the mixer head, ultra-fast freezing device, and accessories required for collecting a sample are described. Ways of solving a number of problems emerging on freezing of the reaction mixture and preparing the samples for EPR spectroscopy are proposed. The kinetics of electron transfer reaction in the first enzyme of the respiratory chain, Complex I (NADH: ubiquinone oxidoreductase), is presented as an illustration of the freeze-quench approach. Time-resolved EPR spectra indicating the redox state of FeS clusters of the wild-type and mutant (R274A in subunit NuoCD) Complex I from Escherichia coli are shown.

  6. 2D electron momentum distributions for transfer ionization in fast proton Helium collisions

    CERN Document Server

    Schoeffler, M S; Houamer, S; Galstyan, A G; Titze, J N; Schmidt, L Ph H; Jahnke, T; Schmidt-Boecking, H; Doerner, R; Popov, Yu V; Gusev, A A; Cappello, C Dal

    2013-01-01

    The momentum distribution of the electron in the reaction p+He $\\rightarrow$ H + He$^{2+}$ + $e$ is measured for projectile energies $E_p$=300 and 630 keV/u at very small scattering angles of hydrogen. We mainly present two dimensional distributions parallel $(k_{||})$ and perpendicular $(k_{\\perp})$ to the projectile beam. Theoretical calculations were carried out within the Plane Wave First Born Approximation (PWFBA), which includes both electron emission mechanisms, shake-off and sequential capture and ionization. It is shown that electron correlations in the target wave function play the most important role in the explanation of experimentally observed backward emission. Second order effects have to be involved to correctly describe the forward emission of the electron.

  7. Fast repair of dAMP hydroxyl radical adduct by verbascoside via electron transfer

    Institute of Scientific and Technical Information of China (English)

    石益民; 王文锋; 姚思德; 林维真; 韩镇辉; 师彦平; 贾忠建; 郑荣梁

    1999-01-01

    DNA damaged by oxygen radicals has been implicated as a causative event in a number of degenerative diseases, including cancer and aging. So it is very impotant to look for ways in which either oxygen radicals are scavenged prior to DNA damage or damaged DNA is repaired to supplement the cells’ inadequate repair capacity. The repair activity and its mechanism of verbaseoside, isolated from Pedicularis species, towards dAMP-OH·was studied with pulse radiolytic technique. On pulse irradiation of nitrous oxide saturated 2 mmol/L dAMP aqueous solution containing verbascoside, the transient absorption spectrum of the hydroxyl adduct of dAMP decayed with the formation of that of the phenoxyl radical of verbascoside well under 100 microseconds after electron pulse irradiation. The result indicated that dAMP hydroxyl adducts can be repaired by verbascoside. The rate constants of the repair reaction was deduced to be 5.9×108 dm3·mol-1·s-1. A deeper understanding of this new repair mechanism will undo

  8. Electron transfer reactions

    CERN Document Server

    Cannon, R D

    2013-01-01

    Electron Transfer Reactions deals with the mechanisms of electron transfer reactions between metal ions in solution, as well as the electron exchange between atoms or molecules in either the gaseous or solid state. The book is divided into three parts. Part 1 covers the electron transfer between atoms and molecules in the gas state. Part 2 tackles the reaction paths of oxidation states and binuclear intermediates, as well as the mechanisms of electron transfer. Part 3 discusses the theories and models of the electron transfer process; theories and experiments involving bridged electron transfe

  9. Revealing the Origin of Fast Electron Transfer in TiO2-Based Dye-Sensitized Solar Cells.

    Science.gov (United States)

    Wei, Hai; Luo, Jun-Wei; Li, Shu-Shen; Wang, Lin-Wang

    2016-07-01

    In dye-sensitized solar cells (DSCs), the electron transfer from photoexcited dye molecules to semiconductor substrates remains a major bottleneck. Replacing TiO2 with ZnO is expected to enhance the efficiency of DSCs, owing to the latter possesses a much larger electron mobility, but similar bandgap and band positions as TiO2 remain. However, the record efficiency of ZnO-based DSCs is only 7% compared with 13% of TiO2-based DSCs due to the even slower electron-transfer rate in ZnO-based DSCs, which becomes a long-standing puzzle. Here, we computationally investigate the electron transfer from the dye molecule into ZnO and TiO2, respectively, by performing the first-principles calculations within the frame of the Marcus theory. The predicted electron-transfer rate in the TiO2-based DSC is about 1.15 × 10(9) s(-1), a factor of 15 faster than that of the ZnO-based DSC, which is in good agreement with experimental data. We find that the much larger density of states of the TiO2 compared with ZnO near the conduction band edge is the dominant factor, which is responsible for the faster electron-transfer rate in TiO2-based DSCs. These denser states provide additional efficient channels for the electron transfer. We also provide design principles to boost the efficiency of DSCs through surface engineering of high mobility photoanode semiconductors.

  10. Fast regeneration of carotenoids from radical cations by isoflavonoid dianions: importance of the carotenoid keto group for electron transfer.

    Science.gov (United States)

    Han, Rui-Min; Chen, Chang-Hui; Tian, Yu-Xi; Zhang, Jian-Ping; Skibsted, Leif H

    2010-01-14

    Electron transfer to radical cations of beta-carotene, zeaxanthin, canthaxanthin, and astaxanthin from each of the three acid/base forms of the diphenolic isoflavonoid daidzein and its C-glycoside puerarin, as studied by laser flash photolysis in homogeneous methanol/chloroform (1/9) solution, was found to depend on carotenoid structures and more significantly on the deprotonation degree of the isoflavonoids. None of the carotenoid radical cations reacted with the neutral forms of the isoflavonoids while the monoanionic and dianionic forms of the isoflavonoids regenerated the oxidized carotenoid. Electron transfer to the beta-carotene radical cation from the puerarin dianion followed second order kinetics with the rate constant at 25 degrees C k(2) = 5.5 x 10(9) M(-1) s(-1), zeaxanthin 8.5 x 10(9) M(-1) s(-1), canthaxanthin 6.5 x 10(10) M(-1) s(-1), and astaxanthin 11.1 x 10(10) M(-1) s(-1) approaching the diffusion limit and establishing a linear free energy relationship between rate constants and driving force. Comparable results found for the daidzein dianion indicate that the steric hindrance from the glucoside is not important suggesting the more reducing but less acidic 4'-OH/4'-O(-) as electron donors. On the basis of the rate constants obtained from kinetic analyses, the keto group of carotenoids is concluded to facilitate electron transfer. The driving force was estimated from oxidation potentials, as determined by cyclic-voltametry for puerarin and daidzein in aqueous solutions at varying pH conditions, which led to the standard reduction potentials E degrees = 1.13 and 1.10 V versus NHE corresponding to the uncharged puerarin and daidzein. For pH > pK(a2), the apparent potentials of both puerarin and daidzein became constants and were E degrees = 0.69 and 0.65 V, respectively. Electron transfer from isoflavonoids to the carotenoid radical cation, as formed during oxidative stress, is faster for astaxanthin than for the other carotenoids, which may relate

  11. Electron transfer in peptides.

    Science.gov (United States)

    Shah, Afzal; Adhikari, Bimalendu; Martic, Sanela; Munir, Azeema; Shahzad, Suniya; Ahmad, Khurshid; Kraatz, Heinz-Bernhard

    2015-02-21

    In this review, we discuss the factors that influence electron transfer in peptides. We summarize experimental results from solution and surface studies and highlight the ongoing debate on the mechanistic aspects of this fundamental reaction. Here, we provide a balanced approach that remains unbiased and does not favor one mechanistic view over another. Support for a putative hopping mechanism in which an electron transfers in a stepwise manner is contrasted with experimental results that support electron tunneling or even some form of ballistic transfer or a pathway transfer for an electron between donor and acceptor sites. In some cases, experimental evidence suggests that a change in the electron transfer mechanism occurs as a result of donor-acceptor separation. However, this common understanding of the switch between tunneling and hopping as a function of chain length is not sufficient for explaining electron transfer in peptides. Apart from chain length, several other factors such as the extent of the secondary structure, backbone conformation, dipole orientation, the presence of special amino acids, hydrogen bonding, and the dynamic properties of a peptide also influence the rate and mode of electron transfer in peptides. Electron transfer plays a key role in physical, chemical and biological systems, so its control is a fundamental task in bioelectrochemical systems, the design of peptide based sensors and molecular junctions. Therefore, this topic is at the heart of a number of biological and technological processes and thus remains of vital interest.

  12. Electron Transfer Chain Catalysis

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    @@ Electron-transfer chain (ETC) catalysis belongs to the family of chain reactions where the electron is the catalyst. The ETC mechanism could be initiated by chemical activation, electrochemistry, or photolysis. If this pathway is applied to the preparation of organometallic complexes, it utilizes the greatly enhanced reactivity of organometallic 17e and 19e radicals. The chemical propagation is followed by the cross electron-transfer while the electron-transfer step is also followed by the chemical propagation, creating a loop in which reactants are facilely transformed into products. Interestingly the overall reaction is without any net redox change.

  13. Electron Transfer Chain Catalysis

    Institute of Scientific and Technical Information of China (English)

    LIU; LingKang

    2001-01-01

    Electron-transfer chain (ETC) catalysis belongs to the family of chain reactions where the electron is the catalyst. The ETC mechanism could be initiated by chemical activation, electrochemistry, or photolysis. If this pathway is applied to the preparation of organometallic complexes, it utilizes the greatly enhanced reactivity of organometallic 17e and 19e radicals. The chemical propagation is followed by the cross electron-transfer while the electron-transfer step is also followed by the chemical propagation, creating a loop in which reactants are facilely transformed into products. Interestingly the overall reaction is without any net redox change.  ……

  14. Transfer ionization in collisions with a fast highly charged ion.

    Science.gov (United States)

    Voitkiv, A B

    2013-07-26

    Transfer ionization in fast collisions between a bare ion and an atom, in which one of the atomic electrons is captured by the ion whereas another one is emitted, crucially depends on dynamic electron-electron correlations. We show that in collisions with a highly charged ion a strong field of the ion has a very profound effect on the correlated channels of transfer ionization. In particular, this field weakens (strongly suppresses) electron emission into the direction opposite (perpendicular) to the motion of the ion. Instead, electron emission is redirected into those parts of the momentum space which are very weakly populated in fast collisions with low charged ions.

  15. Stepwise Two-Photon-Induced Fast Photoswitching via Electron Transfer in Higher Excited States of Photochromic Imidazole Dimer.

    Science.gov (United States)

    Kobayashi, Yoichi; Katayama, Tetsuro; Yamane, Takuya; Setoura, Kenji; Ito, Syoji; Miyasaka, Hiroshi; Abe, Jiro

    2016-05-11

    Stepwise two-photon excitations have been attracting much interest because of their much lower power thresholds compared with simultaneous two-photon processes and because some stepwise two-photon processes can be initiated by a weak incoherent excitation light source. Here we apply stepwise two-photon optical processes to the photochromic bridged imidazole dimer, whose solution instantly changes color upon UV irradiation and quickly reverts to the initial color thermally at room temperature. We synthesized a zinc tetraphenylporphyrin (ZnTPP)-substituted bridged imidazole dimer, and wide ranges of time-resolved spectroscopic studies revealed that a ZnTPP-linked bridged imidazole dimer shows efficient visible stepwise two-photon-induced photochromic reactions upon excitation at the porphyrin moiety. The fast photoswitching property combined with stepwise two-photon processes is important not only for the potential for novel photochromic materials that are sensitive to the incident light intensity but also for fundamental photochemistry using higher excited states.

  16. Electron Transfer Pathways in Cell

    OpenAIRE

    Yan Liu

    2012-01-01

    Analysis of the electron salvation process data indicates that the electron transfer between the electron donor and acceptor is hindered by the electron salvation process. It is proposed that the electron transfer in the cell environment must be assisted by intermediate messenger called the “transport protein”.

  17. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1993-01-01

    Advances in Electron Transfer Chemistry, Volume 3 presents studies that discuss findings in the various aspects of electron chemistry. The book is comprised of four chapters; each chapter reviews a work that tackles an issue in electron transfer chemistry. Chapter 1 discusses the photoinduced electron transfer in flexible biaryl donor-acceptor molecules. Chapter 2 tackles light-induced electron transfer in inorganic systems in homogeneous and heterogeneous phases. The book also covers internal geometry relaxation effects on electron transfer rates of amino-centered systems. The sequential elec

  18. Lithium Ion Coupled Electron-Transfer Rates in Superconcentrated Electrolytes: Exploring the Bottlenecks for Fast Charge-Transfer Rates with LiMn2O4 Cathode Materials.

    Science.gov (United States)

    Nikitina, Victoria A; Zakharkin, Maxim V; Vassiliev, Sergey Yu; Yashina, Lada V; Antipov, Evgeny V; Stevenson, Keith J

    2017-09-19

    The charge-transfer kinetics of lithium ion intercalation into LixMn2O4 cathode materials was examined in dilute and concentrated aqueous and carbonate LiTFSI solutions using electrochemical methods. Distinctive trends in ion intercalation rates were observed between water-based and ethylene carbonate/diethyl carbonate solutions. The influence of the solution concentration on the rate of lithium ion transfer in aqueous media can be tentatively attributed to the process associated with Mn dissolution, whereas in carbonate solutions the rate is influenced by the formation of a concentration-dependent solid electrolyte interface (SEI). Some indications of SEI layer formation at electrode surfaces in carbonate solutions after cycling are detected by X-ray photoelectron spectroscopy. The general consequences related to the application of superconcentrated electrolytes for use in advanced energy storage cathodes are outlined and discussed.

  19. Fast liquid transfer between two surfaces

    Science.gov (United States)

    Chen, Huanchen; Tang, Tian; Amirfazli, Alidad

    2014-11-01

    Liquid transfer process between two surfaces typically ends by breaking of a stretched liquid bridge. The amount of liquid remaining on each of the surfaces relative to total volume is usually of interest in applications (e.g. offset or electronic printing, wet adhesion systems, etc.). Literature shows that depending on stretching velocity, U, surface wettability and liquid properties, the behaviour of the liquid bridge can be categorized into: quasi-static where the surface force dominates and dynamic where contributions from viscous and inertia forces are not negligible. Through a systematic experimental study, we demonstrate for the first time that the division of liquid between surfaces in the quasi-static regime is a constant which depends on the receding contact angles. In the dynamic regime (fast transfer), liquid division takes a complicated form. An analytical-empirical model is developed and verified by experimental results that can predict splitting of the liquid between two surfaces as a function of U, surface wettability and liquid viscosity. The model also successfully predicts an even split between surfaces at extremely high velocities as it was observed by us and others.

  20. Electronic Correlations in Electron Transfer Systems

    Science.gov (United States)

    Bulla, Ralf; Tornow, Sabine; Anders, Frithjof

    Electron transfer processes play a central role in many chemical and biological systems. Already the transfer of a single electron from the donor to the acceptor can be viewed as a complicated many-body problem, due to the coupling of the electron to the infinitely many environmental degrees of freedom, realized by density fluctuations of the solvent or molecular vibrations of the protein matrix. We focus on the quantum mechanical modelling of two-electron transfer processes whose dynamics is governed by the Coulomb interaction between the electrons as well as the environmental degrees of freedoms represented by a bosonic bath. We identify the regime of parameters in which concerted transfer of the two electrons occurs and discuss the influence of the Coulomb repulsion and the coupling strength to the environment on the electron transfer rate. Calculations are performed using the non-perturbative numerical renormalization group approach for both equilibrium and non-equilibrium properties.

  1. FAST TRACK COMMUNICATION: Synthesis and electron transfer property of sulfhydryl-containing multi-walled carbon nanotube/gold nanoparticle heterojunctions

    Science.gov (United States)

    Feng, Xiumei; Hu, Jianqiang; Chen, Xiaohua; Xie, Jingsi; Liu, Yuying

    2009-02-01

    One-dimensional metal/semiconductor heterojunction nanomaterials have opened many new opportunities for future nanodevices because of their novel structures and unique electrical and optical properties. In this work, sulfhydryl-containing multi-walled carbon nanotube/gold nanoparticle (MWCNT/Au) heterojunctions were synthesized in high yield by a sulfhydryl- functionalized self-assembly strategy. The component, size, structure, morphology and bond mode of the MWCNT/Au heterojunctions thus prepared were investigated and demonstrated by transmission electron microscopy, scanning electron microscopy, x-ray diffraction, energy-dispersive x-ray spectroscopy, Fourier-transform infrared and UV-visible measurements. Cyclic voltammogram and electrochemical impedance spectroscopy studies indicate that the MWCNT/Au heterojunctions have a novel electron transfer property, which retards electron transfer of the horseradish peroxidase or the ferricyanide in the underlying electrodes. We believe that MWCNT/Au heterojunctions with high stability and a unique electrical property are expected to find potential applications for nanodevices.

  2. FAST TRACK COMMUNICATION: Effects of charge transfer interaction of graphene with electron donor and acceptor molecules examined using Raman spectroscopy and cognate techniques

    Science.gov (United States)

    Voggu, Rakesh; Das, Barun; Sekhar Rout, Chandra; Rao, C. N. R.

    2008-11-01

    The effects of the interaction of few-layer graphene with electron donor and acceptor molecules have been investigated by employing Raman spectroscopy, and the results compared with those from electrochemical doping. The G-band softens progressively with increasing concentration of tetrathiafulvalene (TTF) which is an electron donor, while the band stiffens with increasing concentration of tetracyanoethylene (TCNE) which is an electron acceptor. Interaction with both TTF and TCNE broadens the G-band. Hole and electron doping by electrochemical means, however, stiffen and sharpen the G-band. The 2D-band position is also affected by interaction with TTF and TCNE. More importantly, the intensity of the 2D-band decreases markedly with the concentration of either. The ratio of intensities of the 2D-band and G-band decreases with an increase in TTF or TCNE concentration, and provides a means for carrier titration in the charge transfer system. Unlike the intensity of the 2D-band, that of the D-band increases on interaction with TTF or TCNE. All of these effects occur due to molecular charge transfer, also evidenced by the occurrence of charge transfer bands in the electronic absorption spectra. The electrical resistivity of graphene varies in opposite directions on interaction with TTF and TCNE, the resistivity depending on the concentration of either compound.

  3. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1995-01-01

    Advances in Electron Transfer Chemistry, Volume 4 presents the reaction mechanisms involving the movement of single electrons. This book discusses the electron transfer reactions in organic, biochemical, organometallic, and excited state systems. Organized into four chapters, this volume begins with an overview of the photochemical behavior of two classes of sulfonium salt derivatives. This text then examines the parameters that control the efficiencies for radical ion pair formation. Other chapters consider the progress in the development of parameters that control the dynamics and reaction p

  4. Two-Electron Transfer Pathways.

    Science.gov (United States)

    Lin, Jiaxing; Balamurugan, D; Zhang, Peng; Skourtis, Spiros S; Beratan, David N

    2015-06-18

    The frontiers of electron-transfer chemistry demand that we develop theoretical frameworks to describe the delivery of multiple electrons, atoms, and ions in molecular systems. When electrons move over long distances through high barriers, where the probability for thermal population of oxidized or reduced bridge-localized states is very small, the electrons will tunnel from the donor (D) to acceptor (A), facilitated by bridge-mediated superexchange interactions. If the stable donor and acceptor redox states on D and A differ by two electrons, it is possible that the electrons will propagate coherently from D to A. While structure-function relations for single-electron superexchange in molecules are well established, strategies to manipulate the coherent flow of multiple electrons are largely unknown. In contrast to one-electron superexchange, two-electron superexchange involves both one- and two-electron virtual intermediate states, the number of virtual intermediates increases very rapidly with system size, and multiple classes of pathways interfere with one another. In the study described here, we developed simple superexchange models for two-electron transfer. We explored how the bridge structure and energetics influence multielectron superexchange, and we compared two-electron superexchange interactions to single-electron superexchange. Multielectron superexchange introduces interference between singly and doubly oxidized (or reduced) bridge virtual states, so that even simple linear donor-bridge-acceptor systems have pathway topologies that resemble those seen for one-electron superexchange through bridges with multiple parallel pathways. The simple model systems studied here exhibit a richness that is amenable to experimental exploration by manipulating the multiple pathways, pathway crosstalk, and changes in the number of donor and acceptor species. The features that emerge from these studies may assist in developing new strategies to deliver multiple

  5. Theory of Fast Electron Transport for Fast Ignition

    CERN Document Server

    Robinson, A P L; Davies, J R; Gremillet, L; Honrubia, J J; Johzaki, T; Kingham, R J; Sherlock, M; Solodov, A A

    2013-01-01

    Fast Ignition Inertial Confinement Fusion is a variant of inertial fusion in which DT fuel is first compressed to high density and then ignited by a relativistic electron beam generated by a fast (< 20 ps) ultra-intense laser pulse, which is usually brought in to the dense plasma via the inclusion of a re-entrant cone. The transport of this beam from the cone apex into the dense fuel is a critical part of this scheme, as it can strongly influence the overall energetics. Here we review progress in the theory and numerical simulation of fast electron transport in the context of Fast Ignition. Important aspects of the basic plasma physics, descriptions of the numerical methods used, a review of ignition-scale simulations, and a survey of schemes for controlling the propagation of fast electrons are included. Considerable progress has taken place in this area, but the development of a robust, high-gain FI `point design' is still an ongoing challenge.

  6. Fast Electronics in High-Energy Physics

    Energy Technology Data Exchange (ETDEWEB)

    Weigand, Clyde

    1958-08-08

    A brief review of fast electronics is given, leading up to the present state of the art. Cherenkov counters in high-energy physics are discussed, including an example of a velocity-selecting Cherenkov counter. An electronic device to aid in aligning external beams from high-energy accelerators is described. A scintillation-counter matrix to identify bubble chamber tracks is discussed. Some remarks on the future development of electronics in high-energy physics experiments are included.

  7. Fast electron scattering as a tool to study target structure

    CERN Document Server

    Amusia, M Ya

    2006-01-01

    We concentrate on several relatively new aspects of the study of fast electron scattering by atoms and atom-like objects, namely endohedral atoms and fullerenes. We show that the corresponding cross sections, being expressed via so-called Generalized Oscillator Strengths (GOS), give information on the electronic structure of the target and on the role of electron correlations in it. We consider what sort of information became available when analyzing the dependence of GOS upon their multipolarity, transferred momentum and energy. We demonstrate the role of nondipole corrections in the small-angle fast-electron inelastic scattering. There dipole contribution dominates while non-dipole corrections can be considerably and controllably enhanced as compared to the case of low and medium energy photoionization. We show also that analyses of GOS for discrete level excitations permit to clarify their multipolarity. The results of calculations of Compton excitation and ionization cross-sections for noble gas atoms are...

  8. Fast electrons in small solar flares

    Science.gov (United States)

    Lin, R. P.

    1975-01-01

    This review summarizes both the direct spacecraft observations of nonrelativistic solar electrons, and observations of the X-ray and radio emission generated by these particles at the sun and in the interplanetary medium. These observations bear on the basic astrophysical process of particle acceleration in tenuous plasmas. We find that in many small solar flares, the nearly 5-100 keV electrons accelerated during flash phase constitute the bulk of the total flare energy. Thus the basic flare mechanism in these flares essentially converts the available flare energy into fast electrons. These electrons may produce the other flare electromagnetic emissions through their interactions with the solar atmosphere. In large proton flares these electrons may provide the energy to eject material from the sun and to create a shock wave which could accelerate nuclei and electrons to much higher energies.

  9. Experimental Approaches to Studying Biological Electron Transfer.

    Science.gov (United States)

    Scott, Robert A.; And Others

    1985-01-01

    Provides an overview on biological electron-transfer reactions, summarizing what is known about how distance, spatial organization, medium, and other factors affect electron transfer. Experimental approaches, including studies of bimolecular electron transfer reactions (electrostatic effects and precursor complexes), are considered. (JN)

  10. Development of buffers for fast semidry transfer of proteins.

    Science.gov (United States)

    Garić, Dušan; Humbert, Laure; Fils-Aimé, Nadège; Korah, Juliana; Zarfabian, Yasaman; Lebrun, Jean-Jacques; Ali, Suhad

    2013-10-15

    Western blot is an extensively used method for protein detection in cell biology. To optimize this procedure, here we examined a panel of buffers for their ability to efficiently transfer proteins from SDS-polyacrylamide gels onto nitrocellulose membranes in a short 12-min period, designated here as fast semidry transfer. Our results show for the first time that HEPES- and HEPPS/EPPS-based buffers represent the most efficient buffers for fast semidry transfer.

  11. Fast transfer of crossmodal time interval training.

    Science.gov (United States)

    Chen, Lihan; Zhou, Xiaolin

    2014-06-01

    Sub-second time perception is essential for many important sensory and perceptual tasks including speech perception, motion perception, motor coordination, and crossmodal interaction. This study investigates to what extent the ability to discriminate sub-second time intervals acquired in one sensory modality can be transferred to another modality. To this end, we used perceptual classification of visual Ternus display (Ternus in Psychol Forsch 7:81-136, 1926) to implicitly measure participants' interval perception in pre- and posttests and implemented an intra- or crossmodal sub-second interval discrimination training protocol in between the tests. The Ternus display elicited either an "element motion" or a "group motion" percept, depending on the inter-stimulus interval between the two visual frames. The training protocol required participants to explicitly compare the interval length between a pair of visual, auditory, or tactile stimuli with a standard interval or to implicitly perceive the length of visual, auditory, or tactile intervals by completing a non-temporal task (discrimination of auditory pitch or tactile intensity). Results showed that after fast explicit training of interval discrimination (about 15 min), participants improved their ability to categorize the visual apparent motion in Ternus displays, although the training benefits were mild for visual timing training. However, the benefits were absent for implicit interval training protocols. This finding suggests that the timing ability in one modality can be rapidly acquired and used to improve timing-related performance in another modality and that there may exist a central clock for sub-second temporal processing, although modality-specific perceptual properties may constrain the functioning of this clock.

  12. Secondary ionization and heating by fast electrons

    CERN Document Server

    Furlanetto, Steven

    2009-01-01

    We examine the fate of fast electrons (with energies E>10 eV) in a thermal gas of primordial composition. To follow their interactions with the background gas, we construct a Monte Carlo model that includes: (1) electron-electron scattering (which transforms the electron kinetic energy into heat), (2) collisional ionization of hydrogen and helium (which produces secondary electrons that themselves scatter through the medium), and (3) collisional excitation (which produces secondary photons, whose fates we also follow approximately). For the last process, we explicitly include all transitions to upper levels n<=4, together with a well-motivated extrapolation to higher levels. In all cases, we use recent calculated cross-sections at E<1 keV and the Bethe approximation to extrapolate to higher energies. We compute the fractions of energy deposited as heat, ionization (tracking HI and the helium species separately), and excitation (tracking HI Lyman-alpha separately) under a broad range of conditions approp...

  13. Heterostructure Intervalley Transferred Electron Effects

    Institute of Scientific and Technical Information of China (English)

    XUE Fang-Shi

    2001-01-01

    A Gunn active layer is used as an X electron probe to detect the X tunnelling current in the GaAs-AlAs heterostructure, from which a new heterostructure intervalley transferred electron (HITE) device is obtained. In the 8 mm band, the highest pulse output power of these diodes is 2.65 W and the highest conversion efficiency is 18%. The dc and rf performance of the HITE devices was simulated by the band mixing resonant tunnelling theory and Monte Carlo transport simulation. The HITE effect has transformed the transit-time dipole-layer mode in the Gunn diode into a relaxation oscillation mode in the HITE device. From the comparison of simulated results to the measured data, the HITE effect is demonstrated straightforwardly

  14. Exocellular electron transfer in anaerobic microbial communities

    NARCIS (Netherlands)

    Stams, A.J.M.; Bok, de F.A.M.; Plugge, C.M.; Eekert, van M.H.A.; Dolfing, J.; Schraa, G.

    2006-01-01

    Exocellular electron transfer plays an important role in anaerobic microbial communities that degrade organic matter. Interspecies hydrogen transfer between microorganisms is the driving force for complete biodegradation in methanogenic environments. Many organic compounds are degraded by obligatory

  15. Exocellular electron transfer in anaerobic microbial communities

    NARCIS (Netherlands)

    Stams, A.J.M.; Bok, de F.A.M.; Plugge, C.M.; Eekert, van M.H.A.; Dolfing, J.; Schraa, G.

    2006-01-01

    Exocellular electron transfer plays an important role in anaerobic microbial communities that degrade organic matter. Interspecies hydrogen transfer between microorganisms is the driving force for complete biodegradation in methanogenic environments. Many organic compounds are degraded by obligatory

  16. Supramolecular electron transfer by anion binding.

    Science.gov (United States)

    Fukuzumi, Shunichi; Ohkubo, Kei; D'Souza, Francis; Sessler, Jonathan L

    2012-10-11

    Anion binding has emerged as an attractive strategy to construct supramolecular electron donor-acceptor complexes. In recent years, the level of sophistication in the design of these systems has advanced to the point where it is possible to create ensembles that mimic key aspects of the photoinduced electron-transfer events operative in the photosynthetic reaction centre. Although anion binding is a reversible process, kinetic studies on anion binding and dissociation processes, as well as photoinduced electron-transfer and back electron-transfer reactions in supramolecular electron donor-acceptor complexes formed by anion binding, have revealed that photoinduced electron transfer and back electron transfer occur at time scales much faster than those associated with anion binding and dissociation. This difference in rates ensures that the linkage between electron donor and acceptor moieties is maintained over the course of most forward and back electron-transfer processes. A particular example of this principle is illustrated by electron-transfer ensembles based on tetrathiafulvalene calix[4]pyrroles (TTF-C4Ps). In these ensembles, the TTF-C4Ps act as donors, transferring electrons to various electron acceptors after anion binding. Competition with non-redox active substrates is also observed. Anion binding to the pyrrole amine groups of an oxoporphyrinogen unit within various supramolecular complexes formed with fullerenes also results in acceleration of the photoinduced electron-transfer process but deceleration of the back electron transfer; again, this is ascribed to favourable structural and electronic changes. Anion binding also plays a role in stabilizing supramolecular complexes between sulphonated tetraphenylporphyrin anions ([MTPPS](4-): M = H(2) and Zn) and a lithium ion encapsulated C(60) (Li(+)@C(60)); the resulting ensemble produces long-lived charge-separated states upon photoexcitation of the porphyrins.

  17. Fast electron bremsstrahlung in axisymmetric magnetic configuration

    Science.gov (United States)

    Peysson, Y.; Decker, J.

    2008-09-01

    The nonthermal bremsstrahlung is calculated in a plasma with arbitrary axisymmetric magnetic configuration, taking into account the relativistic angular anisotropy of the radiation cross section at high photon energies, the helical winding of the field lines on the magnetic flux surfaces, and the poloidal variation of the electron distribution function including particle trapping effects. The fast electron dynamics during current drive in tokamaks and reverse field pinches can be investigated in detail by coupling this calculation to a bounce-averaged relativistic Fokker-Planck solver, which calculates the electron distribution function. The asymmetry between high- and low-field side hard x-ray emission intensity that has been measured on the Tore-Supra tokamak [Equipe TORE SUPRA, in Proceedings of the 15th Conference on Plasma Physics and Controlled Nuclear Fusion Research, Seville (International Atomic Energy Agency, Vienna, 1995) Vol. 1, IAEA-CN-60/A1-5 (Institute of Physics, Bristol, U.K., 1995), p. 105] is explained for the first time by the role of trapped electrons. A much stronger poloidal asymmetry is predicted for the line-integrated fast electron bremsstrahlung in the poloidal plane of the Madison Symmetric Torus [R. N. Dexter et al., Fusion Tech. 19, 131 (1991)], since the helical winding of the magnetic field lines is much larger for a reverse field pinch configuration. In this case, the hard x-ray emission is no longer a flux surface quantity, which prevents local reconstructions using a standard Abel inversion, whatever the geometrical arrangement of the lines of sight.

  18. Optically Forbidden Excitations of 2s Electron of Neon Studied by Fast Electron Impact

    Institute of Scientific and Technical Information of China (English)

    GE Min; ZHU Lin-Fan; LIU Cun-Ding; XU Ke-Zun

    2008-01-01

    The electron energy loss spectrum in the energy region of 42-48.5 eV of neon is measured with an angle-resolved fast-electron energy-loss spectrometer at an incident electron energy of 2500eV. Besides the dipole-allowed autoionization transitions of 2s-1np (n = 3, 4) and 2p-23s3p, the dipole-forbidden ones of 2s-1ns (n = 3 - 6) and 2s-13d are observed. The line profile parameters, i.e. ET, F and q for these transitions, are determined, and the momentum transfer dependence behaviour is discussed.

  19. Hierarchical control of electron-transfer

    DEFF Research Database (Denmark)

    Westerhoff, Hans V.; Jensen, Peter Ruhdal; Egger, Louis;

    1997-01-01

    In this chapter the role of electron transfer in determining the behaviour of the ATP synthesising enzyme in E. coli is analysed. It is concluded that the latter enzyme lacks control because of special properties of the electron transfer components. These properties range from absence of a strong...... back pressure by the protonmotive force on the rate of electron transfer to hierarchical regulation of the expression of the gens that encode the electron transfer proteins as a response to changes in the bioenergetic properties of the cell.The discussion uses Hierarchical Control Analysis...

  20. Recent Developments in Electron Transfer Reactions

    OpenAIRE

    Marcus, Rudolph A.

    1987-01-01

    Earlier results and more recent developments in electron transfer reactions are reviewed. The more recent results include inverted behavior, electronic orientation effects on reaction rates, solvent dynamics, early steps in photosynthesis, and light emission from metal electrodes.

  1. Fast Electron Beam Simulation and Dose Calculation

    CERN Document Server

    Trindade, A; Peralta, L; Lopes, M C; Alves, C; Chaves, A

    2003-01-01

    A flexible multiple source model capable of fast reconstruction of clinical electron beams is presented in this paper. A source model considers multiple virtual sources emulating the effect of accelerator head components. A reference configuration (10 MeV and 10x10 cm2 field size) for a Siemens KD2 linear accelerator was simulated in full detail using GEANT3 Monte Carlo code. Our model allows the reconstruction of other beam energies and field sizes as well as other beam configurations for similar accelerators using only the reference beam data. Electron dose calculations were performed with the reconstructed beams in a water phantom and compared with experimental data. An agreement of 1-2% / 1-2 mm was obtained, equivalent to the accuracy of full Monte Carlo accelerator simulation. The source model reduces accelerator simulation CPU time by a factor of 7500 relative to full Monte Carlo approaches. The developed model was then interfaced with DPM, a fast radiation transport Monte Carlo code for dose calculati...

  2. Fast flexible electronics with strained silicon nanomembranes.

    Science.gov (United States)

    Zhou, Han; Seo, Jung-Hun; Paskiewicz, Deborah M; Zhu, Ye; Celler, George K; Voyles, Paul M; Zhou, Weidong; Lagally, Max G; Ma, Zhenqiang

    2013-01-01

    Fast flexible electronics operating at radio frequencies (>1 GHz) are more attractive than traditional flexible electronics because of their versatile capabilities, dramatic power savings when operating at reduced speed and broader spectrum of applications. Transferrable single-crystalline Si nanomembranes (SiNMs) are preferred to other materials for flexible electronics owing to their unique advantages. Further improvement of Si-based device speed implies significant technical and economic advantages. While the mobility of bulk Si can be enhanced using strain techniques, implementing these techniques into transferrable single-crystalline SiNMs has been challenging and not demonstrated. The past approach presents severe challenges to achieve effective doping and desired material topology. Here we demonstrate the combination of strained- NM-compatible doping techniques with self-sustained-strain sharing by applying a strain-sharing scheme between Si and SiGe multiple epitaxial layers, to create strained print-transferrable SiNMs. We demonstrate a new speed record of Si-based flexible electronics without using aggressively scaled critical device dimensions.

  3. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    OpenAIRE

    2007-01-01

    This contribution describes molecular dynamics, semi-empirical and ab-initio studies of the primary photo-induced electron transfer reaction in DNA photolyase. DNA photolyases are FADH−-containing proteins that repair UV-damaged DNA by photo-induced electron transfer. A DNA photolyase recognizes and binds to cyclobutatne pyrimidine dimer lesions of DNA. The protein repairs a bound lesion by transferring an electron to the lesion from FADH−, upon photo-excitation of FADH− with 350–450 nm light...

  4. Vibrationally Resolved Electron Transfer Rates in Solution

    Science.gov (United States)

    Spears, Kenneth G.

    2002-03-01

    We have re-examined our earlier report of electron transfer in the [Co(Cp)_2|V(CO)_6] radical-pair using ultrafast infrared transient absorption spectroscopy in room temperature solutions. The radical-pair is created from the [Co(Cp)_2^+|V(CO)_6^-] ion-pair by ultrafast visible charge-transfer excitation. Transient absorption experiments with ps time constants. A small ET component with a 75 ps time constant is due to some separation and reformation of the radical-pairs. Transient absorption experiments monitoring the recovery of the ion-pair state shows that both fast components are due to ET rather than some other vibrational relaxation (VR) process in the radical state. We analyze the visible charge-transfer band and assign the two fast ET decay times to two ion-pair contact geometries with absorption origins different by about 1250 ± 350 cm-1. For excitation at 800 and 700 nm the 700 fs ET lifetime depends on the vibrational quantum state of the nontotally symmetric CO stretch in the V(CO)6 radical, where the lifetime decreases by 10% for the first vibrational quantum and 45% for the second quantum. There is no quantum effect for the second ion-pair geometry with a 5 ps ET lifetime. Standard ET rate models cannot explain the rate dependence upon vibrational quantum state for a nontotally symmetric vibration, and it may arise from a breakdown of the Condon approximation. We also report rates for IVR of CO stretching modes and for VR of low frequency vibrations. At excitation wavelengths of 620 and 555 nm there is sufficient internal vibrational energy in low-frequency vibrations to cause geometric inter-conversion between energetically similar Jahn-Teller geometries in the V(CO)6 radical. This process creates a 200 fs rise time for the V(CO)6 radical species to assume a stable geometry, which requires VR of low frequency vibrations to the solvent. These results demonstrate that earlier ET measurements from our group on the same molecule had insufficient time

  5. Photoinduced electron transfer across molecular bridges: electron- and hole-transfer superexchange pathways.

    Science.gov (United States)

    Natali, Mirco; Campagna, Sebastiano; Scandola, Franco

    2014-06-21

    Photoinduced electron transfer plays key roles in many areas of chemistry. Superexchange is an effective model to rationalize photoinduced electron transfer, particularly when molecular bridges between donor and acceptor subunits are present. In this tutorial review we discuss, within a superexchange framework, the complex role played by the bridge, with an emphasis on differences between thermal and photoinduced electron transfer, oxidative and reductive photoinduced processes, charge separation and charge recombination. Modular bridges are also considered, with specific attention to the distance dependence of donor-acceptor electronic coupling and electron transfer rate constants. The possibility of transition, depending on the bridge energetics, from coherent donor-acceptor electron transfer to incoherent charge injection and hopping through the bridge is also discussed. Finally, conceptual analogies between bridge effects in photoinduced electron transfer and optical intervalence transfer are outlined. Selected experimental examples, instrumental to illustration of the principles, are discussed.

  6. Linear circuit transfer functions an introduction to fast analytical techniques

    CERN Document Server

    Basso, Christophe P

    2016-01-01

    Linear Circuit Transfer Functions: An introduction to Fast Analytical Techniques teaches readers how to determine transfer functions of linear passive and active circuits by applying Fast Analytical Circuits Techniques. Building on their existing knowledge of classical loop/nodal analysis, the book improves and expands their skills to unveil transfer functions in a swift and efficient manner. Starting with simple examples, the author explains step-by-step how expressing circuits time constants in different configurations leads to writing transfer functions in a compact and insightful way. By learning how to organize numerators and denominators in the fastest possible way, readers will speed-up analysis and predict the frequency resp nse of simple to complex circuits. In some cases, they will be able to derive the final expression by inspection, without writing a line of algebra. Key features: * Emphasizes analysis through employing time constant-based methods discussed in other text books but not widely us...

  7. Electron Cyclotron Maser Emissions from Evolving Fast Electron Beams

    CERN Document Server

    Tang, J F; Chen, L; Zhao, G Q; Tan, C M

    2016-01-01

    Fast electron beams (FEBs) are common products of solar active phenomena. Solar radio bursts are an important diagnostic tool in the understanding of FEBs as well as the solar plasma environment in which they are propagating along solar magnetic fields. In particular, the evolutions of the energy spectrum and velocity distribution of FEBs due to the interaction with the ambient plasma and field when propagating can significantly influence the efficiency and property of their emissions. In this paper, we discuss some possible evolutions of the energy spectrum and velocity distribution of FEBs due to the energy loss processes and the pitch-angle effect caused by the magnetic field inhomogeneity, and analyze the effects of these evolutions on electron cyclotron maser (ECM) emission, which is one of the most important mechanisms of producing solar radio bursts by FEBs. The results show that the growth rates all decrease with the energy loss factor $Q$, but increase with the magnetic mirror ratio $\\sigma$ as well ...

  8. Electron transfer by excited benzoquinone anions: slow rates for two-electron transitions.

    Science.gov (United States)

    Zamadar, Matibur; Cook, Andrew R; Lewandowska-Andralojc, Anna; Holroyd, Richard; Jiang, Yan; Bikalis, Jin; Miller, John R

    2013-09-05

    Electron transfer (ET) rate constants from the lowest excited state of the radical anion of benzoquinone, BQ(-•)*, were measured in THF solution. Rate constants for bimolecular electron transfer reactions typically reach the diffusion-controlled limit when the free-energy change, ΔG°, reaches -0.3 eV. The rate constants for ET from BQ(-•)* are one-to-two decades smaller at this energy and do not reach the diffusion-controlled limit until -ΔG° is 1.5-2.0 eV. The rates are so slow probably because a second electron must also undergo a transition to make use of the energy of the excited state. Similarly, ET, from solvated electrons to neutral BQ to form the lowest excited state, is slow, while fast ET is observed at a higher excited state, which can be populated in a transition involving only one electron. A simple picture based on perturbation theory can roughly account for the control of electron transfer by the need for transition of a second electron. The picture also explains how extra driving force (-ΔG°) can restore fast rates of electron transfer.

  9. Hot-Electron Transfer from Semiconductor Nanocrystals

    National Research Council Canada - National Science Library

    William A. Tisdale; Kenrick J. Williams; Brooke A. Timp; David J. Norris; Eray S. Aydil; X.-Y. Zhu

    2010-01-01

    ... that limits device efficiency. Although fabricating the semiconductor in a nanocrystalline morphology can slow this cooling, the transfer of hot carriers to electron and hole acceptors has not yet been thoroughly demonstrated...

  10. Improved thermally conducting electron transfer polymers

    Science.gov (United States)

    Jenkins, R. K.; Byrd, N. R.; Lister, J. L.

    1972-01-01

    Development of polymers with improved heat transfer coefficients for use in encapsulating electronic modules is discussed. Chemical reactions for synthesizing the polymers are described and thermodynamic and physical properties are analyzed.

  11. Fast Energy Transfer and Molecular Dynamics in the Electronic Ground State Of C{sub 2}H{sub 2} and H{sub 2}CO Viewed By Time Resolved FS-CARS

    Energy Technology Data Exchange (ETDEWEB)

    Knopp, G.; Beaud, P.; Radi, P.; Tulej, M.; Gerber, T.

    2004-03-01

    The molecular dynamics in the electronic ground state of C{sub 2}H{sub 2} and of H{sub 2}CO have been interrogated by the femto second CARS method. For a discussion of collision induced rotational and vibrational energy transfer in the electronic ground state of the polyatomic acetylene (C{sub 2H}2) molecule the transient signals were evaluated with the recently developed angular momentum and energy corrected scaling law. (author)

  12. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    Science.gov (United States)

    Skourtis, Spiros S.; Prytkova, Tatiana; Beratan, David N.

    2007-12-01

    This contribution describes molecular dynamics, semi-empirical and ab-initio studies of the primary photo-induced electron transfer reaction in DNA photolyase. DNA photolyases are FADH--containing proteins that repair UV-damaged DNA by photo-induced electron transfer. A DNA photolyase recognizes and binds to cyclobutatne pyrimidine dimer lesions of DNA. The protein repairs a bound lesion by transferring an electron to the lesion from FADH-, upon photo-excitation of FADH- with 350-450 nm light. We compute the lowest singlet excited states of FADH- in DNA photolyase using INDO/S configuration interaction, time-dependent density-functional, and time-dependent Hartree-Fock methods. The calculations identify the lowest singlet excited state of FADH- that is populated after photo-excitation and that acts as the electron donor. For this donor state we compute conformationally-averaged tunneling matrix elements to empty electron-acceptor states of a thymine dimer bound to photolyase. The conformational averaging involves different FADH--thymine dimer confromations obtained from molecular dynamics simulations of the solvated protein with a thymine dimer docked in its active site. The tunneling matrix element computations use INDO/S-level Green's function, energy splitting, and Generalized Mulliken-Hush methods. These calculations indicate that photo-excitation of FADH- causes a π→π* charge-transfer transition that shifts electron density to the side of the flavin isoalloxazine ring that is adjacent to the docked thymine dimer. This shift in electron density enhances the FADH--to-dimer electronic coupling, thus inducing rapid electron transfer.

  13. Flavin Charge Transfer Transitions Assist DNA Photolyase Electron Transfer

    Science.gov (United States)

    Skourtis, Spiros S.; Prytkova, Tatiana; Beratan, David N.

    2012-01-01

    This contribution describes molecular dynamics, semi-empirical and ab-initio studies of the primary photo-induced electron transfer reaction in DNA photolyase. DNA photolyases are FADH−-containing proteins that repair UV-damaged DNA by photo-induced electron transfer. A DNA photolyase recognizes and binds to cyclobutatne pyrimidine dimer lesions of DNA. The protein repairs a bound lesion by transferring an electron to the lesion from FADH−, upon photo-excitation of FADH− with 350–450 nm light. We compute the lowest singlet excited states of FADH− in DNA photolyase using INDO/S configuration interaction, time-dependent density-functional, and time-dependent Hartree-Fock methods. The calculations identify the lowest singlet excited state of FADH− that is populated after photo-excitation and that acts as the electron donor. For this donor state we compute conformationally-averaged tunneling matrix elements to empty electron- acceptor states of a thymine dimer bound to photolyase. The conformational averaging involves different FADH− - thymine dimer confromations obtained from molecular dynamics simulations of the solvated protein with a thymine dimer docked in its active site. The tunneling matrix element computations use INDO/S-level Green’s function, energy splitting, and Generalized Mulliken-Hush methods. These calculations indicate that photo-excitation of FADH− causes a π → π* charge-transfer transition that shifts electron density to the side of the flavin isoalloxazine ring that is adjacent to the docked thymine dimer. This shift in electron density enhances the FADH− - to - dimer electronic coupling, thus inducing rapid electron transfer. PMID:23226907

  14. Electron Transfer for Large Molecules through Delocalization

    Energy Technology Data Exchange (ETDEWEB)

    Neuhauser, D.; Reslan, R.; Hernandez, S.; Arnsen, C.; Lopata, K.; Govind, N.; Gao, Y.; Tolbert, S.; Schwartz, B.; Rubin, Y.; Nardes, A.; Kopidakis, N.

    2012-01-01

    Electron transfer for large molecules lies in between a Marcus-Theory two-state transfer and a Landauer description. We discuss a delocalization formalism which,through the introduction of artificial electric fields which emulate bulk dipole fields, allows calculation between a pair of identical molecules (A+A- (R)A-+A) with several open states. Dynamical electron polarization effects can be inserted with TDDFT and are crucial for large separations.

  15. Advances in electron transfer chemistry, v.6

    CERN Document Server

    Mariano, PS

    1999-01-01

    It is clear that electron transfer chemisty is now one of the most active areas of chemical study. Advances in Electron Transfer Chemistry has been designed to allow scientists who are developing new knowledge in this rapidly expanding area to describe their most recent research findings. This volume will serve those interested in learning about current breakthroughs in this rapidly expanding area of chemical research.

  16. Thermally conducting electron transfer polymers

    Science.gov (United States)

    Byrd, N. R.; Jenkins, R. K.; Lister, J. L.

    1969-01-01

    New polymeric material exhibits excellent physical shock protection, high electrical resistance, and thermal conductivity. It is especially useful for electronic circuitry, such as subminiaturization of components and modular construction of circuits.

  17. Heat Transfer Augmentation for Electronic Cooling

    Directory of Open Access Journals (Sweden)

    Suabsakul Gururatana

    2012-01-01

    Full Text Available Problem statement: The performance of electronic devices has been improving along with the rapid technology development. Cooling of electronic systems is consequently essential in controlling the component temperature and avoiding any hot spot. The study aims to review the present electronic cooling methods which are widely used in electronic devices. Approach: There are several methods to cool down the electronics components such as the pin-fin heat sink, confined jet impingement, heat pipe, micro heat sink and so on. Results: The cooling techniques can obviously increase heat transfer rate. Nonetheless, for active and passive cooling methods the pressure drop could extremely rise, when the heat transfer rate is increased. Conclusion: When the cooling techniques are used, it is clearly seen that the heat transfer increases with pressure drop. To avoid excessive expense due to high pressure drop, optimization method is required to obtain optimum cost and cooling rate.

  18. Photoselected electron transfer pathways in DNA photolyase.

    Science.gov (United States)

    Prytkova, Tatiana R; Beratan, David N; Skourtis, Spiros S

    2007-01-16

    Cyclobutane dimer photolyases are proteins that bind to UV-damaged DNA containing cyclobutane pyrimidine dimer lesions. They repair these lesions by photo-induced electron transfer. The electron donor cofactor of a photolyase is a two-electron-reduced flavin adenine dinucleotide (FADH(-)). When FADH(-) is photo-excited, it transfers an electron from an excited pi --> pi* singlet state to the pyrimidine dimer lesion of DNA. We compute the lowest excited singlet states of FADH(-) using ab initio (time-dependent density functional theory and time-dependent Hartree-Fock), and semiempirical (INDO/S configuration interaction) methods. The calculations show that the two lowest pi --> pi* singlet states of FADH(-) are localized on the side of the flavin ring that is proximal to the dimer lesion of DNA. For the lowest-energy donor excited state of FADH(-), we compute the conformationally averaged electronic coupling to acceptor states of the thymine dimer. The coupling calculations are performed at the INDO/S level, on donor-acceptor cofactor conformations obtained from molecular dynamics simulations of the solvated protein with a thymine dimer docked in its active site. These calculations demonstrate that the localization of the (1)FADH(-)* donor state on the flavin ring enhances the electronic coupling between the flavin and the dimer by permitting shorter electron-transfer pathways to the dimer that have single through-space jumps. Therefore, in photolyase, the photo-excitation itself enhances the electron transfer rate by moving the electron towards the dimer.

  19. Effects of surface wettability on fast liquid transfer

    Science.gov (United States)

    Chen, H.; Tang, T.; Amirfazli, A.

    2015-11-01

    A systematic experimental study was performed to understand the role of surface contact angles in affecting the process of fast liquid transfer. Surfaces with different wettabilities were used, and the transfer ratio (α, the amount of liquid transferred to the acceptor surface over the total amount of liquid) was measured for each pair of surfaces. A numerical model based on the volume of fluid method was developed to help understand the experimental results. The surface wettability was shown to significantly affect the boundaries between three regimes based on stretching speeds: quasi-static (surface force dominated), transition (surface/viscous/inertia forces all important) and dynamic (viscous/inertia forces dominated). Specifically, the values of the boundary speeds were found to increase with |α0 - 0.5|, where α0 is the transfer ratio in the quasi-static regime, and α0 is governed by the surface receding contact angles. Based on our results, an empirical equation to describe the transfer ratio as function of stretching speed was proposed. This equation can also be used as a prediction tool for the value of α for a fast transfer system.

  20. Fast electron microscopy via compressive sensing

    Science.gov (United States)

    Larson, Kurt W; Anderson, Hyrum S; Wheeler, Jason W

    2014-12-09

    Various technologies described herein pertain to compressive sensing electron microscopy. A compressive sensing electron microscope includes a multi-beam generator and a detector. The multi-beam generator emits a sequence of electron patterns over time. Each of the electron patterns can include a plurality of electron beams, where the plurality of electron beams is configured to impart a spatially varying electron density on a sample. Further, the spatially varying electron density varies between each of the electron patterns in the sequence. Moreover, the detector collects signals respectively corresponding to interactions between the sample and each of the electron patterns in the sequence.

  1. Electron transfer across a thermal gradient.

    Science.gov (United States)

    Craven, Galen T; Nitzan, Abraham

    2016-08-23

    Charge transfer is a fundamental process that underlies a multitude of phenomena in chemistry and biology. Recent advances in observing and manipulating charge and heat transport at the nanoscale, and recently developed techniques for monitoring temperature at high temporal and spatial resolution, imply the need for considering electron transfer across thermal gradients. Here, a theory is developed for the rate of electron transfer and the associated heat transport between donor-acceptor pairs located at sites of different temperatures. To this end, through application of a generalized multidimensional transition state theory, the traditional Arrhenius picture of activation energy as a single point on a free energy surface is replaced with a bithermal property that is derived from statistical weighting over all configurations where the reactant and product states are equienergetic. The flow of energy associated with the electron transfer process is also examined, leading to relations between the rate of heat exchange among the donor and acceptor sites as functions of the temperature difference and the electronic driving bias. In particular, we find that an open electron transfer channel contributes to enhanced heat transport between sites even when they are in electronic equilibrium. The presented results provide a unified theory for charge transport and the associated heat conduction between sites at different temperatures.

  2. Ultrafast Photoinduced Electron Transfer from Peroxide Dianion.

    Science.gov (United States)

    Anderson, Bryce L; Maher, Andrew G; Nava, Matthew; Lopez, Nazario; Cummins, Christopher C; Nocera, Daniel G

    2015-06-18

    The encapsulation of peroxide dianion by hexacarboxamide cryptand provides a platform for the study of electron transfer of isolated peroxide anion. Photoinitiated electron transfer (ET) between freely diffusing Ru(bpy)3(2+) and the peroxide dianion occurs with a rate constant of 2.0 × 10(10) M(-1) s(-1). A competing electron transfer quenching pathway is observed within an ion pair. Picosecond transient spectroscopy furnishes a rate constant of 1.1 × 10(10) s(-1) for this first-order process. A driving force dependence for the ET rate within the ion pair using a series of Ru(bpy)3(2+) derivatives allows for the electronic coupling and reorganization energies to be assessed. The ET reaction is nonadiabatic and dominated by a large inner-sphere reorganization energy, in accordance with that expected for the change in bond distance accompanying the conversion of peroxide dianion to superoxide anion.

  3. Unusual distance dependences of electron transfer rates.

    Science.gov (United States)

    Kuss-Petermann, Martin; Wenger, Oliver S

    2016-07-28

    Usually the rates for electron transfer (kET) decrease with increasing donor-acceptor distance, but Marcus theory predicts a regime in which kET is expected to increase when the transfer distance gets longer. Until recently, experimental evidence for such counter-intuitive behavior had been very limited, and consequently this effect is much less well-known than the Gaussian free energy dependence of electron transfer rates leading to the so-called inverted driving-force effect. This article presents the theoretical concepts that lead to the prediction of electron transfer rate maxima at large donor-acceptor distances, and it discusses conditions that are expected to favor experimental observations of such behavior. It continues with a consideration of specific recent examples in which electron transfer rates were observed to increase with increasing donor-acceptor distance, and it closes with a discussion of the importance of this effect in the context of light-to-chemical energy conversion.

  4. Electron transfer in ion-atom collisions

    Energy Technology Data Exchange (ETDEWEB)

    Lin, C D

    1979-01-01

    Recent theoretical development in the understanding of electron transfer processes is reviewed. K-K electron transfer processes are studied for projectiles (nuclear charge Z/sub B/) and targets (nuclear charge Z/sub A/) in which Z/sub A/ and Z/sub B/ range from Z/sub A/ much greater than Z/sub B/ to Z/sub A/ approx. = Z/sub B/, over the energy range 0.1 < v/v/sub e/ < 2. (GHT)

  5. Quantifying electron transfer reactions in biological systems

    DEFF Research Database (Denmark)

    Sjulstok, Emil Sjulstok; Olsen, Jógvan Magnus Haugaard; Solov'yov, Ilia A

    2015-01-01

    Various biological processes involve the conversion of energy into forms that are usable for chemical transformations and are quantum mechanical in nature. Such processes involve light absorption, excited electronic states formation, excitation energy transfer, electrons and protons tunnelling...... which for example occur in photosynthesis, cellular respiration, DNA repair, and possibly magnetic field sensing. Quantum biology uses computation to model biological interactions in light of quantum mechanical effects and has primarily developed over the past decade as a result of convergence between...... quantum physics and biology. In this paper we consider electron transfer in biological processes, from a theoretical view-point; namely in terms of quantum mechanical and semi-classical models. We systematically characterize the interactions between the moving electron and its biological environment...

  6. Facile Interfacial Electron Transfer of Hemoglobin

    Directory of Open Access Journals (Sweden)

    Chunhai Fan

    2005-12-01

    Full Text Available Abstract: We herein describe a method of depositing hemoglobin (Hb and sulfonated polyaniline (SPAN on GC electrodes that facilitate interfacial protein electron transfer. Well-defined, reproducible, chemically reversible peaks of Hb and SPAN can be obtained in our experiments. We also observed enhanced peroxidase activity of Hb in SPAN films. These results clearly showed that SPAN worked as molecular wires and effectively exchanged electrons between Hb and electrodes.Mediated by Conjugated Polymers

  7. The description of charge transfer in fast negative ions scattering on water covered Si(100) surfaces

    Science.gov (United States)

    Chen, Lin; Qiu, Shunli; Liu, Pinyang; Xiong, Feifei; Lu, Jianjie; Liu, Yuefeng; Li, Guopeng; Liu, Yiran; Ren, Fei; Xiao, Yunqing; Gao, Lei; Zhao, Qiushuang; Ding, Bin; Li, Yuan; Guo, Yanling; Chen, Ximeng

    2016-11-01

    Doping has significantly affected the characteristics and performance of semiconductor electronic devices. In this work, we study the charge transfer processes for 8.5-22.5 keV C- and F- ions scattering on H2O-terminated p-type Si(100) surfaces with two different doping concentrations. We find that doping has no influence on negative-ion formation for fast collisions in this relatively high energy range. Moreover, we build a model to calculate negative ion fractions including the contribution from positive ions. The calculations support the nonadiabatic feature of charge transfer.

  8. Transfer Printed Crystalline Nanomembrane for Versatile Electronic Applications

    Science.gov (United States)

    Seo, Jung-Hun

    Flexible electronics have traditionally been addressed low-frequency applications, since the materials for the traditional flexible electronics, such as polymer and non-crystalline inorganic semiconductors, have poor electronic properties. Fast flexible electronics that operate at radio frequencies (RF), particularly at microwave frequencies, could lead to a number of novel RF applications where rigid chip-based solid-state electronics cannot easily fulfill. Single-crystal semiconductor nanomembranes (NM) that can be released from a number of wafer sources are mechanically very flexible yet exhibit outstanding electronic properties that are equivalent to their bulky counterparts. These thin flexible single-crystal materials can furthermore be placed, via transfer printing techniques, to nearly any substrate, including flexible polymers, thus creating the opportunity to realize RF flexible electronics. In this thesis, various RF transistors made of semiconductor NMs on plastic substrates will be discussed. In addition, as a photonic application, the demonstration of large-area Si NM surface normal ultra-compact photonic crystal reflectors fabricated using the laser interference lithography technique (LIL) will be discussed. Particularly, the mechanism of LIL and NM transfer without using an adhesive layer will be introduced and their optical performance will be addressed. Lastly, the realization of selective substitutional boron doping, using heavily doped Si NM as a doping source, will be discussed. A detailed mechanism using computational modeling and experimental analyses will be provided. The fabrication of high voltage diamond p-i diodes and their performance will be discussed.

  9. Single electron capture in fast ion-atom collisions

    Science.gov (United States)

    Milojević, Nenad

    2014-12-01

    Single-electron capture cross sections in collisions between fast bare projectiles and heliumlike atomic systems are investigated by means of the four-body boundary-corrected first Born (CB1-4B) approximation. The prior and post transition amplitudes for single charge exchange encompassing symmetric and asymmetric collisions are derived in terms of twodimensional real integrals in the case of the prior form and five-dimensional quadratures for the post form. The dielectronic interaction V12 = 1/r12 = 1/|r1 - r2| explicitly appears in the complete perturbation potential Vf of the post transition probability amplitude T+if. An illustrative computation is performed involving state-selective and total single capture cross sections for the p - He (prior and post form) and He2+, Li3+Be4+B5+C6+ - He (prior form) collisions at intermediate and high impact energies. We have also studied differential cross sections in prior and post form for single electron transfer from helium by protons. The role of dynamic correlations is examined as a function of increased projectile energy. Detailed comparisons with the measurements are carried out and the obtained theoretical cross sections are in reasonable agreement with the available experimental data.

  10. 75 FR 16579 - Electronic Fund Transfers

    Science.gov (United States)

    2010-04-01

    ... From the Federal Register Online via the Government Publishing Office ] Part II Federal Reserve System 12 CFR Part 205 Electronic Fund Transfers; Final Rule #0;#0;Federal Register / Vol. 75 , No. 62... Consumers from Hidden Gift Card Fees Secretly Draining Shoppers' Pockets'', Press Release, Mar. 27,...

  11. Electronic Energy Transfer in Polarizable Heterogeneous Environments

    DEFF Research Database (Denmark)

    Svendsen, Casper Steinmann; Kongsted, Jacob

    2015-01-01

    Theoretical prediction of transport and optical properties of protein-pigment complexes is of significant importance when aiming at understanding the structure versus function relationship in such systems. Electronic energy transfer (EET) couplings represent a key property in this respect since...

  12. Clocked, fast electronics trigger for high energy physics

    Energy Technology Data Exchange (ETDEWEB)

    Gray, R.; Rutherfoord, J.P.

    1986-04-01

    For a Fermilab experiment we have designed and built gated-pulse-stretcher modules which allow us to clock all of the fast electronics with the accelerator rf, thus simplifying the trigger design. (orig.).

  13. Nonlocal bacterial electron transfer to hematite surfaces

    Science.gov (United States)

    Rosso, Kevin M.; Zachara, John M.; Fredrickson, Jim K.; Gorby, Yuri A.; Smith, Steven C.

    2003-03-01

    Mechanisms by which dissimilatory iron-reducing bacteria utilize iron and manganese oxide minerals as terminal electron acceptors for respiration are poorly understood. In the absence of exogenous electron shuttle compounds, extracellular electron transfer is generally thought to occur through the interfacial contact area between mineral surfaces and attached cells. Possible alternative reduction pathways have been proposed based on the discovery of a link between an excreted quinone and dissimilatory reduction. In this study, we utilize a novel experimental approach to demonstrate that Shewanella putrefaciens reduces the surface of crystalline iron oxides at spatial locations that are distinct from points of attachment.

  14. Collimation of fast electrons in critical density plasma channel

    OpenAIRE

    2015-01-01

    Significantly collimated fast electron beam with a divergence angle 10° (FWHM) is generated through the interaction of ultra-intense laser light with a uniform critical density plasma in experiments and 2D PIC simulations. In the experiment, the uniform critical density plasma is created by ionizing an ultra-low density foam target. The spacial distribution of the fast electron is observed by Imaging Plate. 2D PIC simulation and post process analysis reveal magnetic collimation of energetic e...

  15. Electron transfer rates and equilibrium within cytochrome c oxidase

    DEFF Research Database (Denmark)

    Farver, O; Einarsdóttir, O; Pecht, I

    2000-01-01

    identical within experimental error and independent of the enzyme concentration. This demonstrates that a fast intramolecular electron equilibration is taking place between CuA and heme a. The rate constants for CuA --> heme a ET and the reverse (heme a --> CuA) process were found to be 13 000 s-1 and 3700......Intramolecular electron transfer (ET) between the CuA center and heme a in bovine cytochrome c oxidase was investigated by pulse radiolysis. CuA, the initial electron acceptor, was reduced by 1-methyl nicotinamide radicals in a diffusion-controlled reaction, as monitored by absorption changes...... at 830 nm. After the initial reduction phase, the 830 nm absorption was partially restored, corresponding to reoxidation of the CuA center. Concomitantly, the absorption at 445 nm and 605 nm increased, indicating reduction of heme a. The rate constants for heme a reduction and CuA reoxidation were...

  16. Suppression effects of Weibel instability for fast electron divergence

    Directory of Open Access Journals (Sweden)

    Sakagami H.

    2013-11-01

    Full Text Available Quasi-static magnetic fields, which are induced by the Weibel instability and grow to more than hundred Megagauss, lead to large divergence angle of fast electrons, hence lower energy coupling. To suppress the divergence, two different structures, namely density trough and punched out holes, are introduced to targets. In the density trough target, the Weibel instability is enhanced and the divergence is getting worse. On the other hand, the divergence angle is improved but the number of electrons is degraded for fast electrons (<3 MeV in the punched out target.

  17. Biotechnological Aspects of Microbial Extracellular Electron Transfer

    Science.gov (United States)

    Kato, Souichiro

    2015-01-01

    Extracellular electron transfer (EET) is a type of microbial respiration that enables electron transfer between microbial cells and extracellular solid materials, including naturally-occurring metal compounds and artificial electrodes. Microorganisms harboring EET abilities have received considerable attention for their various biotechnological applications, in addition to their contribution to global energy and material cycles. In this review, current knowledge on microbial EET and its application to diverse biotechnologies, including the bioremediation of toxic metals, recovery of useful metals, biocorrosion, and microbial electrochemical systems (microbial fuel cells and microbial electrosynthesis), were introduced. Two potential biotechnologies based on microbial EET, namely the electrochemical control of microbial metabolism and electrochemical stimulation of microbial symbiotic reactions (electric syntrophy), were also discussed. PMID:26004795

  18. Modelling the inelastic scattering of fast electrons

    Energy Technology Data Exchange (ETDEWEB)

    Allen, L.J., E-mail: lja@unimelb.edu.au [School of Physics, University of Melbourne, Parkville, Victoria 3010 (Australia); D' Alfonso, A.J., E-mail: a.j@dalfonso.com.au [School of Physics, University of Melbourne, Parkville, Victoria 3010 (Australia); Findlay, S.D. [School of Physics, Monash University, Clayton, Victoria 3800 (Australia)

    2015-04-15

    Imaging at atomic resolution based on the inelastic scattering of electrons has become firmly established in the last three decades. Harald Rose pioneered much of the early theoretical work on this topic, in particular emphasising the role of phase and the importance of a mixed dynamic form factor. In this paper we review how the modelling of inelastic scattering has subsequently developed and how numerical implementation has been achieved. A software package μSTEM is introduced, capable of simulating various imaging modes based on inelastic scattering in both scanning and conventional transmission electron microscopy. - Highlights: • Harald Rose was a pioneer of important work on atomic resolution imaging using inelastic scattering. • We review how the modelling of inelastic scattering has subsequently developed and been applied. • A software package μSTEM is introduced, capable of simulating various inelastic imaging modes.

  19. Promoting Interspecies Electron Transfer with Biochar

    Science.gov (United States)

    Chen, Shanshan; Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Malvankar, Nikhil S.; Liu, Fanghua; Fan, Wei; Nevin, Kelly P.; Lovley, Derek R.

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with Geobacter sulfurreducens or Methanosarcina barkeri in which ethanol was the electron donor. Cells were attached to the biochar, yet not in close contact, suggesting that electrons were likely conducted through the biochar, rather than biological electrical connections. The finding that biochar can stimulate DIET may be an important consideration when amending soils with biochar and can help explain why biochar may enhance methane production from organic wastes under anaerobic conditions. PMID:24846283

  20. Promoting interspecies electron transfer with biochar

    DEFF Research Database (Denmark)

    Chen, Shanshan; Rotaru, Amelia-Elena; Shrestha, Pravin Malla

    2014-01-01

    Biochar, a charcoal-like product of the incomplete combustion of organic materials, is an increasingly popular soil amendment designed to improve soil fertility. We investigated the possibility that biochar could promote direct interspecies electron transfer (DIET) in a manner similar...... to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with Geobacter sulfurreducens or Methanosarcina barkeri in which ethanol was the electron donor. Cells were...... attached to the biochar, yet not in close contact, suggesting that electrons were likely conducted through the biochar, rather than biological electrical connections. The finding that biochar can stimulate DIET may be an important consideration when amending soils with biochar and can help explain why...

  1. Education and solar conversion. Demonstrating electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Smestad, Greg P. [Institute of Physical Chemistry, ICP-2, Swiss Federal Institute of Technology, EPFL, CH-1015 Lausanne (Switzerland)

    1998-07-23

    A simplified solar cell fabrication procedure is presented that uses natural anthocyanin or chlorophyll dyes extracted from plants. This procedure illustrates how interdisciplinary science can be taught at lower division university and upper division high school levels for an understanding of renewable energy as well as basic science concepts. Electron transfer occurs on the Earth in the mitochondrial membranes found in living cells, and in the thylakoid membranes found in the photosynthetic cells of green plants. Since we depend on the results of this electron and energy transfer, e.g. in our use of petroleum and agricultural products, it is desirable to understand and communicate how the electron transfer works. The simplified solar cell fabrication procedure, based on nanocrystalline dye-sensitized solar cells, has therefore been developed so that it can be inexpensively reproduced and utilized in the teaching of basic principles in biology, chemistry, physics, and environmental science. A water-based solution of commercial nanocrystalline titanium dioxide (TiO{sub 2}) powder is used to deposit a highly porous semiconductor electron acceptor. This acceptor couples the light-driven processes occurring at an organic dye to the macroscopic world and an external electrical circuit. Materials science and semiconductor physics are emphasized during the deposition of the sintered TiO{sub 2} nanocrystalline ceramic film. Chelation, complexation and molecular self-assembly are demonstrated during the attachment of the dye molecule to the surface of the TiO{sub 2} semiconductor particles. Environmental chemistry and energy conversion can be linked to these concepts via the regenerative oxidation and reduction cycle found in the cell. The resulting device, made in under 3 h, can be used as a light detector or power generator that produces 0.4-0.5 V at open circuit, and 1-2 mA per square cm under solar illumination

  2. Heat transfer in high density electronics packaging

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In order to get an insight into the thermal characteristic and to evaluate the thermal reliability of the "System in Packaging"(SIP), a new solution of electronics packaging, a heat transfer model of SIP was developed to predict the heat dissipation capacity and to investigate the effect of different factors on the temperature distribution in the electronics. The affecting parameters under consideration include the thermophysical properties of the substrates, the coefficient of convection heat transfer, the thickness of the chip, and the density of power dissipation. ALGOR, a kind of finite element analysis software,was used to do the model simulation. Based on the sinulation and analysis of the heat conduction and convection resistance, criteria for the thermal design were established and possible measurement for enhancing power dissipation was provided, The results show that the heat transfer model provides a new and effective way to the thermal design and thermal analysis of SIP and to the mechanical analysis for the further investigation of SIP.

  3. Shutterless ion mobility spectrometer with fast pulsed electron source

    Science.gov (United States)

    Bunert, E.; Heptner, A.; Reinecke, T.; Kirk, A. T.; Zimmermann, S.

    2017-02-01

    Ion mobility spectrometers (IMS) are devices for fast and very sensitive trace gas analysis. The measuring principle is based on an initial ionization process of the target analyte. Most IMS employ radioactive electron sources, such as 63Ni or 3H. These radioactive materials have the disadvantage of legal restrictions and the electron emission has a predetermined intensity and cannot be controlled or disabled. In this work, we replaced the 3H source of our IMS with 100 mm drift tube length with our nonradioactive electron source, which generates comparable spectra to the 3H source. An advantage of our emission current controlled nonradioactive electron source is that it can operate in a fast pulsed mode with high electron intensities. By optimizing the geometric parameters and developing fast control electronics, we can achieve very short electron emission pulses for ionization with high intensities and an adjustable pulse width of down to a few nanoseconds. This results in small ion packets at simultaneously high ion densities, which are subsequently separated in the drift tube. Normally, the required small ion packet is generated by a complex ion shutter mechanism. By omitting the additional reaction chamber, the ion packet can be generated directly at the beginning of the drift tube by our pulsed nonradioactive electron source with only slight reduction in resolving power. Thus, the complex and costly shutter mechanism and its electronics can also be omitted, which leads to a simple low-cost IMS-system with a pulsed nonradioactive electron source and a resolving power of 90.

  4. Fast and Reliable Evaluation of Preservice Teacher Electronic Portfolios

    Science.gov (United States)

    Sulzen, James; Young, Michael F.

    2007-01-01

    This study describes a rubric supporting fast and reliable assessment of preservice teacher electronic portfolios. The assessment calls for raters to quickly scan a portfolio to gain an overall impression, then dichotomously score a large number of indicators (e.g., educational philosophy, educational technology use, imaginative use of…

  5. Electron transfer pathways in microbial oxygen biocathodes

    Energy Technology Data Exchange (ETDEWEB)

    Freguia, Stefano, E-mail: stefano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Tsujimura, Seiya, E-mail: seiya@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan); Kano, Kenji, E-mail: kkano@kais.kyoto-u.ac.j [Bio-analytical and Physical Chemistry Laboratory, Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8205 (Japan)

    2010-01-01

    The ability of some bacteria to enhance the rate of cathodic oxygen reduction to water has been recently discovered, opening the way to an entirely renewable and environmentally friendly concept of biocathode. In this study we reveal that several mechanisms may induce catalytic effects by bacteria. These comprise mechanisms that are putatively beneficial to the bacteria as well as mechanisms which are merely side effects, including quinone autoxidation and direct O{sub 2} reduction by heme compounds. Here we showed that 1 muM of ACNQ is able to generate a significant catalytic wave for oxygen reduction, with onset at approximately 0 V vs. SHE. Similarly, adsorption of hemin on a carbon surface catalyses O{sub 2} reduction to H{sub 2}O{sub 2} with an onset of +0.2 V vs. SHE. To evaluate the catalytic pathways of live cells on cathodic oxygen reduction, two species of electrochemically active bacteria were selected as pure cultures, namely Acinetobacter calcoaceticus and Shewanella putrefaciens. The former appears to exploit a self-excreted redox compound with redox characteristics matching those of pyrroloquinoline quinone (PQQ) for extracellular electron transfer. The latter appears to utilise outer membrane-bound redox compounds. Interaction of quinones and cytochromes with the membrane-bound electron transfer chain is yet to be proven.

  6. Mediated Electron Transfer at Redox Active Monolayers

    Directory of Open Access Journals (Sweden)

    Michael E.G. Lyons

    2001-12-01

    Full Text Available A theoretical model describing the transport and kinetic processes involved in heterogeneous redox catalysis of solution phase reactants at electrode surfaces coated with redox active monolayers is presented. Although the analysis presented has quite general applicability, a specific focus of the paper is concerned with the idea that redox active monolayers can be used to model an ensemble of individual molecular nanoelectrodes. Three possible rate determining steps are considered: heterogeneous electron transfer between immobilized mediator and support electrode ; bimolecular chemical reaction between redox mediator and reactant species in the solution phase, and diffusional mass transport of reactant in solution. A general expression for the steady state reaction flux is derived which is valid for any degree of reversibility of both the heterogeneous electron transfer reaction involving immobilized mediator species and of the bimolecular cross exchange reaction between immobilized mediator and solution phase reactant. The influence of reactant transport in solution is also specifically considered. Simplified analytical expressions for the net reaction flux are derived for experimentally reasonable situations and a kinetic case diagram is constructed outlining the relationships between the various approximate solutions. The theory enables simple diagnostic plots to be constructed which can be used to analyse experimental data.

  7. Glow discharges with electrostatic confinement of fast electrons

    Science.gov (United States)

    Kolobov, V. I.; Metel, A. S.

    2015-06-01

    This review presents a unified treatment of glow discharges with electrostatic confinement of fast electrons. These discharges include hollow cathode discharges, wire and cage discharges, reflect discharges with brush and multirod cathodes, and discharges in crossed electric and magnetic fields. Fast electrons bouncing inside electrostatic traps provide efficient ionization of gas at very low gas pressures. The electrostatic trap effect (ETE) was first observed by Paschen in hollow cathode discharges almost a century ago. The key parameters that define fundamental characteristics of ETE discharges are the ionization length λN, the penetration range, Λ, and the diffusion length λ of the fast electrons, and two universal geometric parameters of the traps: effective width a and length L. Peculiarities of electron kinetics and ion collection mechanism explain experimental observations for different trap geometries. The ETE is observed only at Λ > a, when the penetration range of the γ-electrons emitted by the cathode exceeds the trap width. In the optimal pressure range, when λN > a, and Λ current, Uc tends to its upper limit W/eβγ, where β is the percentage of ions arriving at the cathode and W is the gas ionization cost. In the low-pressure range, Λ > L, Uc rises from hundreds to thousands of volts. The sign of the anode potential fall, Ua, depends on the anode surface Sa and its position. When Sa is large compared to a critical value S*, Ua is negative and small. At Sa value of Ua becomes positive and rises up to 0.5-1 kV with decreasing p ultimately causing discharge extinction. Scaling laws indicate common physics between vacuum discharges and atmospheric pressure micro-discharges. We discuss peculiarities of electron kinetics under different conditions using semi-analytical models. Recent experimental results and applications of glow discharges with electrostatic confinement of fast electrons are described.

  8. INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS

    NARCIS (Netherlands)

    Bartoloni, Fernando Heering; Monteiro Leite Ciscato, Luiz Francisco; Augusto, Felipe Alberto; Baader, Wilhelm Josef

    2010-01-01

    INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS. Chemiluminescence properties of the peroxyoxalate reaction in the presence of activators bearing electron withdrawing substituents were studied, to evaluate the possible occurrence of an inverse electron tr

  9. INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS

    NARCIS (Netherlands)

    Bartoloni, Fernando Heering; Monteiro Leite Ciscato, Luiz Francisco; Augusto, Felipe Alberto; Baader, Wilhelm Josef

    2010-01-01

    INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS. Chemiluminescence properties of the peroxyoxalate reaction in the presence of activators bearing electron withdrawing substituents were studied, to evaluate the possible occurrence of an inverse electron tr

  10. INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS

    NARCIS (Netherlands)

    Bartoloni, Fernando Heering; Monteiro Leite Ciscato, Luiz Francisco; Augusto, Felipe Alberto; Baader, Wilhelm Josef

    2010-01-01

    INVERSE ELECTRON TRANSFER IN PEROXYOXALATE CHEMIEXCITATION USING EASILY REDUCIBLE ACTIVATORS. Chemiluminescence properties of the peroxyoxalate reaction in the presence of activators bearing electron withdrawing substituents were studied, to evaluate the possible occurrence of an inverse electron

  11. Fast Magnetic Reconnection Due to Anisotropic Electron Pressure

    CERN Document Server

    Cassak, P A; Fermo, R L; Beidler, M T; Shay, M A; Swisdak, M; Drake, J F; Karimabadi, H

    2015-01-01

    A new regime of fast magnetic reconnection with an out-of-plane (guide) magnetic field is reported in which the key role is played by an electron pressure anisotropy described by the Chew-Goldberger-Low gyrotropic equations of state in the generalized Ohm's law, which even dominates the Hall term. A description of the physical cause of this behavior is provided and two-dimensional fluid simulations are used to confirm the results. The electron pressure anisotropy causes the out-of-plane magnetic field to develop a quadrupole structure of opposite polarity to the Hall magnetic field and gives rise to dispersive waves. In addition to being important for understanding what causes reconnection to be fast, this mechanism should dominate in plasmas with low plasma beta and a high in-plane plasma beta with electron temperature comparable to or larger than ion temperature, so it could be relevant in the solar wind and some tokamaks.

  12. Electron transfer at sensitized semiconductor electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Spitler, M.T.

    1977-03-01

    Electron transfer from the excited state of sensitizing dyes to the conduction band of semiconductors has been studied through photoelectrochemical techniques. Two systems were analyzed in detail: rhodamine B on ZnO and rose bengal on TiO/sub 2/. Prior to electrochemical experimentation, the adsorption characteristics of these dyes were investigated using ZnO, ZnS, and TiO/sub 2/ single crystals as substrates. Absorbance measurements of the adsorbed dye were taken as a function of the solution concentration of the dye. Adsorption isotherms heats of adsorption were also established; they were similar to literature data reported for adsorption of these dyes on powdered substrates. Using the absorbance data, the quantum efficiency for photoinjection of electrons from rhodamine B into a ZnO electrode was determined to be 2.7 x 10/sup -2/. This value was independent of the dye surface concentration down to 50% coverage of the electrode. With the assumption that not all of the rhodamine B adsorbed on the electrode has the same rate of electron injection, a kinetic model for the time decay of the photocurrent was developed; data were analyzed according to this theory. A rate constant for photoreduction of the adsorbed dye was determined for the reducing agents. 86 references.

  13. Transfer line TT70 (electrons from PS to SPS)

    CERN Multimedia

    CERN PhotoLab

    1981-01-01

    As injectors for LEP, PS and SPS had to be converted to the acceleration of electrons and positrons. So far, only positively charged particles had been transferred from the PS to the SPS, for the negatively charged electrons a new transfer line, TT70, had to be built. Due to the difference in level of the two machines, the transfer line slopes and tilts.

  14. Controlling the fast electron divergence in a solid target with multiple laser pulses

    Science.gov (United States)

    Volpe, L.; Feugeas, J.-L.; Nicolai, Ph.; Santos, J. J.; Touati, M.; Breil, J.; Batani, D.; Tikhonchuk, V.

    2014-12-01

    Controlling the divergence of laser-driven fast electrons is compulsory to meet the ignition requirements in the fast ignition inertial fusion scheme. It was shown recently that using two consecutive laser pulses one can improve the electron-beam collimation. In this paper we propose an extension of this method by using a sequence of several laser pulses with a gradually increasing intensity. Profiling the laser-pulse intensity opens a possibility to transfer to the electron beam a larger energy while keeping its divergence under control. We present numerical simulations performed with a radiation hydrodynamic code coupled to a reduced kinetic module. Simulation with a sequence of three laser pulses shows that the proposed method allows one to improve the efficiency of the double pulse scheme at least by a factor of 2. This promises to provide an efficient energy transport in a dense matter by a collimated beam of fast electrons, which is relevant for many applications such as ion-beam sources and could present also an interest for fast ignition inertial fusion.

  15. GPU-accelerated computation of electron transfer.

    Science.gov (United States)

    Höfinger, Siegfried; Acocella, Angela; Pop, Sergiu C; Narumi, Tetsu; Yasuoka, Kenji; Beu, Titus; Zerbetto, Francesco

    2012-11-05

    Electron transfer is a fundamental process that can be studied with the help of computer simulation. The underlying quantum mechanical description renders the problem a computationally intensive application. In this study, we probe the graphics processing unit (GPU) for suitability to this type of problem. Time-critical components are identified via profiling of an existing implementation and several different variants are tested involving the GPU at increasing levels of abstraction. A publicly available library supporting basic linear algebra operations on the GPU turns out to accelerate the computation approximately 50-fold with minor dependence on actual problem size. The performance gain does not compromise numerical accuracy and is of significant value for practical purposes. Copyright © 2012 Wiley Periodicals, Inc.

  16. Visualizing fast electron energy transport into laser-compressed high-density fast-ignition targets

    Science.gov (United States)

    Jarrott, L. C.; Wei, M. S.; McGuffey, C.; Solodov, A. A.; Theobald, W.; Qiao, B.; Stoeckl, C.; Betti, R.; Chen, H.; Delettrez, J.; Döppner, T.; Giraldez, E. M.; Glebov, V. Y.; Habara, H.; Iwawaki, T.; Key, M. H.; Luo, R. W.; Marshall, F. J.; McLean, H. S.; Mileham, C.; Patel, P. K.; Santos, J. J.; Sawada, H.; Stephens, R. B.; Yabuuchi, T.; Beg, F. N.

    2016-05-01

    Recent progress in kilojoule-scale high-intensity lasers has opened up new areas of research in radiography, laboratory astrophysics, high-energy-density physics, and fast-ignition (FI) laser fusion. FI requires efficient heating of pre-compressed high-density fuel by an intense relativistic electron beam produced from laser-matter interaction. Understanding the details of electron beam generation and transport is crucial for FI. Here we report on the first visualization of fast electron spatial energy deposition in a laser-compressed cone-in-shell FI target, facilitated by doping the shell with copper and imaging the K-shell radiation. Multi-scale simulations accompanying the experiments clearly show the location of fast electrons and reveal key parameters affecting energy coupling. The approach provides a more direct way to infer energy coupling and guide experimental designs that significantly improve the laser-to-core coupling to 7%. Our findings lay the groundwork for further improving efficiency, with 15% energy coupling predicted in FI experiments using an existing megajoule-scale laser driver.

  17. Respiratory electron transfer in Escherichia coli : components, energetics and regulation

    NARCIS (Netherlands)

    Bekker, M.

    2009-01-01

    The respiratory chain that is housed in the bacterial cytoplasmic membrane, generally transfers electrons from NADH to oxygen; in the absence of oxygen it can use several alternative electron acceptors, such as nitrate and fumarate. Transfer of electrons through this chain is usually coupled to the

  18. Soliton-like Solutions and Electron Transfer in DNA.

    Science.gov (United States)

    Lakhno, V D

    2000-06-01

    We consider various mechanisms of long-range electron transfer in DNAwhich enable us to explain recent controversial experiments. We show thatcontinuous super-exchange theory can explain the values of electron rateconstants in short fragments of DNA. The soliton-type electron transfer inlong segments of DNA is also dealt with.

  19. Soliton-like Solutions and Electron Transfer in DNA

    OpenAIRE

    Lakhno, V.D.

    2000-01-01

    We consider various mechanisms of long-range electron transfer in DNAwhich enable us to explain recent controversial experiments. We show thatcontinuous super-exchange theory can explain the values of electron rateconstants in short fragments of DNA. The soliton-type electron transfer inlong segments of DNA is also dealt with.

  20. Electronic and Nuclear Factors in Charge and Excitation Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Piotr Piotrowiak

    2004-09-28

    We report the and/or state of several subprojects of our DOE sponsored research on Electronic and Nuclear Factors in Electron and Excitation Transfer: (1) Construction of an ultrafast Ti:sapphire amplifier. (2) Mediation of electronic interactions in host-guest molecules. (3) Theoretical models of electrolytes in weakly polar media. (4) Symmetry effects in intramolecular excitation transfer.

  1. Respiratory electron transfer in Escherichia coli : components, energetics and regulation

    NARCIS (Netherlands)

    Bekker, M.

    2009-01-01

    The respiratory chain that is housed in the bacterial cytoplasmic membrane, generally transfers electrons from NADH to oxygen; in the absence of oxygen it can use several alternative electron acceptors, such as nitrate and fumarate. Transfer of electrons through this chain is usually coupled to the

  2. Fast instability caused by electron cloud in combined function magnets

    Directory of Open Access Journals (Sweden)

    S. A. Antipov

    2017-04-01

    Full Text Available One of the factors which may limit the intensity in the Fermilab Recycler is a fast transverse instability. It develops within a hundred turns and, in certain conditions, may lead to a beam loss. The high rate of the instability suggests that its cause is electron cloud. We studied the phenomena by observing the dynamics of stable and unstable beams, simulating numerically the buildup of the electron cloud, and developed an analytical model of an electron cloud driven instability with the electrons trapped in combined function dipoles. We found that beam motion can be stabilized by a clearing bunch, which confirms the electron cloud nature of the instability. The clearing suggest electron cloud trapping in Recycler combined function magnets. Numerical simulations show that up to 1% of the particles can be trapped by the magnetic field. Since the process of electron cloud buildup is exponential, once trapped this amount of electrons significantly increases the density of the cloud on the next revolution. In a Recycler combined function dipole this multiturn accumulation allows the electron cloud to reach final intensities orders of magnitude greater than in a pure dipole. The estimated resulting instability growth time of about 30 revolutions and the mode frequency of 0.4 MHz are consistent with experimental observations and agree with the simulation in the pei code. The created instability model allows investigating the beam stability for the future intensity upgrades.

  3. Fast Instability Caused by Electron Cloud in Combined Function Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Antipov, S. A. [Chicago U.; Adamson, P. [Fermilab; Burov, A. [Fermilab; Nagaitsev, S. [Fermilab; Yang, M. J. [Fermilab

    2016-12-12

    One of the factors which may limit the intensity in the Fermilab Recycler is a fast transverse instability. It develops within a hundred turns and, in certain conditions, may lead to a beam loss. The high rate of the instability suggest that its cause is electron cloud. We studied the phenomena by observing the dynamics of stable and unstable beam, simulating numerically the build-up of the electron cloud, and developed an analytical model of an electron cloud driven instability with the electrons trapped in combined function di-poles. We found that beam motion can be stabilized by a clearing bunch, which confirms the electron cloud nature of the instability. The clearing suggest electron cloud trapping in Recycler combined function mag-nets. Numerical simulations show that up to 1% of the particles can be trapped by the magnetic field. Since the process of electron cloud build-up is exponential, once trapped this amount of electrons significantly increases the density of the cloud on the next revolution. In a Recycler combined function dipole this multi-turn accumulation allows the electron cloud reaching final intensities orders of magnitude greater than in a pure dipole. The estimated resulting instability growth rate of about 30 revolutions and the mode fre-quency of 0.4 MHz are consistent with experimental observations and agree with the simulation in the PEI code. The created instability model allows investigating the beam stability for the future intensity upgrades.

  4. Test and calibration of the IDS fast-timing electronics

    CERN Document Server

    AUTHOR|(CDS)2160817

    2016-01-01

    The ISOLDE decay station(IDS) is one of the permanent experimental setups at the ISOLDE facility of CERN. IDS is used to study decay properties of radioactive nuclei. Thus, fast-timing electronics are necessary for extracting nuclear half-lives. The aims of this work are testing and optimization of the IDS fast-timing electronics as well as measuring a nuclear level half-life in the decay of $^{152}$Eu. The energy resolution of LaBr$_3$ $\\gamma$-detectors was characterized and optimized. A nuclear level lifetime of $^{152}$Eu was measured after obtaining the best parameters for energy resolution and time walk. Dedicated sorting scripts were developed in ROOT in order of perform the characterization and optimization automatically.

  5. Theory of interrelated electron and proton transfer processes

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2003-01-01

    A simple theory of elementary act of interrelated reactions of electron and proton transfer is developed. Mechanisms of synchronous and multistage transfer and coherent transitions via a dynamically populated intermediate state are discussed. Formulas for rate constants of adiabatic and nonadiaba......A simple theory of elementary act of interrelated reactions of electron and proton transfer is developed. Mechanisms of synchronous and multistage transfer and coherent transitions via a dynamically populated intermediate state are discussed. Formulas for rate constants of adiabatic...

  6. [Electron transfer between globular proteins. Evaluation of a matrix element].

    Science.gov (United States)

    Lakhno, V D; Chuev, G N; Ustinin, M N

    1998-01-01

    The dependence of the matrix element of the probability of interprotein electron transfer on the mutual orientation of the donor and acceptor centers and the distance between them was calculated. The calculations were made under the assumption that electron transfer proceeds mainly by a collective excitation of polaron nature, like a solvated electron state. The results obtained are consistent with experimental data and indicate the nonexponential behavior of this dependence in the case when the distance transfer is less than 20 A.

  7. Electron transfer and interfacial behavior of redox proteins

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    This paper reviews the recent progress in the electron transfer and interfacial behavior of redox proteins. Significant achievements in the relevant fields are summarized including the direct electron transfer between proteins and electrodes, the thermodynamic and kinetic properties, catalytic activities and activity regulation of the redox proteins. It has been demonstrated that the electrochemical technique is an effective tool for protein studies, especially for probing into the electron transfer and interfacial behavior of redox proteins.

  8. Transcriptomic and genetic analysis of direct interspecies electron transfer

    DEFF Research Database (Denmark)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Summers, Zarath M

    2013-01-01

    The possibility that metatranscriptomic analysis could distinguish between direct interspecies electron transfer (DIET) and H2 interspecies transfer (HIT) in anaerobic communities was investigated by comparing gene transcript abundance in cocultures in which Geobacter sulfurreducens was the elect......The possibility that metatranscriptomic analysis could distinguish between direct interspecies electron transfer (DIET) and H2 interspecies transfer (HIT) in anaerobic communities was investigated by comparing gene transcript abundance in cocultures in which Geobacter sulfurreducens....... These results demonstrate that there are unique gene expression patterns that distinguish DIET from HIT and suggest that metatranscriptomics may be a promising route to investigate interspecies electron transfer pathways in more-complex environments....

  9. Single-element Electron-transfer Optical Detector System

    Science.gov (United States)

    Jordan, Jeffrey D. (Inventor)

    2004-01-01

    An optical detector system includes an electrically resistive screen that is substantially transparent to radiation energy having a wavelength of interest. An electron transfer element (e.g., a low work function photoactive material or a carbon nanotube (CNT)-based element) has a first end and a second end with its first end spaced apart from the screen by an evacuated gap. When radiation energy passes through the screen with a bias voltage being applied thereto, transfer of electrons through the electron transfer element is induced from its first to its second end such that a quantity indicative of the electrons transferred can be detected.

  10. Cation-modulated electron-transfer channel: H-atom transfer vs proton-coupled electron transfer with a variable electron-transfer channel in acylamide units.

    Science.gov (United States)

    Chen, Xiaohua; Bu, Yuxiang

    2007-08-08

    The mechanism of proton transfer (PT)/electron transfer (ET) in acylamide units was explored theoretically using density functional theory in a representative model (a cyclic coupling mode between formamide and the N-dehydrogenated formamidic radical, FF). In FF, PT/ET normally occurs via a seven-center cyclic proton-coupled electron transfer (PCET) mechanism with a N-->N PT and an O-->O ET. However, when different hydrated metal ions are bound to the two oxygen sites of FF, the PT/ET mechanism may significantly change. In addition to their inhibition of PT/ET rate, the hydrated metal ions can effectively regulate the FF PT/ET cooperative mechanism to produce a single pathway hydrogen atom transfer (HAT) or a flexible proton coupled electron transfer (PCET) mechanism by changing the ET channel. The regulation essentially originates from the change in the O...O bond strength in the transition state, subject to the binding ability of the hydrated metal ions. In general, the high valent metal ions and those with large binding energies can promote HAT, and the low valent metal ions and those with small binding energies favor PCET. Hydration may reduce the Lewis acidity of cations, and thus favor PCET. Good correlations among the binding energies, barrier heights, spin density distributions, O...O contacts, and hydrated metal ion properties have been found, which can be used to interpret the transition in the PT/ET mechanism. These findings regarding the modulation of the PT/ET pathway via hydrated metal ions may provide useful information for a greater understanding of PT/ET cooperative mechanisms, and a possible method for switching conductance in nanoelectronic devices.

  11. Syntrophic growth with direct interspecies electron transfer as the primary mechanism for energy exchange.

    Science.gov (United States)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Aklujkar, Muktak; Liu, Fanghua; Shrestha, Minita; Summers, Zarath M; Malvankar, Nikhil; Flores, Dan Carlo; Lovley, Derek R

    2013-12-01

    Direct interspecies electron transfer (DIET) through biological electrical connections is an alternative to interspecies H2 transfer as a mechanism for electron exchange in syntrophic cultures. However, it has not previously been determined whether electrons received via DIET yield energy to support cell growth. In order to investigate this, co-cultures of Geobacter metallireducens, which can transfer electrons to wild-type G. sulfurreducens via DIET, were established with a citrate synthase-deficient G. sulfurreducens strain that can receive electrons for respiration through DIET only. In a medium with ethanol as the electron donor and fumarate as the electron acceptor, co-cultures with the citrate synthase-deficient G. sulfurreducens strain metabolized ethanol as fast as co-cultures with wild-type, but the acetate that G. metallireducens generated from ethanol oxidation accumulated. The lack of acetate metabolism resulted in less fumarate reduction and lower cell abundance of G. sulfurreducens. RNAseq analysis of transcript abundance was consistent with a lack of acetate metabolism in G. sulfurreducens and revealed gene expression levels for the uptake hydrogenase, formate dehydrogenase, the pilus-associated c-type cytochrome OmcS and pili consistent with electron transfer via DIET. These results suggest that electrons transferred via DIET can serve as the sole energy source to support anaerobic respiration. © 2013 John Wiley & Sons Ltd and Society for Applied Microbiology.

  12. Studies of electron and proton isochoric heating for fast ignition

    Energy Technology Data Exchange (ETDEWEB)

    Mackinnon, A; Key, M; Akli, K; Beg, F; Clarke, R; Clarke, D; Chen, M; Chung, H; Chen, S; Freeman, R; Green, J; Gu, P; Gregori, G; Highbarger, K; Habara, H; Hatchett, S; Hey, D; Heathcote, R; Hill, J; King, J; Kodama, R; Koch, J; Lancaster, K; Langdon, B; Murphy, C; Norreys, P; Neely, D; Nakatsutsumi, M; Nakamura, H; Patel, N; Patel, P; Pasley, J; Snavley, R; Stephens, R; Stoeckl, C; Foord, M; Tabak, M; Theobald, W; Storm, M; Tanaka, K; Tempo, M; Toley, M; Town, R; Wilks, S; VanWoerkom, L; Weber, R; Yabuuchi, T; Zhang, B

    2006-10-02

    Isochoric heating of inertially confined fusion plasmas by laser driven MeV electrons or protons is an area of great topical interest in the inertial confinement fusion community, particularly with respect to the fast ignition (FI) proposal to use this technique to initiate burn in a fusion capsule. Experiments designed to investigate electron isochoric heating have measured heating in two limiting cases of interest to fast ignition, small planar foils and hollow cones. Data from Cu K{alpha} fluorescence, crystal x-ray spectroscopy of Cu K shell emission, and XUV imaging at 68eV and 256 eV are used to test PIC and Hybrid PIC modeling of the interaction. Isochoric heating by focused proton beams generated at the concave inside surface of a hemi-shell and from a sub hemi-shell inside a cone have been studied with the same diagnostic methods plus imaging of proton induced K{alpha}. Conversion efficiency to protons has also been measured and modeled. Conclusions from the proton and electron heating experiments will be presented. Recent advances in modeling electron transport and innovative target designs for reducing igniter energy and increasing gain curves will also be discussed.

  13. Kinetics of electron transfer from photoexcited superlattice electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Nozik, A.J.; Turner, J.A.; Peterson, M.W.

    1988-05-05

    A kinetic model has been developed that quantitatively describes electron transfer from photoexcited superlattice electrodes into liquid solutions. The model permits electron transfer from all quantum levels as well as from surface states; it also takes into account recombination in the bulk, space charge layer, and surfaces states, and band-edge movement. The model calculations define the values of the rate constants for heterogeneous electron transfer and hot electron thermalization among the various energy levels in the supperlattice quantum wells that are necessary to achieve hot electron transfer from excited quantum states. The question of whether hot electron transfer is manifested by a dependence of the photocurrent action spectra on acceptor redox potential is examined in detail.

  14. Fast electronic resistance switching involving hidden charge density wave states

    Science.gov (United States)

    Vaskivskyi, I.; Mihailovic, I. A.; Brazovskii, S.; Gospodaric, J.; Mertelj, T.; Svetin, D.; Sutar, P.; Mihailovic, D.

    2016-05-01

    The functionality of computer memory elements is currently based on multi-stability, driven either by locally manipulating the density of electrons in transistors or by switching magnetic or ferroelectric order. Another possibility is switching between metallic and insulating phases by the motion of ions, but their speed is limited by slow nucleation and inhomogeneous percolative growth. Here we demonstrate fast resistance switching in a charge density wave system caused by pulsed current injection. As a charge pulse travels through the material, it converts a commensurately ordered polaronic Mott insulating state in 1T-TaS2 to a metastable electronic state with textured domain walls, accompanied with a conversion of polarons to band states, and concurrent rapid switching from an insulator to a metal. The large resistance change, high switching speed (30 ps) and ultralow energy per bit opens the way to new concepts in non-volatile memory devices manipulating all-electronic states.

  15. Fast Frontend Electronics for high luminosity particle detectors

    CERN Document Server

    Cardinali, M; Bondy, M I Ferretti; Hoek, M; Lauth, W; Rosner, C; Sfienti, C; Thiel, M

    2015-01-01

    Future experiments of nuclear and particle physics are moving towards the high luminosity regime, in order to access suppressed processes like rare B decays or exotic charmonium resonances. In this scenario, high rate capability is a key requirement for electronics instrumentation, together with excellent timing resolution for precise event reconstruction. The development of dedicated FrontEnd Electronics (FEE) for detectors has become increasingly challenging. A current trend in R&D is towards multipurpose FEE which can be easily adapted to a great variety of detectors, without impairing the required high performance. We report on high-precision timing solutions which utilise high-bandwidth preamplifiers and fast discriminators providing Time-over-Threshold information, which can be used for charge measurements or walk corrections thus improving the obtainable timing resolution. The output signal are LVDS and can be directly fed into a multi-hit TDC readout. The performance of the electronics was investi...

  16. Electronic transfer of sensitive patient data.

    Science.gov (United States)

    Detterbeck, A M W; Kaiser, J; Hirschfelder, U

    2015-01-01

    The purpose of this study was to develop decision-making aids and recommendations for dental practitioners regarding the utilization and sharing of sensitive digital patient data. In the current environment of growing digitization, healthcare professionals need detailed knowledge of secure data management to maximize confidentiality and minimize the risks involved in both archiving patient data and sharing it through electronic channels. Despite well-defined legal requirements, an all-inclusive technological solution does not currently exist. The need for a preliminary review and critical appraisal of common practices of data transfer prompted a search of the literature and the Web to identify viable methods of secure data exchange and to develop a flowchart. A strong focus was placed on the transmission of datasets both smaller than and larger than 10 MB, and on secure communication by smartphone. Although encryption of patient-related data should be routine, it is often difficult to implement. Pretty Good Privacy (PGP) and Secure/Multipurpose Internet Mail Extensions (S/MIME) are viable standards for secure e-mail encryption. Sharing of high-volume data should be accomplished with the help of file encryption. Careful handling of sensitive patient data is mandatory, and it is the end-user's responsibility to meet any requirements for encryption, preferably by using free, open-source (and hence transparent) software.

  17. Effects of laser intensity on the emission direction of fast electrons in laser-solid interactions

    Institute of Scientific and Technical Information of China (English)

    张军; 张杰; 邱阳; 盛政明; 李玉同; 金展; 滕浩

    2003-01-01

    The dependence of emission direction of fast electrons on the laser intensity has been investigated. The experimental results show that, at nonrelativistic laser intensities, the emission of fast electrons is mainly in the polarization plane. With the increase of the laser intensity, fast electrons emit towards the laser propagation direction from laser polarization direction. At relativistic laser intensities, fast electrons move away from the laser polarization plane, closely to the reflection direction of the incident laser beam.

  18. Inner Shell Excitations of Lithium Studied by Fast Electron Impact

    Institute of Scientific and Technical Information of China (English)

    JIANG Wei-Chun; ZHU Lin-Fan; XU Ke-Zun

    2008-01-01

    Electron energy loss spectra for the inner shell excitations of atomic lithium are measured at an incident electron energy of 2500eV and scattering angles of 0°, 2°, 4° and 6°. Two optically forbidden transitions of (1s2s2)2S and (1s2s3S)3s2 S are observed. The generalized oscillator strength ratios for 1s(2s2p3P)2 P0 to 1s(2s2p1P)2P0 were determined, and they are independent of the momentum transfer.

  19. Calculation of fusion gain in fast ignition with magnetic target by relativistic electrons and protons

    Directory of Open Access Journals (Sweden)

    A Parvazian

    2010-12-01

    Full Text Available Fast ignition is a new method for inertial confinement fusion (ICF in which the compression and ignition steps are separated. In the first stage, fuel is compressed by laser or ion beams. In the second phase, relativistic electrons are generated by pettawat laser in the fuel. Also, in the second phase 5-35 MeV protons can be generated in the fuel. Electrons or protons can penetrate in to the ultra-dense fuel and deposit their energy in the fuel . More recently, cylindrical rather than spherical fuel chambers with magnetic control in the plasma domain have been also considered. This is called magnetized target fusion (MTF. Magnetic field has effects on relativistic electrons energy deposition rate in fuel. In this work, fast ignition method in cylindrical fuel chambers is investigated and transportation of the relativistic electrons and protons is calculated using MCNPX and FLUKA codes with 0. 25 and 0. 5 tesla magnetic field in single and dual hot spot. Furthermore, the transfer rate of relativistic electrons and high energy protons to the fuel and fusion gain are calculated. The results show that the presence of external magnetic field guarantees higher fusion gain, and relativistic electrons are much more appropriate objects for ignition. MTF in dual hot spot can be considered as an appropriate substitution for the current ICF techniques.

  20. Photoinitiated electron transfer in multichromophoric species: Synthetic tetrads and pentads

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1993-03-01

    This project involves the design, synthesis and study of molecules which mimic some of the important aspects of photosynthetic electron and energy transfer. This research project is leading to a better understanding of the energy conserving steps of photosynthesis via the study of synthetic model systems which abstract features of the natural photosynthetic apparatus. The knowledge gained from these studies will aid in the design of artificial photosynthetic reaction centers which employ the basic chemistry and physics of photosynthesis to help meet mankind`s energy needs. The approach to artificial photosynthesis employed in this project is to use synthetic pigments, electron donors, and electron acceptors similar to those found in biological reaction centers, but to replace the protein component with covalent bonds. These chemical linkages determine the electronic coupling between the various moieties by controlling separation, relative orientation, and overlap of electronic orbitals. The model systems are designed to mimic the following aspects of natural photosynthetic electron transfer: electron donation from a tetrapyrrole excited single state, electron transfer between tetrapyrroles, electron transfer from tetrapyrroles to quinones, and electron transfer between quinones with different redox properties. In addition, they mimic carotenoid antenna function in photosynthesis (singlet-singlet energy transfer from carotenoid polyenes to chlorophyll) and carotenoid photoprotection from singlet oxygen damage (triplet-triplet energy transfer from chlorophyll to carotenoids).

  1. 78 FR 66251 - Electronic Fund Transfers(Regulation E)

    Science.gov (United States)

    2013-11-05

    ... PROTECTION 12 CFR Part 1005 RIN 3170-AA33 Electronic Fund Transfers (Regulation E) AGENCY: Bureau of Consumer... countries that qualify for an exception in subpart B of Regulation E, which implements the Electronic Fund....consumerfinance.gov/remittances-transfer-rule-amendment-to-regulation-e/ . SUPPLEMENTARY INFORMATION: The...

  2. 14 CFR 1260.69 - Electronic funds transfer payment methods.

    Science.gov (United States)

    2010-01-01

    .... Electronic Funds Transfer Payment Methods October 2000 (a) Payments under this grant will be made by the Government by electronic funds transfer through the Treasury Fedline Payment System (FEDLINE) or the Automated Clearing House (ACH), at the option of the Government. After award, but no later than 14 days...

  3. 14 CFR 1274.931 - Electronic funds transfer payment methods.

    Science.gov (United States)

    2010-01-01

    ... cooperative agreement will be made by the Government by electronic funds transfer through the Treasury Fedline Payment System (FEDLINE) or the Automated Clearing House (ACH), at the option of the Government. After... 14 Aeronautics and Space 5 2010-01-01 2010-01-01 false Electronic funds transfer payment methods...

  4. Time-resolved EPR identifies unexpected electron transfer in cryptochrome**

    Science.gov (United States)

    Biskup, Till; Hitomi, Kenichi; Getzoff, Elizabeth D.; Krapf, Sebastian; Koslowski, Thorsten; Schleicher, Erik

    2012-01-01

    Tuning photoinduced electron transfer: Subtle differences in local sequence and conformation can produce diversity and specificity in electron transfer (ET) in proteins, despite high structural conservation of redox partners. For individual ET steps, distance is not necessarily the decisive parameter; orientation and solvent accessibility of ET partners, and therefore, stabilization of charge-separated states contribute substantially. PMID:22086606

  5. 77 FR 6310 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-02-07

    ... PROTECTION 12 CFR Part 1005 RIN 3170-AA15 Electronic Fund Transfers (Regulation E) AGENCY: Bureau of Consumer... Financial Protection (Bureau) is proposing to amend Regulation E, which implements the Electronic Fund... phrase ``normal course of business'' in the definition of ``remittance transfer provider.''...

  6. 76 FR 708 - Electronic Funds Transfer of Depository Taxes; Correction

    Science.gov (United States)

    2011-01-06

    ... Internal Revenue Service 26 CFR Parts 1, 31, 40, and 301 RIN 1545-BJ13 Electronic Funds Transfer of...) providing guidance relating to Federal tax deposits (FTDs) by Electronic Funds Transfer (EFT). The temporary... Days and Legal Holidays'', line 8 from the bottom of the page, the language ``section 7503, the term...

  7. 76 FR 709 - Electronic Funds Transfer of Depository Taxes; Correction

    Science.gov (United States)

    2011-01-06

    ... Internal Revenue Service 26 CFR Parts 40 and 301 RIN 1545-BJ13 Electronic Funds Transfer of Depository... deposits (FTDs) by Electronic Funds Transfer (EFT). The temporary and final regulations provide rules under...)-3 0 Par. 2. Section 40.6302(c)-3, paragraph (c) is amended by removing the language in the third...

  8. THE ELECTRONIC COURSE OF HEAT AND MASS TRANSFER

    Directory of Open Access Journals (Sweden)

    Alexander P. Solodov

    2013-01-01

    Full Text Available The Electronic course of heat and mass transfer in power engineering is presented containing the full Electronic book as the structured hypertext document, the full set of Mathcad-documents with the whole set of educative computer models of heat and mass transfer, the computer labs, and selected educational presentations. 

  9. Electron and hole transfer from indium phosphide quantum dots.

    Science.gov (United States)

    Blackburn, J L; Selmarten, D C; Ellingson, R J; Jones, M; Micic, O; Nozik, A J

    2005-02-24

    Electron- and hole-transfer reactions are studied in colloidal InP quantum dots (QDs). Photoluminescence quenching and time-resolved transient absorption (TA) measurements are utilized to examine hole transfer from photoexcited InP QDs to the hole acceptor N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) and electron transfer to nanocrystalline titanium dioxide (TiO2) films. Core-confined holes are effectively quenched by TMPD, resulting in a new approximately 4-ps component in the TA decay. It is found that electron transfer to TiO2 is primarily mediated through surface-localized states on the InP QDs.

  10. Heme electron transfer in peroxidases: the propionate e-pathway.

    Science.gov (United States)

    Guallar, Victor

    2008-10-23

    Computational modeling offers a new insight about the electron transfer pathway in heme peroxidases. Available crystal structures have revealed an intriguing arrangement of the heme propionate side chains in heme-heme and heme-substrate complexes. By means of mixed quantum mechanical/molecular mechanics calculations, we study the involvement of these propionate groups into the substrate oxidation in ascorbate peroxidase and into the heme to heme electron transfer in bacterial cytochrome c peroxidase. By selectively turning on/off different quantum regions, we obtain the electron transfer pathway which directly involves the porphyrin ring and the heme propionates. Furthermore, in ascorbate peroxidase the presence of the substrate appears to be crucial for the activation of the electron transfer channel. The results might represent a general motif for electron transfer from/to the heme group and change our view for the propionate side chains as simple electrostatic binding anchors. We name the new mechanism "the propionate e-pathway".

  11. Density matrix theory for reductive electron transfer in DNA

    Energy Technology Data Exchange (ETDEWEB)

    Kleinekathoefer, Ulrich [Institut fuer Physik, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany)]. E-mail: kleinekathoefer@physik.tu-chemnitz.de; Li Guangqi [Institut fuer Physik, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany); Schreiber, Michael [Institut fuer Physik, Technische Universitaet Chemnitz, 09107 Chemnitz (Germany)

    2006-07-15

    Reductive electron transfer in DNA is investigated using the reduced density matrix formalism. For reductive electron transfer in DNA an electron donor is attached to the DNA. The photo-excitation of this donor by ultrashort laser pulses is described explicitly in the current investigation, as well as the transfer of the electron from the donor to the acceptor. In addition, the effect of an additional bridge molecule is studied. All these studies are performed using three different quantum master equations: a Markovian one and two non-Markovian ones derived from either a time-local or a time-nonlocal formalism. The deviations caused by these three different approaches are discussed.

  12. Superexcited states of carbon monoxide studied by fast-electron impact

    Institute of Scientific and Technical Information of China (English)

    Fan Lan-Lan; Zhong Zhi-Ping; Zhu Lin-Fan; Liu Xiao-Jing; Cheng Hua-Dong; Yuan Zhen-Sheng; Xu Ke-Zun

    2005-01-01

    Absolute optical oscillator strength density and double differential cross section spectra of CO below 120 eV are determined by fast electron impact. Some peaks above the first ionization threshold stand out as the momentum transfer square K2 increases. The doubly excited Rydberg states converging to C 2∑+, D 2Π, and F 2Π states of CO+, respectively, are confirmed in our spectra. Another peak at around 32eV is assigned to the transition of (3σ)-1(2π)1 1Π← X1∑+.

  13. Fast Transverse Instability and Electron Cloud Measurements in Fermilab Recycler

    Energy Technology Data Exchange (ETDEWEB)

    Eldred, Jeffery; Adamson, Philip; Capista, David; Eddy, Nathan; Kourbanis, Ioanis; Morris, Denton; Thangaraj, Jayakar; Yang, Ming-Jen; Zwaska, Robert; Ji, Yichen

    2015-03-01

    A new transverse instability is observed that may limit the proton intensity in the Fermilab Recycler. The instability is fast, leading to a beam-abort loss within two hundred turns. The instability primarily affects the first high-intensity batch from the Fermilab Booster in each Recycler cycle. This paper analyzes the dynamical features of the destabilized beam. The instability excites a horizontal betatron oscillation which couples into the vertical motion and also causes transverse emittance growth. This paper describes the feasibility of electron cloud as the mechanism for this instability and presents the first measurements of the electron cloud in the Fermilab Recycler. Direct measurements of the electron cloud are made using a retarding field analyzer (RFA) newly installed in the Fermilab Recycler. Indirect measurements of the electron cloud are made by propagating a microwave carrier signal through the beampipe and analyzing the phase modulation of the signal. The maximum betatron amplitude growth and the maximum electron cloud signal occur during minimums of the bunch length oscillation.

  14. Electron loss of fast projectiles in the collisions with molecules

    CERN Document Server

    Matveev, V I; Rakhimov, Kh Yu

    2011-01-01

    The single and multiple electron loss of fast highly charged projectiles in the collisions with neutral molecules are studied within the framework of a nonperturbative approach. The cross sections for single, double, and triple electron losses are calculated for the collision system $Fe^{q+}\\to N_2$ ($q$=24, 25, 26) at the collision energies 10, 100, and 1000 MeV/u. The effects caused by the collision multiplicity and the orientation of the axis of target molecule are treated. It is shown that collision multiplicity effect leads to considerable differences for the cases of perpendicular and parallel orientations of the molecular axes with respect to the direction of the projectile motion, while for chaotic orientation such effect is negligible.

  15. Non-dipole effects in angular distributions of secondary electrons in fast particle-atom scattering

    CERN Document Server

    Amusia, M Ya; Liverts, E Z

    2010-01-01

    We demonstrate that the angular distribution of electrons knocked out from an atom by a fast charge particle is determined not only by dipole but also by quadrupole transitions, the contribution of which can be considerably enhanced as compared to the case of photoionization. To obtain these matrix elements one has to study the angular distribution of electrons emitted by the atom in its collision with a fast charged particle. The distribution has to be measured relative to the momentum q transferred from the projectile to the target atom. The situation is similar, but not identical to the photoionization studies, where the matrix elements of continuous spectrum atomic quadrupole transitions can be determined by measuring the so-called non-dipole angular anisotropy parameters of photoelectrons. However, they are strongly suppressed as compared to the dipole matrix elements by small ratio of atomic size to the photon wavelength. This suppression is controlled in fast electron-atom collisions, where it can be m...

  16. Variable Electron Transfer Pathways in an Amphibian Cryptochrome

    Science.gov (United States)

    Biskup, Till; Paulus, Bernd; Okafuji, Asako; Hitomi, Kenichi; Getzoff, Elizabeth D.; Weber, Stefan; Schleicher, Erik

    2013-01-01

    Electron transfer reactions play vital roles in many biological processes. Very often the transfer of charge(s) proceeds stepwise over large distances involving several amino acid residues. By using time-resolved electron paramagnetic resonance and optical spectroscopy, we have studied the mechanism of light-induced reduction of the FAD cofactor of cryptochrome/photolyase family proteins. In this study, we demonstrate that electron abstraction from a nearby amino acid by the excited FAD triggers further electron transfer steps even if the conserved chain of three tryptophans, known to be an effective electron transfer pathway in these proteins, is blocked. Furthermore, we were able to characterize this secondary electron transfer pathway and identify the amino acid partner of the resulting flavin-amino acid radical pair as a tyrosine located at the protein surface. This alternative electron transfer pathway could explain why interrupting the conserved tryptophan triad does not necessarily alter photoreactions of cryptochromes in vivo. Taken together, our results demonstrate that light-induced electron transfer is a robust property of cryptochromes and more intricate than commonly anticipated. PMID:23430261

  17. Fast ethylamine gas sensing based on intermolecular charge-transfer complexation

    Institute of Scientific and Technical Information of China (English)

    Eun Mi Lee; Seon Young Gwon; Young A Son; Sung Hoon Kim

    2012-01-01

    We have investigated the fast ethylamine gas sensing of 2-chloro-3,5-dinitrobenzotrifluoride (CDBF) loaded poly(acrylonitrile)nanofiber based on an intermolecular charge-transfer complexation.Reversible response and recovery were achieved using alternating gas exposure.This system shows a fast ethylamine gas sensing within 0.4 s.

  18. Dissipative two-electron transfer: A numerical renormalization group study

    Science.gov (United States)

    Tornow, Sabine; Bulla, Ralf; Anders, Frithjof B.; Nitzan, Abraham

    2008-07-01

    We investigate nonequilibrium two-electron transfer in a model redox system represented by a two-site extended Hubbard model and embedded in a dissipative environment. The influence of the electron-electron interactions and the coupling to a dissipative bosonic bath on the electron transfer is studied in different temperature regimes. At high temperatures, Marcus transfer rates are evaluated, and at low temperatures, we calculate equilibrium and nonequilibrium population probabilities of the donor and acceptor with the nonperturbative numerical renormalization group approach. We obtain the nonequilibrium dynamics of the system prepared in an initial state of two electrons at the donor site and identify conditions under which the electron transfer involves one concerted two-electron step or two sequential single-electron steps. The rates of the sequential transfer depend nonmonotonically on the difference between the intersite and on-site Coulomb interaction, which become renormalized in the presence of the bosonic bath. If this difference is much larger than the hopping matrix element, the temperature as well as the reorganization energy, simultaneous transfer of both electrons between donor and acceptor can be observed.

  19. Electron dynamics and intermolecular energy transfer in aqueous solutions studied by X-ray electron spectroscopy

    Science.gov (United States)

    Winter, Bernd

    2009-03-01

    X-ray photoelectron spectroscopy measurements from a vacuum liquid microjet are performed to investigate the electronic structure of aqueous solutions. Here, focus is on the excited-state dynamics of chloride and hydroxide anions in water, following core-level excitation. A series of Cl^-(aq) charge-transfer-to-solvent (CTTS) states, and their ultrafast relaxation, on the time scale of the core hole, is identified from the occurrence of spectator Auger decay. Resonant oxygen 1s excitation of aqueous hydroxide, in contrast, leads to non-local decay, involving energy transfer into a neighboring water molecule. This channel is argued to arise from the weak hydrogen donor bond of OH^-(aq), and thus identifies a special transient hydration configuration, which can explain hydroxide's unusual and fast transport in water. Analogous measurements from pure water point to a similar relaxation channel, which is concluded from a strong isotope effect. The characteristic resonance spectral features are considerably stronger for H2O(aq) than for D2O(aq). As for OH^-(aq) the results can be understood in terms of energy transfer from the excited water molecule to a neighbor water molecule.

  20. K-shell Analysis Reveals Distinct Functional Parts in an Electron Transfer Network and Its Implications for Extracellular Electron Transfer

    Science.gov (United States)

    Ding, Dewu; Li, Ling; Shu, Chuanjun; Sun, Xiao

    2016-01-01

    Shewanella oneidensis MR-1 is capable of extracellular electron transfer (EET) and hence has attracted considerable attention. The EET pathways mainly consist of c-type cytochromes, along with some other proteins involved in electron transfer processes. By whole genome study and protein interactions inquisition, we constructed a large-scale electron transfer network containing 2276 interactions among 454 electron transfer related proteins in S. oneidensis MR-1. Using the k-shell decomposition method, we identified and analyzed distinct parts of the electron transfer network. We found that there was a negative correlation between the ks (k-shell values) and the average DR_100 (disordered regions per 100 amino acids) in every shell, which suggested that disordered regions of proteins played an important role during the formation and extension of the electron transfer network. Furthermore, proteins in the top three shells of the network are mainly located in the cytoplasm and inner membrane; these proteins can be responsible for transfer of electrons into the quinone pool in a wide variety of environmental conditions. In most of the other shells, proteins are broadly located throughout the five cellular compartments (cytoplasm, inner membrane, periplasm, outer membrane, and extracellular), which ensures the important EET ability of S. oneidensis MR-1. Specifically, the fourth shell was responsible for EET and the c-type cytochromes in the remaining shells of the electron transfer network were involved in aiding EET. Taken together, these results show that there are distinct functional parts in the electron transfer network of S. oneidensis MR-1, and the EET processes could achieve high efficiency through cooperation through such an electron transfer network. PMID:27148219

  1. A molecular shift register based on electron transfer

    Science.gov (United States)

    Hopfield, J. J.; Onuchic, Josenelson; Beratan, David N.

    1988-01-01

    An electronic shift-register memory at the molecular level is described. The memory elements are based on a chain of electron-transfer molecules and the information is shifted by photoinduced electron-transfer reactions. This device integrates designed electronic molecules onto a very large scale integrated (silicon microelectronic) substrate, providing an example of a 'molecular electronic device' that could actually be made. The design requirements for such a device and possible synthetic strategies are discussed. Devices along these lines should have lower energy usage and enhanced storage density.

  2. Fast and simple model for atmospheric radiative transfer

    NARCIS (Netherlands)

    Seidel, F.C.; Kokhanovsky, A.A.; Schaepman, M.E.

    2010-01-01

    Radiative transfer models (RTMs) are of utmost importance for quantitative remote sensing, especially for compensating atmospheric perturbation. A persistent trade-off exists between approaches that prefer accuracy at the cost of computational complexity, versus those favouring simplicity at the

  3. Photoinduced electron transfer between benzyloxy dendrimer phthalocyanine and benzoquinone

    Science.gov (United States)

    Zhang, Tiantian; Ma, Dongdong; Pan, Sujuan; Wu, Shijun; Jiang, Yufeng; Zeng, Di; Yang, Hongqin; Peng, Yiru

    2016-10-01

    Photo-induced electron transfer (PET) is an important and fundamental process in natural photosynthesis. To mimic such interesting PET process, a suitable donor and acceptor couple were properly chosen. Dendrimer phthalocyanines and their derivatives have emerged as promising materials for artificial photosynthesis systems. In this paper, the electron transfer between the light harvest dendrimer phthalocyanine (donor) and the 1,4-benzoquinone (acceptor) was studied by UV/Vis and fluorescence spectroscopic methods. It was found that fluorescence of phthalocyanine was quenched by benzoquinone (BQ) via excited state electron transfer, from the phthalocyanine to the BQ upon excitation at 610 nm. The Stern-Volmer constant (KSV) of electron transfer was calculated. Our study suggests that this dendritic phthalocyanine is an effective new electron donor and transmission complex and could be used as a potential artificial photosynthesis system.

  4. Excited state electron transfer in systems with a well-defined geometry. [cyclophane

    Energy Technology Data Exchange (ETDEWEB)

    Kaufmann, K.J.

    1980-12-01

    The effect of temperature, dielectric strength and ligand on the structure of the mesopyropheophorbide cyclophanes will be studied. ESR, NMR, emission and absorption spectroscopy, as well as circular dichroism will be used. The changes in structure will be correlated with changes in the photochemical activity. Electron acceptors such as benzoquinone will be utilized to stabilize the charge separation. Charge separation in porphyrin quinone dimers will also be studied. It was found that electron transfer in the cyclophane system is relatively slow. This is presumably due to an orientation requirement for fast electron transfer. Solvent dielectric also is important in producing a charge separation. Decreasing the temperature effects the yield of charge transfer, but not the kinetics.

  5. Research on Calibration Transfer across Infrared Spectrometric Instruments for Fast Evaluation of Crude Oils

    Institute of Scientific and Technical Information of China (English)

    Li Jingyan; Chu Xiaoli; Tian Songbai

    2015-01-01

    The spectral analysis method is suitable for the process control and the process analysis such as the fast evalua-tion of crude oils. In this study, model transfer between the same type of spectrometer and different type of spectrometers was discussed respectively, and the results have shown that the transfer of calibration model can satisfy the demand of rapid analysis.

  6. Intermolecular and intramolecular electron transfer from eosin ester to viologen

    Institute of Scientific and Technical Information of China (English)

    张丰雷; 张曼华; 沈涛

    1996-01-01

    The covalently -(CH2)10- linked eosin-butylviologen compound has been synthesized. The photoinduced electron transfer of eosin ester and butylviologen as well as the influence of addition of cyclodextrin or amylose into the solution of linked compound on the system have been studied by the absorption spectra, fluorescence spectra and fluorescence lifetime. The results indicated that the intramolecular electron transfer is much more efficient than the intermolecular one. Due to the formation of inclusion complex, the process of intramolecular electron transfer was changed after adding cydodextrin or amylose.

  7. Enhanced surface acceleration of fast electrons by using sub-wavelength grating targets

    CERN Document Server

    Hu, Guang-yue; Wang, Wen-tao; Wang, Jing-wei; Huang, Lin-gen; Wang, Xin; Xu, Yi; Liu, Jian-sheng; Shen, Bai-fei; Yu, Wei; Li, Ru-xin; Xu, Zhi-zhan

    2010-01-01

    Surface acceleration of fast electrons in intense laser-plasma interaction is improved by using sub-wavelength grating targets. The fast electron beam emitted along the target surface was enhanced by more than three times relative to that by using planar target. The total number of the fast electrons ejected from the front side of target was also increased by about one time. The method to enhance the surface acceleration of fast electron is effective for various targets with sub-wavelength structured surface, and can be applied widely in the cone-guided fast ignition, energetic ion acceleration, plasma device, and other high energy density physics experiments.

  8. REFLECTIONS ON THE TWO-STATE ELECTRON TRANSFER MODEL.

    Energy Technology Data Exchange (ETDEWEB)

    Brunschwig, B.S.

    2000-01-12

    There is general agreement that the two most important factors determining electron transfer rates in solution are the degree of electronic interaction between the donor and acceptor sites, and the changes in the nuclear configurations of the donor, acceptor, and surrounding medium that occur upon the gain or loss of an electron Ll-51. The electronic interaction of the sites will be very weak, and the electron transfer slow, when the sites are far apart or their interaction is symmetry or spin forbidden. Since electron motion is much faster than nuclear motion, energy conservation requires that, prior to the actual electron transfer, the nuclear configurations of the reactants and the surrounding medium adjust from their equilibrium values to a configuration (generally) intermediate between that of the reactants and products. In the case of electron transfer between , two metal complexes in a polar solvent, the nuclear configuration changes involve adjustments in the metal-ligand and intraligand bond lengths and angles, and changes in the orientations of the surrounding solvent molecules. In common with ordinary chemical reactions, an electron transfer reaction can then be described in terms of the motion of the system on an energy surface from the reactant equilibrium configuration (initial state) to the product equilibrium configuration (final state) via the activated complex (transition state) configuration.

  9. Qualitative difference between the angular anisotropy parameters in fast electron scattering and photoionization

    CERN Document Server

    Amusia, M Ya; Liverts, E Z

    2011-01-01

    It is demonstrated for the first time that in spite of well known big similarities between atomic ionization by photons and fast electrons, a qualitative difference exists in angular anisotropy parameters of electrons knocked out in these processes. The difference is disclosed here and attributed to distinction between normal (transverse) and virtual (longitudinal) photons. Formulas are derived for dipole and non-dipole angular anisotropy parameters in fast electronatom scattering. The ratio of quadrupole-to-dipole matrix elements is determined by the parameter \\omega R/v << 1 where \\omega is the transferred in collision energy, R is the ionized shell radius and v is the speed of projectile. This factor can be much bigger than in the case of photoionization, where one has the speed of light c that is much bigger than v . We illustrate general formulas by concrete results for outer s-subshells of noble gas atoms Ar and Xe. Even for very small transferred momentum q, in the so-called optical limit, the de...

  10. [Electron transfer between globular proteins. Dependence of the rate of transfer on distance].

    Science.gov (United States)

    Lakhno, V D; Chuev, G N; Ustinin, M N; Komarov, V M

    1998-01-01

    Based on the assumption that electron transfer between globular proteins occurs by a collective excitation of polaron type, the dependence of the rate of this process on the distance between the donor and acceptor centers with regard to their detailed electron structure was calculated. The electron structure of the heme was calculated by the quantum-chemical MNDO-PM3 method. The results were compared with experimental data on interprotein and intraglobular electron transfer. It is shown that, in the framework of this model, the electron transfer is not exponential and does not require a particular transfer pathway since the whole protein macromolecule is involved in the formation of the electron excited state.

  11. Fast heat transfer calculations in supercritical fluids versus hydrodynamic approach

    CERN Document Server

    Nikolayev, Vadim; Garrabos, Y; Beysens, D

    2016-01-01

    This study investigates the heat transfer in a simple pure fluid whose temperature is slightly above its critical temperature. We propose a efficient numerical method to predict the heat transfer in such fluids when the gravity can be neglected. The method, based on a simplified thermodynamic approach, is compared with direct numerical simulations of the Navier-Stokes and energy equations performed for CO2 and SF6. A realistic equation of state is used to describe both fluids. The proposed method agrees with the full hydrodynamic solution and provides a huge gain in computation time. The connection between the purely thermodynamic and hydrodynamic descriptions is also discussed.

  12. Fast Electronics for the Dafne Transverse Feedback Systems

    CERN Document Server

    Drago, A; Serio, M

    2001-01-01

    Transverse feedback systems for controlling the vertical coupled-bunch instabilities in the positron and electron main rings are installed at DAFNE. They started to be operative respectively from June and September 2000. For the horizontal plane, similar systems have been installed in summer 2001 with less kicker power. Design specifications and the basic system concepts are presented. Real time bunch-by-bunch offset correction is implemented using digital signal processors and dual-port RAM's. Fast analog to digital sampling is performed at the maximum bunch frequency (368 MHz). The system manages at full speed a continuous flow of 8-bits data and it has the capability to invert the sign or put to zero the output for any combination of bunches. A conversion from digital to analog produces the output correcting signal.

  13. Fast Electronics for the Dafne Transverse Feedback Systems

    Science.gov (United States)

    Drago, Alessandro

    Transverse feedback systems for controlling the vertical coupled-bunch instabilities in the positron and electron main rings are installed at DAFNE. They started to be operative respectively from June and September 2000. For the horizontal plane, similar systems have been installed in summer 2001 with less kicker power. Design specifications and the basic system concepts are presented. Real time bunch-by-bunch offset correction is implemented using digital signal processors and dual-port RAM's. Fast analog to digital sampling is performed at the maximum bunch frequency (368 MHz). The system manages at full speed a continuous flow of 8-bits data and it has the capability to invert the sign or put to zero the output for any combination of bunches. A conversion from digital to analog produces the output correcting signal.

  14. Fast and simple model for atmospheric radiative transfer

    NARCIS (Netherlands)

    Seidel, F.C.; Kokhanovsky, A.A.; Schaepman, M.E.

    2010-01-01

    Radiative transfer models (RTMs) are of utmost importance for quantitative remote sensing, especially for compensating atmospheric perturbation. A persistent trade-off exists between approaches that prefer accuracy at the cost of computational complexity, versus those favouring simplicity at the cos

  15. Extracellular electron transfer mechanisms between microorganisms and minerals

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Liang; Dong, Hailiang; Reguera, Gemma; Beyenal, Haluk; Lu, Anhuai; Liu, Juan; Yu, Han-Qing; Fredrickson, James K.

    2016-08-30

    Electrons can be transferred from microorganisms to multivalent metal ions that are associated with minerals and vice versa. As the microbial cell envelope is neither physically permeable to minerals nor electrically conductive, microorganisms have evolved strategies to exchange electrons with extracellular minerals. In this Review, we discuss the molecular mechanisms that underlie the ability of microorganisms to exchange electrons, such as c-type cytochromes and microbial nanowires, with extracellular minerals and with microorganisms of the same or different species. Microorganisms that have extracellular electron transfer capability can be used for biotechnological applications, including bioremediation, biomining and the production of biofuels and nanomaterials.

  16. Combining UV photodissociation with electron transfer for peptide structure analysis.

    Science.gov (United States)

    Shaffer, Christopher J; Marek, Ales; Pepin, Robert; Slovakova, Kristina; Turecek, Frantisek

    2015-03-01

    The combination of near-UV photodissociation with electron transfer and collisional activation provides a new tool for structure investigation of isolated peptide ions and reactive intermediates. Two new types of pulse experiments are reported. In the first one called UV/Vis photodissociation-electron transfer dissociation (UVPD-ETD), diazirine-labeled peptide ions are shown to undergo photodissociation in the gas phase to form new covalent bonds, guided by the ion conformation, and the products are analyzed by electron transfer dissociation. In the second experiment, called ETD-UVPD wherein synthetic labels are not necessary, electron transfer forms new cation-peptide radical chromophores that absorb at 355 nm and undergo specific backbone photodissociation reactions. The new method is applied to distinguish isomeric ions produced by ETD of arginine containing peptides. Copyright © 2015 John Wiley & Sons, Ltd.

  17. Blocking layer modeling for temperature analysis of electron transfer ...

    African Journals Online (AJOL)

    Blocking layer modeling for temperature analysis of electron transfer rate in quantum dot sensitized solar cells. ... Journal of Fundamental and Applied Sciences ... of the quantum dots and free energy of system and finally the Marcus equation.

  18. Fast sub-electron detectors review for interferometry

    Science.gov (United States)

    Feautrier, Philippe; Gach, Jean-Luc; Bério, Philippe

    2016-08-01

    New disruptive technologies are now emerging for detectors dedicated to interferometry. The detectors needed for this kind of applications need antonymic characteristics: the detector noise must be very low, especially when the signal is dispersed but at the same time must also sample the fast temporal characteristics of the signal. This paper describes the new fast low noise technologies that have been recently developed for interferometry and adaptive optics. The first technology is the Avalanche PhotoDiode (APD) infrared arrays made of HgCdTe. In this paper are presented the two programs that have been developed in that field: the Selex Saphira 320x256 [1] and the 320x255 RAPID detectors developed by Sofradir/CEA LETI in France [2], [3], [4]. Status of these two programs and future developments are presented. Sub-electron noise can now be achieved in the infrared using this technology. The exceptional characteristics of HgCdTe APDs are due to a nearly exclusive impaction ionization of the electrons, and this is why these devices have been called "electrons avalanche photodiodes" or e-APDs. These characteristics have inspired a large effort in developing focal plan arrays using HgCdTe APDs for low photon number applications such as active imaging in gated mode (2D) and/or with direct time of flight detection (3D imaging) and, more recently, passive imaging for infrared wave front correction and fringe tracking in astronomical observations. In addition, a commercial camera solution called C-RED, based on Selex Saphira and commercialized by First Light Imaging [5], is presented here. Some groups are also working with instruments in the visible. In that case, another disruptive technology is showing outstanding performances: the Electron Multiplying CCDs (EMCCD) developed mainly by e2v technologies in UK. The OCAM2 camera, commercialized by First Light Imaging [5], uses the 240x240 EMMCD from e2v and is successfully implemented on the VEGA instrument on the CHARA

  19. Supramolecular networks with electron transfer in two dimensions

    Energy Technology Data Exchange (ETDEWEB)

    Stupp, Samuel I.; Stoddart, J. Fraser; Shveyd, Alexander K.; Tayi, Alok S.; Sue, Chi-Hau; Narayanan, Ashwin

    2016-09-13

    Organic charge-transfer (CT) co-crystals in a crossed stack system are disclosed. The co-crystals exhibit bidirectional charge transfer interactions where one donor molecule shares electrons with two different acceptors, one acceptor face-to-face and the other edge-to-face. The assembly and charge transfer interaction results in a pleochroic material whereby the optical absorption continuously changes depending on the polarization angle of incident light.

  20. Analysis of transmission efficiency of SSRF electron beam transfer lines

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    In this article, the main factors which influence transmission efficiency of the SSRF electron beam transfer lines are described, including physical requirements for magnet system, vacuum system, beam diagnostic system,trajectory correction system, etc. The dynamic simulation calculation and transmission efficiency analysis of the SSRF electron beam transfer lines are presented, and the studies show that the design purpose of efficient beam transmission and injection will be achieved.

  1. 75 FR 9120 - Electronic Fund Transfers

    Science.gov (United States)

    2010-03-01

    ... assess overdraft fees for paying automated teller machine (ATM) and one-time debit card transactions that... Transfer Act, limiting a financial institution's ability to assess fees for paying ATM and one- time debit... secured by margin securities in brokerage accounts extended by Securities and Exchange Commission or...

  2. 76 FR 29901 - Electronic Fund Transfers

    Science.gov (United States)

    2011-05-23

    ... protections for consumers who send remittance transfers to consumers or entities in a foreign country, by providing consumers with disclosures and error resolution rights. The proposed amendments implement statutory requirements set forth in the Dodd-Frank Wall Street Reform and Consumer Protection Act. DATES...

  3. Promoting Knowledge Transfer with Electronic Note Taking

    Science.gov (United States)

    Katayama, Andrew D.; Shambaugh, R. Neal; Doctor, Tasneem

    2005-01-01

    We investigated the differences between (a) copying and pasting text versus typed note-taking methods of constructing study notes simultaneously with (b) vertically scaffolded versus horizontally scaffold notes on knowledge transfer. Forty-seven undergraduate educational psychology students participated. Materials included 2 electronic…

  4. Theoretical aspects of electron transfer reactions of complex molecules

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Ulstrup, Jens

    2001-01-01

    Features of electron transfer involving complex molecules are discussed. This notion presently refers to molecular reactants where charge transfer is accompanied by large molecular reorganization, and commonly used displaced harmonic oscillator models do not apply. It is shown that comprehensive ...... vibrational frequency changes, local mode anharmonicity, and rotational reorganization, in both diabatic and adiabatic limits. Systems for which this formalism is appropriate are discussed....

  5. 78 FR 30661 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2013-05-22

    ... Transfers (Regulation E); Final Rule #0;#0;Federal Register / Vol. 78 , No. 99 / Wednesday, May 22, 2013... Electronic Fund Transfers (Regulation E) AGENCY: Bureau of Consumer Financial Protection. ACTION: Final rule.../regulations/final-remittance-rule-amendment-regulation-e/ . SUPPLEMENTARY INFORMATION: I. Summary of the...

  6. Real-time electron dynamics simulation of two-electron transfer reactions induced by nuclear motion

    Science.gov (United States)

    Suzuki, Yasumitsu; Yamashita, Koichi

    2012-04-01

    Real-time electron dynamics of two-electron transfer reactions induced by nuclear motion is calculated by three methods: the numerically exact propagation method, the time-dependent Hartree (TDH) method and the Ehrenfest method. We find that, as long as the nuclei move as localized wave packets, the TDH and Ehrenfest methods can reproduce the exact electron dynamics of a simple charge transfer reaction model containing two electrons qualitatively well, even when nonadiabatic transitions between adiabatic states occur. In particular, both methods can reproduce the cases where a complete two-electron transfer reaction occurs and those where it does not occur.

  7. Electron Donor-Acceptor Quenching and Photoinduced Electron Transfer for Coumarin Dyes.

    Science.gov (United States)

    1983-10-31

    Mechanism of cousarin photodegradation . Ithe behavior of eoiuma dyes is water ad In aqueous detergent media,. and the effsects of medism aud, additives on...D-i36 345 ELECTRON DONOR-ACCEPTOR UENCHING AND PHOTOINDUCED i/i Ai ELECTRON TRANSFER FOR COUMARIN DYES (U) BOSTON UNIY MR DEPT OF CHEMISTRY G JONES...TYPE OF REPORT & PEIOD COVERED Electron Donor-acceptor Quenching and Photo- Technical, 1/1/82-10/31/82 induced Electron Transfer for Coumarin Dyes S

  8. Direct interspecies electron transfer between Geobacter metallireducens and Methanosarcina barkeri

    DEFF Research Database (Denmark)

    Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Liu, Fanghua

    2014-01-01

    Direct interspecies electron transfer (DIET) is potentially an effective form of syntrophy in methanogenic communities, but little is known about the diversity of methanogens capable of DIET. The ability of Methanosarcina barkeri, to participate in DIET was evaluated in co-culture with Geobacter...... metallireducens. Co-cultures formed aggregates that shared electrons via DIET during the stoichiometric conversion of ethanol to methane. Co-cultures could not be initiated with a pilin-deficient G. metallireducens, suggesting that long-range electron transfer along pili was important for DIET. Amendments...... physical contact was not necessary for interspecies H2 transfer. M. barkeri is the second methanogen found to accept electrons via DIET and the first methanogen known to be capable of using either H2 or electrons derived from DIET for CO2 reduction. Furthermore, M. barkeri is genetically tractable, making...

  9. Different mechanisms for hole and electron transfer along identical molecular bridges: the importance of the initial state delocalization.

    Science.gov (United States)

    Gorczak, Natalie; Tarkuç, Simge; Renaud, Nicolas; Houtepen, Arjan J; Eelkema, Rienk; Siebbeles, Laurens D A; Grozema, Ferdinand C

    2014-06-05

    We report measurements of hole and electron transfer along identical oligo-p-phenylene molecular bridges of increasing length. Although the injection barriers for hole and electron transfer are similar, we observed striking differences in the distance dependence and absolute magnitude of the rates of these two processes. Electron transfer is characterized by an almost distance-independent, fast charge-transfer rate. Hole transfer presents a much slower rate that decreases significantly with the length of the bridge. Time-dependent density functional calculations show that the observed differences can be explained by the delocalization of the respective initial excitation. The evaluation of the initial state is therefore essential when comparing charge-transfer rates between different donor-bridge-acceptor systems.

  10. Potential Energy Diagrams: A Conceptual Tool in the Study of Electron Transfer Reactions.

    Science.gov (United States)

    Lewis, Nita A.

    1980-01-01

    Describes how the potential energy diagram may be used to theoretically describe the processes involved in a system undergoing electron transfer. Examines factors important in electron transfer reactions and discusses several classes of electron transfer reactions. (CS)

  11. A modified Fricke gel dosimeter for fast electron blood dosimetry

    Science.gov (United States)

    Del Lama, L. S.; de Góes, E. G.; Sampaio, F. G. A.; Petchevist, P. C. D.; de Almeida, A.

    2014-12-01

    It has been suggested for more than forty years that blood and blood components be irradiated before allogeneic transfusions for immunosuppressed patients in order to avoid the Transfusion-Associated Graft-versus-Host Disease (TA-GVHD). Whole blood, red blood cells, platelets and granulocytes may have viable T cells and should be irradiated before transfusion for different patient clinical conditions. According to international guides, absorbed doses from 25 up to 50 Gy should be delivered to the central middle plane of each blood bag. Although gamma and X-rays from radiotherapy equipments and dedicated cell irradiators are commonly used for this purpose, electron beams from Linear Accelerators (LINACs) could be used as well. In this work, we developed a methodology able to acquire dosimetric data from blood irradiations, especially after fast electrons exposures. This was achieved using a proposed Fricke Xylenol Gel (FXGp) dosimeter, which presents closer radiological characteristics (attenuation coefficients and stopping-powers) to the whole blood, as well as complete absorbed dose range linearity. The developed methodology and the FXGp dosimeter were also able to provide isodose curves and field profiles for the irradiated samples.

  12. Fast character projection electron beam lithography for diffractive optical elements

    Science.gov (United States)

    Harzendorf, Torsten; Fuchs, Frank; Banasch, Michael; Zeitner, Uwe D.

    2014-05-01

    Electron beam lithography becomes attractive also for the fabrication of large scale diffractive optical elements by the use of the character projection (CP) technique. Even in the comparable fast variable shaped beam (VSB) exposure approach for conventional electron beam writers optical nanostructures may require very long writing times exceeding 24 hours per wafer because of the high density of features, as required by e.g. sub-wavelength nanostructures. Using character projection, the writing time can be reduced by more than one order of magnitude, due to the simultaneous exposure of multiple features. The benefit of character projection increases with increasing complexity of the features and decreasing period. In this contribution we demonstrate the CP technique for a grating of hexagonal symmetry at 350nm period. The pattern is designed to provide antireflective (AR) properties, which can be adapted in their spectral and angular domain for applications from VIS to NIR by changing the feature size and the etching depth of the nanostructure. This AR nanostructure can be used on the backside of optical elements e.g. gratings, when an AR coating stack could not be applied for the reason of climatic conditions or wave front accuracy.

  13. A modified Fricke gel dosimeter for fast electron blood dosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Del Lama, L.S., E-mail: lucasdellama@gmail.com [Departamento de Fsica, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo (FFCLRP/USP), Av. Bandeirantes, 3900, CEP 14040-901, Bairro Monte Alegre, Ribeirão Preto, São Paulo (Brazil); Góes, E.G. de [Instituto de Matemática, Estatística e Física, Universidade Federal de Rio Grande (IMEF/FURG), Av. Itália, km 8, CEP 96201-900, Bairro Carreiros, Rio Grande, Rio Grande do Sul (Brazil); Sampaio, F.G.A.; Petchevist, P.C.D.; Almeida, A. de [Departamento de Fsica, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo (FFCLRP/USP), Av. Bandeirantes, 3900, CEP 14040-901, Bairro Monte Alegre, Ribeirão Preto, São Paulo (Brazil)

    2014-12-15

    It has been suggested for more than forty years that blood and blood components be irradiated before allogeneic transfusions for immunosuppressed patients in order to avoid the Transfusion-Associated Graft-versus-Host Disease (TA-GVHD). Whole blood, red blood cells, platelets and granulocytes may have viable T cells and should be irradiated before transfusion for different patient clinical conditions. According to international guides, absorbed doses from 25 up to 50 Gy should be delivered to the central middle plane of each blood bag. Although gamma and X-rays from radiotherapy equipments and dedicated cell irradiators are commonly used for this purpose, electron beams from Linear Accelerators (LINACs) could be used as well. In this work, we developed a methodology able to acquire dosimetric data from blood irradiations, especially after fast electrons exposures. This was achieved using a proposed Fricke Xylenol Gel (FXG{sub p}) dosimeter, which presents closer radiological characteristics (attenuation coefficients and stopping-powers) to the whole blood, as well as complete absorbed dose range linearity. The developed methodology and the FXG{sub p} dosimeter were also able to provide isodose curves and field profiles for the irradiated samples.

  14. Distal [FeS]-Cluster Coordination in [NiFe]-Hydrogenase Facilitates Intermolecular Electron Transfer.

    Science.gov (United States)

    Petrenko, Alexander; Stein, Matthias

    2017-01-05

    Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal iron-sulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from Density Functional Theory (DFT) calculations. The distal cubane FeS-cluster has a three-cysteine and one-histidine coordination [Fe₄S₄](His)(Cys)₃ first ligation sphere. The reorganization energy (inner- and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and an all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe₄S₄](Cys)₄ case. The fast and efficient electron transfer from the distal iron-sulfur cluster is realized by a fine-tuned protein environment, which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering.

  15. Reduced Interocular Transfer of Spatial Adaptation for Fast Stimuli

    Directory of Open Access Journals (Sweden)

    Daniel H Baker

    2012-05-01

    Full Text Available Threshold elevation following monocular adaptation is weaker in the unadapted eye than in the adapted eye. At least 15 studies have measured this interocular transfer (IOT phenomenon, and typically report around 60% transfer. Yet almost all of these studies used spatial frequencies above 3c/deg, very slow temporal parameters, and criterion sensitive methods (method of adjustment, yes/no. In recent work, we (Meese and Baker 2011, i-Perception 2 159–182 found markedly weaker interocular transfer at low spatial and high temporal frequencies. Here, we measure IOT in 9 observers for a broad range of spatiotemporal frequencies (0.5, 2, and 8c/deg; 1, 4, and 15Hz using a 2AFC paradigm. Targets were horizontal Gabor patches with a full-width-at-half height of 1.67 (lower frequencies or 6.68 (8c/deg grating cycles. Adaptors were larger gratings with the same spatiotemporal properties as the targets. Observers adapted for 2 min initially, and 5 s between each trial, with monocular presentation enabled by shutter goggles. We typically found weaker IOT than previously reported (<50%, particularly for our fastest stimuli (lowest spatial and highest temporal frequencies, where it was virtually absent in all cases. Binocular summation and monocular adaptation were normal in all conditions. This implies that adaptation to ‘magno’ stimuli, not investigated in previous studies, occurs at a monocular locus. We also consider possible methodological confounds in classical studies which might have inflated the levels of IOT. These include the formation of retinal afterimages from static adaptors and changes in criterion unrelated to changes in sensitivity.

  16. 77 FR 30923 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-05-24

    ... (ACH) transactions, telephone bill-payment plans, and remote banking service. Regulation E defines an... Part 1005 [Docket No. CFPB-2012-0019] RIN 3170-AA22 Electronic Fund Transfers (Regulation E) AGENCY... methods: Electronic: http://www.regulations.gov . Follow the instructions for submitting comments. Mail...

  17. Numerical Simulation of Transient Moisture Transfer into an Electronic Enclosure

    DEFF Research Database (Denmark)

    Shojaee Nasirabadi, Parizad; Jabbaribehnam, Mirmasoud; Hattel, Jesper Henri

    2016-01-01

    inside the enclosures to be able to protect the electronic systems.In this work, moisture transfer into a typical electronic enclosure is numerically studied using CFD. In order to reduce theCPU-time and make a way for subsequent factorial design analysis, a simplifying modification is applied in which...

  18. Numerical Simulation of Transient Moisture Transfer into an Electronic Enclosure

    DEFF Research Database (Denmark)

    Shojaee Nasirabadi, Parizad; Jabbaribehnam, Mirmasoud; Hattel, Jesper Henri

    2016-01-01

    inside the enclosures to be able to protect the electronic systems.In this work, moisture transfer into a typical electronic enclosure is numerically studied using CFD. In order to reduce theCPU-time and make a way for subsequent factorial design analysis, a simplifying modification is applied in which...

  19. Electron transfer through rigid organic molecular wires enhanced by electronic and electron-vibration coupling.

    Science.gov (United States)

    Sukegawa, Junpei; Schubert, Christina; Zhu, Xiaozhang; Tsuji, Hayato; Guldi, Dirk M; Nakamura, Eiichi

    2014-10-01

    Electron transfer (ET) is a fundamental process in a wide range of biological systems, photovoltaics and molecular electronics. Therefore to understand the relationship between molecular structure and ET properties is of prime importance. For this purpose, photoinduced ET has been studied extensively using donor-bridge-acceptor molecules, in which π-conjugated molecular wires are employed as bridges. Here, we demonstrate that carbon-bridged oligo-p-phenylenevinylene (COPV), which is both rigid and flat, shows an 840-fold increase in the ET rate compared with the equivalent flexible molecular bridges. A 120-fold rate enhancement is explained in terms of enhanced electronic coupling between the electron donor and the electron acceptor because of effective conjugation through the COPVs. The remainder of the rate enhancement is explained by inelastic electron tunnelling through COPV caused by electron-vibration coupling, unprecedented for organic molecular wires in solution at room temperature. This type of nonlinear effect demonstrates the versatility and potential practical utility of COPVs in molecular device applications.

  20. Electron Transfer Dissociation of Doubly Sodiated Glycerophosphocholine Lipids

    Science.gov (United States)

    Liang, Xiaorong; Liu, Jian; LeBlanc, Yves; Covey, Tom; Ptak, A. Celeste; Brenna, J. Thomas; McLuckey, Scott A.

    2009-01-01

    The ability to generate gaseous doubly charged cations of glycerophosphocholine (GPC) lipids via electrospray ionization has made possible the evaluation of electron transfer dissociation (ETD) for their structural characterization. Doubly sodiated GPC cations have been reacted with azobenzene radical anions in a linear ion trap mass spectrometer. The ion/ion reactions proceed through sodium transfer, electron transfer, and complex formation. Electron transfer reactions are shown to give rise to cleavage at each ester linkage with the subsequent loss of a neutral quaternary nitrogen moiety. Electron transfer without dissociation produces [M+2Na]+• radical cations, which undergo collision-induced dissociation (CID) to give products that arise from bond cleavage of each fatty acid chain. The CID of the complex ions yields products similar to those produced directly from the electron transfer reactions of doubly sodiated GPC, although with different relative abundances. These findings indicate that the analysis of GPC lipids by ETD in conjunction with CID can provide some structural information, such as the number of carbons, degree of unsaturation for each fatty acid substituent, and the positions of the fatty acid substituents; some information about the location of the double bonds may be present in low intensity CID product ions. PMID:17719238

  1. Toddlers' word learning and transfer from electronic and print books.

    Science.gov (United States)

    Strouse, Gabrielle A; Ganea, Patricia A

    2017-04-01

    Transfer from symbolic media to the real world can be difficult for young children. A sample of 73 toddlers aged 17 to 23months were read either an electronic book displayed on a touchscreen device or a traditional print book in which a novel object was paired with a novel label. Toddlers in both conditions learned the label within the context of the book. However, only those who read the traditional format book generalized and transferred the label to other contexts. An older group of 28 toddlers aged 24 to 30months did generalize and transfer from the electronic book. Across ages, those children who primarily used screens to watch prerecorded video at home transferred less from the electronic book than those with more diverse home media experiences. Copyright © 2016 Elsevier Inc. All rights reserved.

  2. Bacterial Electron Transfer Chains Primed by Proteomics

    NARCIS (Netherlands)

    Wessels, H.; Almeida, N.M. de; Kartal, B.; Keltjens, J.T.

    2016-01-01

    Electron transport phosphorylation is the central mechanism for most prokaryotic species to harvest energy released in the respiration of their substrates as ATP. Microorganisms have evolved incredible variations on this principle, most of these we perhaps do not know, considering that only a fracti

  3. Promoting interspecies electron transfer with biochar

    DEFF Research Database (Denmark)

    Chen, Shanshan; Rotaru, Amelia-Elena; Shrestha, Pravin Malla;

    2014-01-01

    to that previously reported for granular activated carbon (GAC). Although the biochars investigated were 1000 times less conductive than GAC, they stimulated DIET in co-cultures of Geobacter metallireducens with Geobacter sulfurreducens or Methanosarcina barkeri in which ethanol was the electron donor. Cells were...

  4. 75 FR 31665 - Electronic Fund Transfers

    Science.gov (United States)

    2010-06-04

    ... purposes of this rulemaking. List of Subjects in 12 CFR Part 205 Consumer protection, Electronic fund... the consumer of the right to revoke the opt-in at any time. See Sec. 205.17(d)(6), which permits... a consumer's account, unless the consumer affirmatively consents, or opts in, to the institution's...

  5. Fast and simple model for atmospheric radiative transfer

    Directory of Open Access Journals (Sweden)

    F. C. Seidel

    2010-05-01

    Full Text Available Radiative transfer models (RTMs are of utmost importance for quantitative remote sensing, especially for compensating atmospheric perturbation. A persistent trade-off exists between approaches that prefer accuracy at the cost of computational complexity, versus those favouring simplicity at the cost of reduced accuracy. We propose an approach in the latter category, using analytical equations, parameterizations and a correction factor to efficiently estimate the effect of molecular multiple scattering. We discuss the approximations together with an analysis of the resulting performance and accuracy. The proposed Simple Model for Atmospheric Radiative Transfer (SMART decreases the calculation time by a factor of more than 25 in comparison to the benchmark RTM~6S on the same infrastructure. The approximative computation of the atmospheric reflectance factor by SMART has an uncertainty ranging from about 5% to 10% for nadir spaceborne and airborne observational conditions. The combination of a large solar zenith angle (SZA with high aerosol optical depth (AOD at low wavelengths lead to uncertainties of up to 15%. SMART can be used to simulate the hemispherical conical reflectance factor (HCRF for spaceborne and airborne sensors, as well as for the retrieval of columnar AOD.

  6. Using k-alpha emission to determine fast electron spectra using the Hybrid code ZEPHYROS

    CERN Document Server

    White, Thomas; Gregori, Gianluca

    2014-01-01

    A high intensity laser-solid interaction invariably drives a non-thermal fast electron current through the target, however characterizing these fast electron distributions can prove difficult. An understanding of how these electrons propagate through dense materials is of fundamental interest and has applications relevant to fast ignition schemes and ion acceleration. Here, we utilize an upgraded version of the Hybrid code ZEPHYROS to demonstrate how the resulting k-alpha emission from such an interaction can be used as a diagnostic to obtain the characteristic temperature, divergence and total energy of the fast electron population.

  7. Scaling of cross-sections for asymmetric (, 3) process on helium-like ions by fast electrons

    Indian Academy of Sciences (India)

    M K Srivastava

    2004-11-01

    An approximate simple scaling law is obtained for asymmetric (, 3) process on helium-like ions for double ionization by fast electrons. It is based on the equation $(Z'^{3} /)$ exp$[−Z' (r_{1} + r_{2})]$, $Z' = Z − (5/16)$ for ground state wave function of helium- like ions and $Z'^{2}$ scaling of energies. The scaling law is found to work very well if the lower energy electron is ejected along the momentum transfer direction and the other one is ejected in the opposite direction. It also works quite well if this electron is ejected within about 90° of the momentum transfer direction with the other electron going in the opposite direction. The scaling law becomes increasingly accurate as the target nuclear charge and the energy increase.

  8. Transient W-band EPR study of sequential electron transfer in photosynthetic bacterial reaction centers

    Energy Technology Data Exchange (ETDEWEB)

    Tang, J.; Utschig, L.M.; Poluektov, O.; Thurnauer, M.C. [Argonne National Lab., IL (United States). Chemistry Div.

    1999-06-17

    The key reaction of photosynthetic solar energy conversion involves the photoexcitation of a primary donor (P) followed by rapid, sequential electron transfer to a series of acceptors resulting in charge separation. Electron-spin polarized (ESP) EPR spectra at W-band (95 GHz) were obtained for deuterated Fe-removed/Zn-substituted photosynthetic bacterial reaction centers (RCs) to investigate the influence of the rate of charge separation on the observed P{sup +}Q{sub A}{sup {minus}} charge separated state. Temperature dependent ESP EPR spectra for kinetically characterized Zn-substituted RCs from Rb. sphaeroides R-26 having different rates (k{sub Q}) of the electron transfer from the bacteriopheophytin to the quinone acceptor were obtained. The Zn-RCs exhibited either the native fast (200 ps){sup {minus}1} k{sub Q} or a slow (3--6 ns){sup {minus}1} k{sub Q} at 298 K as determined from transient optical measurements. Sequential electron-transfer polarization modeling of the polarized W-band EPR spectra obtained with these samples was used to address the reason for the differences in the electron-transfer rates. Here, the authors report the k{sub Q} rate constant, the temperature dependence of k{sub Q}, and the reorganization energy for the P{sup +}H{sup {minus}}Q{sub A} and P{sup +}HQ{sub A}{sup {minus}} electron-transfer step determined from SETP modeling of the experimental spectra. The reorganization energy for the electron-transfer process between P{sup +}H{sup {minus}}Q{sub A} and P{sup +}HQ{sub A}{sup {minus}}, and not structural changes in the donor or acceptor, was found to be the dominant factor that is altered during Fe-removal procedures.

  9. Lewis Acid Coupled Electron Transfer of Metal-Oxygen Intermediates.

    Science.gov (United States)

    Fukuzumi, Shunichi; Ohkubo, Kei; Lee, Yong-Min; Nam, Wonwoo

    2015-12-01

    Redox-inactive metal ions and Brønsted acids that function as Lewis acids play pivotal roles in modulating the redox reactivity of metal-oxygen intermediates, such as metal-oxo and metal-peroxo complexes. The mechanisms of the oxidative CH bond cleavage of toluene derivatives, sulfoxidation of thioanisole derivatives, and epoxidation of styrene derivatives by mononuclear nonheme iron(IV)-oxo complexes in the presence of triflic acid (HOTf) and Sc(OTf)3 have been unified as rate-determining electron transfer coupled with binding of Lewis acids (HOTf and Sc(OTf)3 ) by iron(III)-oxo complexes. All logarithms of the observed second-order rate constants of Lewis acid-promoted oxidative CH bond cleavage, sulfoxidation, and epoxidation reactions of iron(IV)-oxo complexes exhibit remarkably unified correlations with the driving forces of proton-coupled electron transfer (PCET) and metal ion-coupled electron transfer (MCET) in light of the Marcus theory of electron transfer when the differences in the formation constants of precursor complexes were taken into account. The binding of HOTf and Sc(OTf)3 to the metal-oxo moiety has been confirmed for Mn(IV) -oxo complexes. The enhancement of the electron-transfer reactivity of metal-oxo complexes by binding of Lewis acids increases with increasing the Lewis acidity of redox-inactive metal ions. Metal ions can also bind to mononuclear nonheme iron(III)-peroxo complexes, resulting in acceleration of the electron-transfer reduction but deceleration of the electron-transfer oxidation. Such a control on the reactivity of metal-oxygen intermediates by binding of Lewis acids provides valuable insight into the role of Ca(2+) in the oxidation of water to dioxygen by the oxygen-evolving complex in photosystem II. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Nanosecond-timescale spin transfer using individual electrons in a quadruple-quantum-dot device

    Energy Technology Data Exchange (ETDEWEB)

    Baart, T. A.; Jovanovic, N.; Vandersypen, L. M. K. [QuTech and Kavli Institute of Nanoscience, Delft University of Technology, P.O. Box 5046, 2600 GA Delft (Netherlands); Reichl, C.; Wegscheider, W. [Solid State Physics Laboratory, ETH Zürich, 8093 Zürich (Switzerland)

    2016-07-25

    The ability to coherently transport electron-spin states between different sites of gate-defined semiconductor quantum dots is an essential ingredient for a quantum-dot-based quantum computer. Previous shuttles using electrostatic gating were too slow to move an electron within the spin dephasing time across an array. Here, we report a nanosecond-timescale spin transfer of individual electrons across a quadruple-quantum-dot device. Utilizing enhanced relaxation rates at a so-called hot spot, we can upper bound the shuttle time to at most 150 ns. While actual shuttle times are likely shorter, 150 ns is already fast enough to preserve spin coherence in, e.g., silicon based quantum dots. This work therefore realizes an important prerequisite for coherent spin transfer in quantum dot arrays.

  11. Preferred sites and pathways for electron transfer in blue copper proteins

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1988-01-01

    Long-range electron transfer reactions proceed within and between metalloproteins at relatively fast rates and with marked specificities. The blue single copper proteins are well known electron carriers with their redox center being of limited accessibility to solvent and solutes. The question......, E.T. proceeds via an extended imidazole ring system, and in plastocyanin and stellacyanin via a weakly coupled pi-system. Therefore, a case emerges for suggesting that this is the common feature of the long-distance intramolecular E.T. in this class of metalloproteins. These pathways are most...

  12. Alternative ground states enable pathway switching in biological electron transfer

    Science.gov (United States)

    Abriata, Luciano A.; Álvarez-Paggi, Damián; Ledesma, Gabriela N.; Blackburn, Ninian J.; Vila, Alejandro J.; Murgida, Daniel H.

    2012-01-01

    Electron transfer is the simplest chemical reaction and constitutes the basis of a large variety of biological processes, such as photosynthesis and cellular respiration. Nature has evolved specific proteins and cofactors for these functions. The mechanisms optimizing biological electron transfer have been matter of intense debate, such as the role of the protein milieu between donor and acceptor sites. Here we propose a mechanism regulating long-range electron transfer in proteins. Specifically, we report a spectroscopic, electrochemical, and theoretical study on WT and single-mutant CuA redox centers from Thermus thermophilus, which shows that thermal fluctuations may populate two alternative ground-state electronic wave functions optimized for electron entry and exit, respectively, through two different and nearly perpendicular pathways. These findings suggest a unique role for alternative or “invisible” electronic ground states in directional electron transfer. Moreover, it is shown that this energy gap and, therefore, the equilibrium between ground states can be fine-tuned by minor perturbations, suggesting alternative ways through which protein–protein interactions and membrane potential may optimize and regulate electron–proton energy transduction. PMID:23054836

  13. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    -molecular mechanics scheme, and tools to analyse statistical data and generate relative free energies and free energy surfaces. The methodology is applied to several charge transfer species and reactions in chemical environments - chemical in the sense that solvent, counter ions and substrate surfaces are taken...... in to account - which directly influence the reactants and resulting reaction through both physical and chemical interactions. All methods are though general and can be applied to different types of chemistry. First, the basis of the various theoretical tools is presented and applied to several test systems...... to show general (or expected) properties. Properties such as in the physical and (semi-)chemical interface between classical and quantum systems and the effects of molecular bond length constraints on the temperature during simulations. As a second step the methodology is applied to the symmetric...

  14. [Electron transfer, ionization, and excitation in atomic collisions]. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1992-12-31

    Fundamental processes of electron transfer, ionization, and excitation in ion-atom and ion-ion collisions are studied. Attention is focussed on one- and two-electron systems and, more recently, quasi-one-electron systems whose electron-target-ion core can be accurately modeled by one-electron potentials. The basic computational approaches can then be taken with few, if any, approximations, and the underlying collisional mechanisms can be more clearly revealed. At intermediate collision energies (e.g., proton energies for p-He{sup +} collisions on the order of 100 kilo-electron volts), many electronic states are strongly coupled during the collision, a coupled-state approach, such as a coupled-Sturmian-pseudostate approach, is appropriate. At higher collision energies (million electron-volt energies) the coupling is weaker with, however, many more states being coupled together, so that high-order perturbation theory is essential.

  15. Plugging in or going wireless: strategies for interspecies electron transfer

    Science.gov (United States)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena

    2014-01-01

    Interspecies exchange of electrons enables a diversity of microbial communities to gain energy from reactions that no one microbe can catalyze. The first recognized strategies for interspecies electron transfer were those that relied on chemical intermediates that are recycled through oxidized and reduced forms. Well-studied examples are interspecies H2 transfer and the cycling of sulfur intermediates in anaerobic photosynthetic communities. Direct interspecies electron transfer (DIET) in which two species establish electrical contact is an alternative. Electrical contacts documented to date include electrically conductive pili, as well as conductive iron minerals and conductive carbon moieties such as activated carbon and biochar. Interspecies electron transfer is central to the functioning of methane-producing microbial communities. The importance of interspecies H2 transfer in many methanogenic communities is clear, but under some circumstances DIET predominates. It is expected that further mechanistic studies and broadening investigations to a wider range of environments will help elucidate the factors that favor specific forms of interspecies electron exchange under different environmental conditions. PMID:24904551

  16. Plugging in or Going Wireless: Strategies for Interspecies Electron Transfer

    Directory of Open Access Journals (Sweden)

    Pravin Malla Shrestha

    2014-05-01

    Full Text Available Interspecies exchange of electrons enables a diversity of microbial communities to gain energy from reactions that no one microbe can catalyze. The first recognized strategies for interspecies electron transfer were those that relied on chemical intermediates that are recycled through oxidized and reduced forms. Well-studied examples are interspecies H2 transfer and the cycling of sulfur intermediates in anaerobic photosynthetic communities. Direct interspecies electron transfer (DIET in which two species establish electrical contacts is an alternative. Electrical contacts documented to date include electrically conductive pili, as well as conductive iron minerals and conductive carbon moieties such as activated carbon and biochar. It seems likely that there are additional alternative strategies for interspecies electrical connections that have yet to be discovered. Interspecies electron transfer is central to the functioning of methane-producing microbial communities. The importance of interspecies H2 transfer in many methanogenic communities is clear, but under some circumstances DIET predominates. It is expected that further mechanistic studies and broadening investigations to a wider range of environments will help elucidate the factors that favor specific forms of interspecies electron exchange under different environmental conditions.

  17. Engineered electron-transfer chain in photosystem 1 based photocathodes outperforms electron-transfer rates in natural photosynthesis.

    Science.gov (United States)

    Kothe, Tim; Pöller, Sascha; Zhao, Fangyuan; Fortgang, Philippe; Rögner, Matthias; Schuhmann, Wolfgang; Plumeré, Nicolas

    2014-08-25

    Photosystem 1 (PS1) triggers the most energetic light-induced charge-separation step in nature and the in vivo electron-transfer rates approach 50 e(-)  s(-1)  PS1(-1). Photoelectrochemical devices based on this building block have to date underperformed with respect to their semiconductor counterparts or to natural photosynthesis in terms of electron-transfer rates. We present a rational design of a redox hydrogel film to contact PS1 to an electrode for photocurrent generation. We exploit the pH-dependent properties of a poly(vinyl)imidazole Os(bispyridine)2Cl polymer to tune the redox hydrogel film for maximum electron-transfer rates under optimal conditions for PS1 activity. The PS1-containing redox hydrogel film displays electron-transfer rates of up to 335±14 e(-)  s(-1)  PS1(-1), which considerably exceeds the rates observed in natural photosynthesis or in other semiartificial systems. Under O2 supersaturation, photocurrents of 322±19 μA cm(-2) were achieved. The photocurrents are only limited by mass transport of the terminal electron acceptor (O2). This implies that even higher electron-transfer rates may be achieved with PS1-based systems in general. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Direct interspecies electron transfer between Geobacter metallireducens and Methanosarcina barkeri.

    Science.gov (United States)

    Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Liu, Fanghua; Markovaite, Beatrice; Chen, Shanshan; Nevin, Kelly P; Lovley, Derek R

    2014-08-01

    Direct interspecies electron transfer (DIET) is potentially an effective form of syntrophy in methanogenic communities, but little is known about the diversity of methanogens capable of DIET. The ability of Methanosarcina barkeri to participate in DIET was evaluated in coculture with Geobacter metallireducens. Cocultures formed aggregates that shared electrons via DIET during the stoichiometric conversion of ethanol to methane. Cocultures could not be initiated with a pilin-deficient G. metallireducens strain, suggesting that long-range electron transfer along pili was important for DIET. Amendments of granular activated carbon permitted the pilin-deficient G. metallireducens isolates to share electrons with M. barkeri, demonstrating that this conductive material could substitute for pili in promoting DIET. When M. barkeri was grown in coculture with the H2-producing Pelobacter carbinolicus, incapable of DIET, M. barkeri utilized H2 as an electron donor but metabolized little of the acetate that P.carbinolicus produced. This suggested that H2, but not electrons derived from DIET, inhibited acetate metabolism. P. carbinolicus-M. barkeri cocultures did not aggregate, demonstrating that, unlike DIET, close physical contact was not necessary for interspecies H2 transfer. M. barkeri is the second methanogen found to accept electrons via DIET and the first methanogen known to be capable of using either H2 or electrons derived from DIET for CO2 reduction. Furthermore, M. barkeri is genetically tractable,making it a model organism for elucidating mechanisms by which methanogens make biological electrical connections with other cells.

  19. Nanoantioxidant-driven plasmon enhanced proton-coupled electron transfer

    Science.gov (United States)

    Sotiriou, Georgios A.; Blattmann, Christoph O.; Deligiannakis, Yiannis

    2015-12-01

    Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol-1 and therefore facilitates PCET. The nanoparticle-driven plasmon-enhancement of PCET brings together the so far unrelated research domains of nanoplasmonics and electron/proton translocation with significant impact on applications based on interfacial electron/proton transfer.Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol-1 and therefore facilitates PCET. The nanoparticle-driven plasmon

  20. A novel fast mass transfer anaerobic inner loop fluidized bed biofilm reactor for PTA wastewater treatment.

    Science.gov (United States)

    Chen, Yingwen; Zhao, Jinlong; Li, Kai; Xie, Shitao

    In this paper, a fast mass transfer anaerobic inner loop fluidized bed biofilm reactor (ILFBBR) was developed to improve purified terephthalic acid (PTA) wastewater treatment. The emphasis of this study was on the start-up mode of the anaerobic ILFBBR, the hydraulic loadings and the operation stability. The biological morphology of the anaerobic biofilm in the reactors was also analyzed. The anaerobic column could operate successfully for 46 days due to the pre-aerating process. The anaerobic column had the capacity to resist shock loadings and maintained a high stable chemical oxygen demand (COD) and terephthalic acid removal rates at a hydraulic retention time of 5-10 h, even under conditions of organic volumetric loadings as high as 28.8 kg COD·m(-3).d(-1). The scanning electron microscope analysis of the anaerobic carrier demonstrated that clusters of prokaryotes grew inside of pores and that the filaments generated by pre-aeration contributed to the anaerobic biofilm formation and stability.

  1. Multi-Element Electron-Transfer Optical Detector System

    Science.gov (United States)

    Jordan, Jeffrey D. (Inventor)

    2004-01-01

    A multi-element optical detector system includes an electrically resistive screen that is substantially transparent to radiation energy having a wavelength of interest. A plurality of electron transfer elements (e.g., a low work function photoactive material or a carbon nanotube (CNT)-based element) are provided with each having a first end and a second end. The first end of each element is spaced apart from the screen by an evacuated gap. When the radiation energy passes through the screen with a bias voltage applied thereto, transfer of electrons through each element is induced from the first end to the second end such that a quantity indicative of the electrons transferred through each element can be detected.

  2. Vibrationally Assisted Electron Transfer Mechanism of Olfaction: Myth or Reality?

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Chang, Po-Yao; Schulten, Klaus

    2012-01-01

    to this suggestion an olfactory receptor is activated by electron transfer assisted through odorant vibrational excitation. The hundreds to thousands of different olfactory receptors in an animal recognize odorants over a discriminant landscape with surface properties and vibrational frequencies as the two major......, thereby, recent experiments performed on Drosophila melanogaster. Our demonstration is based on known physical properties of biological electron transfer and on ab initio calculations on odorants carried out for the purpose of the present study. We identify a range of physical characteristics which...... olfactory receptors and odorants must obey for the vibrationally assisted electron transfer mechanism to function. We argue that the stated characteristics are feasible for realistic olfactory receptors, noting, though, that the receptor structure presently is still unknown, but can be studied through...

  3. Electron transfer in proteins: theory, applications and future perspectives.

    Science.gov (United States)

    Saen-Oon, Suwipa; Lucas, Maria Fatima; Guallar, Victor

    2013-10-07

    The study of electron transfer (ET) by means of computational techniques has experienced a great development in the last few decades. In particular, understanding the atomic details of its mechanism in complex biological systems is currently possible with a large range of different in silico modelling tools. We review here some theories and representative major contributions to this development. We also underline some of our group's main inputs, focusing on long range and protein-protein electron transfer, and analyse future perspectives. At the end of the article, we emphasize the importance of the basic electron transfer knowledge in the frame of medical and bioengineering applications: mitochondrial therapeutic targets, bioengineering for clean energy, and biosensors.

  4. Electron transfer statistics and thermal fluctuations in molecular junctions.

    Science.gov (United States)

    Goswami, Himangshu Prabal; Harbola, Upendra

    2015-02-28

    We derive analytical expressions for probability distribution function (PDF) for electron transport in a simple model of quantum junction in presence of thermal fluctuations. Our approach is based on the large deviation theory combined with the generating function method. For large number of electrons transferred, the PDF is found to decay exponentially in the tails with different rates due to applied bias. This asymmetry in the PDF is related to the fluctuation theorem. Statistics of fluctuations are analyzed in terms of the Fano factor. Thermal fluctuations play a quantitative role in determining the statistics of electron transfer; they tend to suppress the average current while enhancing the fluctuations in particle transfer. This gives rise to both bunching and antibunching phenomena as determined by the Fano factor. The thermal fluctuations and shot noise compete with each other and determine the net (effective) statistics of particle transfer. Exact analytical expression is obtained for delay time distribution. The optimal values of the delay time between successive electron transfers can be lowered below the corresponding shot noise values by tuning the thermal effects.

  5. PHOTOINDUCED CHARGE TRANSFER POLYMERIZATION OF STYRENE INITIATED BY ELECTRON ACCEPTOR

    Institute of Scientific and Technical Information of China (English)

    CAO Weixiao; ZHANG Peng; FENG Xinde

    1995-01-01

    Photoinduced charge transfer polymerization of styrene(St) with electron acceptor as initiator was investigated. In case of fumaronitrile (FN) or maleic anhydride (MA) as initiator the polymerization takes place regularly, whereas the tetrachloro-1, 4-benzenequinone (TCQ), 2, 3-dichloro-5, 6-dicyano-1, 4-benzenequinone (DDQ) . or tetracyano ethylene (TCNE) as initiator the polymerization proceeds reluctantly only after the photoaddition reaction. A mechanism was proposed that free radicals would be formed following the charge and proton transfer in the exciplex formed between St and electron acceptors.

  6. Marcus Electron Transfer Reactions with Bulk Metallic Catalysis

    CERN Document Server

    Widom, A; Srivastava, Y N

    2015-01-01

    Electron transfer organic reaction rates are considered employing the classic physical picture of Marcus wherein the heats of reaction are deposited as the energy of low frequency mechanical oscillations of reconfigured molecular positions. If such electron transfer chemical reaction events occur in the neighborhood of metallic plates, then electrodynamic interface fields must also be considered in addition to mechanical oscillations. Such electrodynamic interfacial electric fields in principle strongly effect the chemical reaction rates. The thermodynamic states of the metal are unchanged by the reaction which implies that metallic plates are purely catalytic chemical agents.

  7. Promoting direct interspecies electron transfer with activated carbon

    DEFF Research Database (Denmark)

    Liu, Fanghua; Rotaru, Amelia-Elena; Shrestha, Pravin M.

    2012-01-01

    of methanogenesis might be to facilitate direct interspecies electron transfer (DIET) between bacteria and methanogens. Metabolism was substantially accelerated when GAC was added to co-cultures of Geobacter metallireducens and Geobacter sulfurreducens grown under conditions previously shown to require DIET. Cells...... were attached to GAC, but did not aggregate as they do when making biological electrical connections between cells. Studies with a series of gene deletion mutants eliminated the possibility that GAC promoted electron exchange via interspecies hydrogen or formate transfer and demonstrated that DIET...

  8. High-pressure effects on intramolecular electron transfer compounds

    CERN Document Server

    He Li Ming; Li Hong; Zhang Bao Wen; Li Yi; Yang Guo Qiang

    2002-01-01

    We explore the effect of pressure on the fluorescence spectra of the intramolecular electron transfer compound N-(1-pyrenylmethyl), N-methyl-4-methoxyaniline (Py-Am) and its model version, with poly(methyl methacrylate) blended in, at high pressure up to 7 GPa. The emission properties of Py-Am and pyrene show distinct difference with the increase of pressure. This difference indicates the strength of the charge transfer interaction resulting from the adjusting of the conformation of Py-Am with increase of pressure. The relationship between the electronic state of the molecule and pressure is discussed.

  9. Photoinduced electron transfer in singly labeled thiouredopyrenetrisulfonate azurin derivatives

    DEFF Research Database (Denmark)

    Borovok, N; Kotlyar, A B; Pecht, I;

    1999-01-01

    efficiency. TUPS derivatives of azurin, singly labeled at specific lysine residues, were prepared and purified to homogeneity by ion exchange HPLC. Transient absorption spectroscopy was used to directly monitor the rates of the electron transfer reaction from the photoexcited triplet state of TUPS to Cu...... of the crystal structure of Pseudomonas aeruginosa azurin and molecular structure calculation of the TUPS modified proteins, electron transfer pathways were calculated. Analysis of the results revealed a good correlation between separation distance from donor to Cu ligating atom (His-N or Cys-S) and the observed...

  10. Investigation of transferred-electron oscillations in diamond

    Science.gov (United States)

    Suntornwipat, N.; Majdi, S.; Gabrysch, M.; Isberg, J.

    2016-05-01

    The recent discovery of Negative Differential Mobility (NDM) in intrinsic single-crystalline diamond enables the development of devices for high frequency applications. The Transferred-Electron Oscillator (TEO) is one example of such devices that uses the benefit of NDM to generate continuous oscillations. This paper presents theoretical investigations of a diamond TEO in the temperature range of 110 to 140 K where NDM has been observed. Our simulations map out the parameter space in which transferred-electron oscillations are expected to occur for a specific device geometry. The results are promising and indicate that it is possible to fabricate diamond based TEO devices.

  11. Reactant-Product Quantum Coherence in Electron Transfer Reactions

    CERN Document Server

    Kominis, I K

    2012-01-01

    We investigate the physical meaning of quantum superposition states between reactants and products in electron transfer reactions. We show that such superpositions are strongly suppressed and to leading orders of perturbation theory do not pertain in electron transfer reactions. This is because of the intermediate manifold of states separating the reactants from the products. We provide an intuitive description of these considerations with Feynman diagrams. We also discuss the relation of such quantum coherences to understanding the fundamental quantum dynamics of spin-selective radical-ion-pair reactions.

  12. Bimolecular Excited-State Electron Transfer with Surprisingly Long-Lived Radical Ions

    KAUST Repository

    Alsam, Amani Abdu

    2015-09-02

    We explored the excited-state interactions of bimolecular, non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and 1,4-dicyanobenzene (DCB) using steady-state and time-resolved techniques, including femto- and nanosecond transient absorption and femtosecond infrared spectroscopies with broadband capabilities. The experimental results demonstrated that photo-induced electron transfer from PFN to DCB occurs on the picosecond time scale, leading to the formation of PFN+• and DCB-• radical ions. Interestingly, real-time observations of the vibrational marker modes on the acceptor side provided direct evidence and insight into the electron transfer process indirectly inferred from UV-Vis experiments. The band narrowing on the picosecond time scale observed on the antisymmetric C-N stretching vibration of the DCB radical anion provides clear experimental evidence that a substantial part of the excess energy is channeled into vibrational modes of the electron transfer product and that the geminate ion pairs dissociate. More importantly, our nanosecond time-resolved data indicate that the charge-separated state is very long lived ( 30 ns) due to the dissociation of the contact radical ion pair into free ions. Finally, the fast electron transfer and slow charge recombination anticipate the current donor−acceptor system with potential applications in organic solar cells.

  13. 12 CFR 205.15 - Electronic fund transfer of government benefits.

    Science.gov (United States)

    2010-01-01

    ... 12 Banks and Banking 2 2010-01-01 2010-01-01 false Electronic fund transfer of government benefits... RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.15 Electronic fund transfer of government... consumer for use in initiating an electronic fund transfer of government benefits from an account,...

  14. Time-dependent calculations of transfer ionization by fast proton-helium collision in one-dimensional kinematics

    Science.gov (United States)

    Serov, Vladislav V.; Kheifets, A. S.

    2014-12-01

    We analyze a transfer ionization (TI) reaction in the fast proton-helium collision H++He →H0+He2 ++ e- by solving a time-dependent Schrödinger equation (TDSE) under the classical projectile motion approximation in one-dimensional kinematics. In addition, we construct various time-independent analogs of our model using lowest-order perturbation theory in the form of the Born series. By comparing various aspects of the TDSE and the Born series calculations, we conclude that the recent discrepancies of experimental and theoretical data may be attributed to deficiency of the Born models used by other authors. We demonstrate that the correct Born series for TI should include the momentum-space overlap between the double-ionization amplitude and the wave function of the transferred electron.

  15. Time-dependent calculations of transfer ionization by fast proton-helium collision in one-dimensional kinematics

    CERN Document Server

    Serov, Vladislav V

    2014-01-01

    We analyze a transfer ionization (TI) reaction in the fast proton-helium collision $\\rm H^+ + He \\to H^0 + He^{2+} + e^-$ by solving a time-dependent Schr\\"odinger equation (TDSE) under the classical projectile motion approximation in one-dimensional kinematics. In addition, we construct various time independent analogues of our model using lowest order perturbation theory in the form of the Born series. By comparing various aspects of the TDSE and the Born series calculations, we conclude that the recent discrepancies of experimental and theoretical data may be attributed to deficiency of the Born models used by other authors. We demonstrate that the correct Born series for TI should include the momentum space overlap between the double ionization amplitude and the wave function of the transferred electron.

  16. Water Activated Graphene Oxide Transfer Using Wax Printed Membranes for Fast Patterning of a Touch Sensitive Device.

    Science.gov (United States)

    Baptista-Pires, Luis; Mayorga-Martínez, Carmen C; Medina-Sánchez, Mariana; Montón, Helena; Merkoçi, Arben

    2016-01-26

    We demonstrate a graphene oxide printing technology using wax printed membranes for the fast patterning and water activation transfer using pressure based mechanisms. The wax printed membranes have 50 μm resolution, longtime stability and infinite shaping capability. The use of these membranes complemented with the vacuum filtration of graphene oxide provides the control over the thickness. Our demonstration provides a solvent free methodology for printing graphene oxide devices in all shapes and all substrates using the roll-to-roll automatized mechanism present in the wax printing machine. Graphene oxide was transferred over a wide variety of substrates as textile or PET in between others. Finally, we developed a touch switch sensing device integrated in a LED electronic circuit.

  17. Conduction mechanism studies on electron transfer of disordered system

    Institute of Scientific and Technical Information of China (English)

    徐慧; 宋祎璞; 李新梅

    2002-01-01

    Using the negative eigenvalue theory and the infinite order perturbation theory, a new method was developed to solve the eigenvectors of disordered systems. The result shows that eigenvectors change from the extended state to the localized state with the increase of the site points and the disordered degree of the system. When electric field is exerted, the electrons transfer from one localized state to another one. The conductivity is induced by the electron transfer. The authors derive the formula of electron conductivity and find the electron hops between localized states whose energies are close to each other, whereas localized positions differ from each other greatly. At low temperature the disordered system has the character of the negative differential dependence of resistivity and temperature.

  18. Charge transfer to ground-state ions produces free electrons

    Science.gov (United States)

    You, D.; Fukuzawa, H.; Sakakibara, Y.; Takanashi, T.; Ito, Y.; Maliyar, G. G.; Motomura, K.; Nagaya, K.; Nishiyama, T.; Asa, K.; Sato, Y.; Saito, N.; Oura, M.; Schöffler, M.; Kastirke, G.; Hergenhahn, U.; Stumpf, V.; Gokhberg, K.; Kuleff, A. I.; Cederbaum, L. S.; Ueda, K.

    2017-01-01

    Inner-shell ionization of an isolated atom typically leads to Auger decay. In an environment, for example, a liquid or a van der Waals bonded system, this process will be modified, and becomes part of a complex cascade of relaxation steps. Understanding these steps is important, as they determine the production of slow electrons and singly charged radicals, the most abundant products in radiation chemistry. In this communication, we present experimental evidence for a so-far unobserved, but potentially very important step in such relaxation cascades: Multiply charged ionic states after Auger decay may partially be neutralized by electron transfer, simultaneously evoking the creation of a low-energy free electron (electron transfer-mediated decay). This process is effective even after Auger decay into the dicationic ground state. In our experiment, we observe the decay of Ne2+ produced after Ne 1s photoionization in Ne-Kr mixed clusters.

  19. Charge transfer to ground-state ions produces free electrons

    Science.gov (United States)

    You, D.; Fukuzawa, H.; Sakakibara, Y.; Takanashi, T.; Ito, Y.; Maliyar, G. G.; Motomura, K.; Nagaya, K.; Nishiyama, T.; Asa, K.; Sato, Y.; Saito, N.; Oura, M.; Schöffler, M.; Kastirke, G.; Hergenhahn, U.; Stumpf, V.; Gokhberg, K.; Kuleff, A. I.; Cederbaum, L. S.; Ueda, K

    2017-01-01

    Inner-shell ionization of an isolated atom typically leads to Auger decay. In an environment, for example, a liquid or a van der Waals bonded system, this process will be modified, and becomes part of a complex cascade of relaxation steps. Understanding these steps is important, as they determine the production of slow electrons and singly charged radicals, the most abundant products in radiation chemistry. In this communication, we present experimental evidence for a so-far unobserved, but potentially very important step in such relaxation cascades: Multiply charged ionic states after Auger decay may partially be neutralized by electron transfer, simultaneously evoking the creation of a low-energy free electron (electron transfer-mediated decay). This process is effective even after Auger decay into the dicationic ground state. In our experiment, we observe the decay of Ne2+ produced after Ne 1s photoionization in Ne–Kr mixed clusters. PMID:28134238

  20. Fast imaging with inelastically scattered electrons by off-axis chromatic confocal electron microscopy.

    Science.gov (United States)

    Zheng, Changlin; Zhu, Ye; Lazar, Sorin; Etheridge, Joanne

    2014-04-25

    We introduce off-axis chromatic scanning confocal electron microscopy, a technique for fast mapping of inelastically scattered electrons in a scanning transmission electron microscope without a spectrometer. The off-axis confocal mode enables the inelastically scattered electrons to be chromatically dispersed both parallel and perpendicular to the optic axis. This enables electrons with different energy losses to be separated and detected in the image plane, enabling efficient energy filtering in a confocal mode with an integrating detector. We describe the experimental configuration and demonstrate the method with nanoscale core-loss chemical mapping of silver (M4,5) in an aluminium-silver alloy and atomic scale imaging of the low intensity core-loss La (M4,5@840  eV) signal in LaB6. Scan rates up to 2 orders of magnitude faster than conventional methods were used, enabling a corresponding reduction in radiation dose and increase in the field of view. If coupled with the enhanced depth and lateral resolution of the incoherent confocal configuration, this offers an approach for nanoscale three-dimensional chemical mapping.

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

    Science.gov (United States)

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

    2015-03-17

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

  2. Photoinduced Reductive Electron Transfer in LNA:DNA Hybrids

    DEFF Research Database (Denmark)

    Wenge, Ulrike; Wengel, Jesper; Wagenknecht, Hans-Achim

    2012-01-01

    Lock it, but not too much: LNA units (locked or bridging nucleic acids) in LNA:DNA hybrids lead to a negative effect on electron transfer (ET), but they also force the nucleic acid structure in the A-type double helix, which allows a better base stacking than the normal B-type and thus positively...... influences the ET. This result is significant for the design of nucleic acids of molecular electronics....

  3. Nanoscale and single-molecule interfacial electron transfer

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Wackerbarth, Hainer; Nielsen, Jens Ulrik

    2003-01-01

    Electrochemical science and technology in the 21st century have reached high levels of sophistication. A fundamental quantum mechanical theoretical frame for interfacial electrochemical electron transfer (ET) was introduced by Revaz Dogonadze. This frame has remained for four decades as a basis...... scanning tunneling microscopy (STM) and single-electron tunneling (SET, or Coulomb blockade) in electrochemical. systems directly in aqueous electrolyte solution and at room temperature. We illustrate the new theoretical formalism and its perspectives by recent cases of electrochemical SET, negative...

  4. Quantum Mechanical Hysteresis and the Electron Transfer Problem

    CERN Document Server

    Etchegoin, P G

    2004-01-01

    We study a simple quantum mechanical symmetric donor-acceptor model for electron transfer (ET) with coupling to internal deformations. The model contains several basic properties found in biological ET in enzymes and photosynthetic centers; it produces tunnelling with hysteresis thus providing a simple explanation for the slowness of the reversed rate and the near 100% efficiency of ET in many biological systems. The model also provides a conceptual framework for the development of molecular electronics memory elements based on electrostatic architectures.

  5. Real-time study of fast-electron transport inside dense hot plasmas.

    Science.gov (United States)

    Sandhu, A S; Ravindra Kumar, G; Sengupta, S; Das, A; Kaw, P K

    2006-03-01

    We offer a method to study transport of fast electrons in dense hot media. The technique relies on temporal profiling of the laser induced magnetic fields and offers a unique capability to map the hot electron currents and their neutralization (or lack of it) by the return currents in the plasma. We report direct quantitative measurements of strong electric inhibition in insulators and turbulence induced anomalous stopping of hot electrons in conductors. The present technique can prove extremely important from the point of view of fast ignition scheme, which relies on the penetration of fast electrons into the fusion core.

  6. Electronic Coupling Dependence of Ultrafast Interfacial Electron Transfer on Nanocrystalline Thin Films and Single Crystal

    Energy Technology Data Exchange (ETDEWEB)

    Lian, Tianquan

    2014-04-22

    The long-term goal of the proposed research is to understand electron transfer dynamics in nanoparticle/liquid interface. This knowledge is essential to many semiconductor nanoparticle based devices, including photocatalytic waste degradation and dye sensitized solar cells.

  7. Photochemistry between a ruthenium(II) pyridylimidazole complex and benzoquinone: simple electron transfer versus proton-coupled electron transfer.

    Science.gov (United States)

    Hönes, Roland; Kuss-Petermann, Martin; Wenger, Oliver S

    2013-02-01

    A ruthenium(II) complex with two 4,4'-bis(trifluoromethyl)-2,2'-bipyridine chelates and a 2-(2'-pyridyl)imidazole ligand was synthesized and characterized by electrochemical and optical spectroscopic means. The respective complex has the potential to act as a combined electron-proton donor when promoted to its long-lived (3)MLCT excited state with visible light. The possibility of proton-coupled electron transfer (PCET) between the ruthenium(II) complex and 1,4-benzoquinone as an electron/proton acceptor was explored by steady-state and time-resolved luminescence spectroscopy, as well as by transient absorption spectroscopy in the nanosecond time regime. Excited-state deactivation is found to occur predominantly via simple oxidative quenching involving no proton motion, but a minor fraction of the photoexcited complex appears to react via PCET since there is spectral evidence for semiquinone as a photoproduct. Presumably, PCET is not kinetically competitive with simple electron transfer because the latter process is sufficiently exergonic and because there is little thermodynamic benefit from coupling proton transfer to the photoinduced electron transfer.

  8. Electron transfer in pH-sensitive nitroxide radicals

    Science.gov (United States)

    Barbon, Antonio; Bortolus, Marco; Isse, Abdirisak A.; Reznikov, Vladimir A.; Weiner, Lev

    2016-11-01

    Two pH-sensitive stable nitroxide radicals are characterized by EPR spectroscopy and cyclic voltammetry in aqueous solution at different pH values. The rates of the photochemically-induced electron transfer reactions from the protonated and deprotonated forms of the radicals to a ruthenium complex are determined.

  9. Correlating electronic and vibrational motions in charge transfer systems

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, Munira [Univ. of Washington, Seattle, WA (United States)

    2014-06-27

    The goal of this research program was to measure coupled electronic and nuclear motions during photoinduced charge transfer processes in transition metal complexes by developing and using novel femtosecond spectroscopies. The scientific highlights and the resulting scientific publications from the DOE supported work are outlined in the technical report.

  10. A molecularly based theory for electron transfer reorganization energy

    Energy Technology Data Exchange (ETDEWEB)

    Zhuang, Bilin; Wang, Zhen-Gang, E-mail: zgw@cheme.caltech.edu [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States)

    2015-12-14

    Using field-theoretic techniques, we develop a molecularly based dipolar self-consistent-field theory (DSCFT) for charge solvation in pure solvents under equilibrium and nonequilibrium conditions and apply it to the reorganization energy of electron transfer reactions. The DSCFT uses a set of molecular parameters, such as the solvent molecule’s permanent dipole moment and polarizability, thus avoiding approximations that are inherent in treating the solvent as a linear dielectric medium. A simple, analytical expression for the free energy is obtained in terms of the equilibrium and nonequilibrium electrostatic potential profiles and electric susceptibilities, which are obtained by solving a set of self-consistent equations. With no adjustable parameters, the DSCFT predicts activation energies and reorganization energies in good agreement with previous experiments and calculations for the electron transfer between metallic ions. Because the DSCFT is able to describe the properties of the solvent in the immediate vicinity of the charges, it is unnecessary to distinguish between the inner-sphere and outer-sphere solvent molecules in the calculation of the reorganization energy as in previous work. Furthermore, examining the nonequilibrium free energy surfaces of electron transfer, we find that the nonequilibrium free energy is well approximated by a double parabola for self-exchange reactions, but the curvature of the nonequilibrium free energy surface depends on the charges of the electron-transferring species, contrary to the prediction by the linear dielectric theory.

  11. Polymer glass transitions switch electron transfer in individual molecules

    NARCIS (Netherlands)

    Siekierzycka, J.R.; Hippius, C.; Würthner, F.; Williams, R.M.; Brouwer, A.M.

    2010-01-01

    Essentially complete photoinduced electron transfer quenching of the fluorescence of a perylene−calixarene compound occurs in poly(methyl acrylate) and poly(vinyl acetate) above their glass transition temperatures (T-g), but the fluorescence is completely recovered upon cooling the polymer matrix to

  12. Electron transfer flavoprotein deficiency: Functional and molecular aspects

    DEFF Research Database (Denmark)

    Schiff, M; Froissart, R; Olsen, Rikke Katrine Jentoft

    2006-01-01

    Multiple acyl-CoA dehydrogenase deficiency (MADD) is a recessively inherited metabolic disorder that can be due to a deficiency of electron transfer flavoprotein (ETF) or its dehydrogenase (ETF-ubiquinone oxidoreductase). ETF is a mitochondrial matrix protein consisting of alpha- (30kDa) and beta...

  13. Direct interspecies electron transfer between Geobacter metallireducens and Methanosarcina barkeri

    DEFF Research Database (Denmark)

    Rotaru, Amelia-Elena; Shrestha, Pravin Malla; Liu, Fanghua;

    2014-01-01

    Direct interspecies electron transfer (DIET) is potentially an effective form of syntrophy in methanogenic communities, but little is known about the diversity of methanogens capable of DIET. The ability of Methanosarcina barkeri, to participate in DIET was evaluated in co-culture with Geobacter...

  14. Adsorption and Interfacial Electron Transfer of Saccharomyces Cerevisiae

    DEFF Research Database (Denmark)

    Hansen, Allan Glargaard; Boisen, Anja; Nielsen, Jens Ulrik

    2003-01-01

    We have studied the adsorption and electron-transfer dynamics of Saccharomyces cerevisiae (yeast) iso-l-cytochrome c adsorbed on Au(lll) electrodes in aqueous phosphate buffer media. This cytochrome possesses a thiol group dos e to the protein surface (Cysl02) suitable for linking the protein...

  15. Nanoantioxidant-driven plasmon enhanced proton-coupled electron transfer.

    Science.gov (United States)

    Sotiriou, Georgios A; Blattmann, Christoph O; Deligiannakis, Yiannis

    2016-01-14

    Proton-coupled electron transfer (PCET) reactions involve the transfer of a proton and an electron and play an important role in a number of chemical and biological processes. Here, we describe a novel phenomenon, plasmon-enhanced PCET, which is manifested using SiO2-coated Ag nanoparticles functionalized with gallic acid (GA), a natural antioxidant molecule that can perform PCET. These GA-functionalized nanoparticles show enhanced plasmonic response at near-IR wavelengths, due to particle agglomeration caused by the GA molecules. Near-IR laser irradiation induces strong local hot-spots on the SiO2-coated Ag nanoparticles, as evidenced by surface enhanced Raman scattering (SERS). This leads to plasmon energy transfer to the grafted GA molecules that lowers the GA-OH bond dissociation enthalpy by at least 2 kcal mol(-1) and therefore facilitates PCET. The nanoparticle-driven plasmon-enhancement of PCET brings together the so far unrelated research domains of nanoplasmonics and electron/proton translocation with significant impact on applications based on interfacial electron/proton transfer.

  16. Solvent-Controlled Acceleration of Electron Transfer in Binary Mixtures

    NARCIS (Netherlands)

    Pugžlys, Audrius; Hartog, Harald P. den; Baltuška, Andrius; Pshenichnikov, Maxim S.; Umapathy, Siva; Wiersma, Douwe A.

    2001-01-01

    We report a 5-fold acceleration of the backward intermolecular electron transfer between a rhodamine 800 dye molecule and N,N-dimethylaniline (DMA). This effect results from the controlled variation of the solvent dynamical properties in binary mixtures of DMA and acetonitrile. The observed

  17. Dimers of Azurin as model systems for electron transfer

    NARCIS (Netherlands)

    Jongh, Thyra Estrid de

    2006-01-01

    This thesis describes the investigation of crosslinked complexes of the blue copper protein azurin by means of spectroscopic techniques such as Uv-Vis and NMR as well as by X-ray crystallography. These non-physiological dimers serve as model systems for interprotein electron transfer (ET) and allow

  18. Electron transfer in syntrophic communities of anaerobic bacteria and archaea

    NARCIS (Netherlands)

    Stams, A.J.M.; Plugge, C.M.

    2009-01-01

    Interspecies electron transfer is a key process in methanogenic and sulphate-reducing environments. Bacteria and archaea that live in syntrophic communities take advantage of the metabolic abilities of their syntrophic partner to overcome energy barriers and break down compounds that they cannot dig

  19. The intramolecular electron transfer between copper sites of nitrite reductase

    DEFF Research Database (Denmark)

    Farver, O; Eady, R R; Abraham, Z H

    1998-01-01

    The intramolecular electron transfer (ET) between the type 1 Cu(I) and the type 2 Cu(II) sites of Alcaligenes xylosoxidans dissimilatory nitrite reductase (AxNiR) has been studied in order to compare it with the analogous process taking place in ascorbate oxidase (AO). This internal process...

  20. Fast low-energy halo-to-halo transfers between Sun–planet systems

    Directory of Open Access Journals (Sweden)

    Shang Haibin

    2014-04-01

    Full Text Available In this paper, the problem of fast low-energy halo-to-halo transfers between Sun–planet systems is discussed under ephemeris constraints. According to the structure of an invariant manifold, employing an invariant manifold and planetary gravity assist to save fuel consumption is analyzed from the view of orbital energy. Then, a pseudo-manifold is introduced to replace the invariant manifold in such a way that more transfer opportunities are allowed. Fast escape and capture can be achieved along the pseudo-manifold. Furthermore, a global searching method that is based on patched-models is proposed to find an appropriate transfer trajectory. In this searching method, the trajectory is divided into several segments that can be designed under simple dynamical models, and an analytical algorithm is developed for connecting the segments. Earth–Mars and Earth–Venus halo-to-halo transfers are designed to demonstrate the proposed approach. Numerical results show that the transfers that combine the pseudo-manifolds and planetary gravity assist can offer significant fuel consumption and flight time savings over traditional transfer schemes.

  1. Fundamental Research on Convective Heat Transfer in Electronic Cooling Technology

    Institute of Scientific and Technical Information of China (English)

    C.F.Ma; Y.P.Gan; 等

    1992-01-01

    During the past six years comprehensive research programs have been conducted at the Beijing Polytechnic University to provide a better understanding of heat transfer characteristics of existing and condidate cooling techniques for electronic and microelestanding of heat transfer characteristics of existing and condidate cooling techniques for electronic and microleectronic devices.This paper provides a review and summary of the programs with emphasis on direct liquid cooling.Included in this review are the heat transfer investigations related to the following cooling modes:liquid free,mixed and forced convection.liquid jet impingement,flowing liquid film cooling,pool boiling,spray cooling,foreign gas jet impingement in liquid pool,and forced convection air-cooling.

  2. STEREO measurements of electron acceleration beyond fast Fermi at the bow shock

    CERN Document Server

    Pulupa, Marc; Opitz, Andrea; Fedorov, Andrei; Lin, Robert P; Sauvaud, Jean-Andre

    2012-01-01

    Solar wind electrons are accelerated and reflected upstream by the terrestrial bow shock into a region known as the electron foreshock. Previously observed electron spectra at low energies are consistent with a fast Fermi mechanism, based on the adiabatic conservation of the magnetic moment ({\\mu}) of the accelerated electrons. At higher energies, suprathermal power law tails are observed beyond the level predicted by fast Fermi. The SWEA and STE electron detectors on STEREO enable measurements of foreshock electrons with good energy resolution and sensitivity over the entire foreshock beam. We investigate the electron acceleration mechanism by comparing observed STEREO electron spectra with predictions based on a Liouville mapping of upstream electrons through a shock encounter. The foreshock electron beam extends up to several tens of keV, energies for which the Larmor radii of electrons is tens of km or greater. These radii are comparable to the scale sizes of the shock, and {\\mu} conservation no longer ap...

  3. Kinetics study of ultrafast electron transfer from sensitized dyes to silver halide microcrystals

    Institute of Scientific and Technical Information of China (English)

    Yang Shao-Peng; Fan Guo-Zhi; Fan Shan-Shan; Cao Ning; Li Xiao-Wei; Jiang Xiao-Li; Fu Guang-Sheng

    2006-01-01

    Spectral sensitization micromechanism of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr microcrystals with different dye concentrations is studied by using picosecond time-resolved fluorescence spectroscopy,and the dependences of electron transfer and spectral efficiency sensitization on different conditions are analysed in detail. With the steady spectroscopy, the wavelengths of absorption and fluorescence of J-aggregate adsorbed on AgBr microcrystals are found to shift to red relative to dye monomer. The spectrum of fluorescence has a red shift relative to the absorption peak. With the time-resolved fluorescence spectroscopy, the fluorescence decay curves of cyanine dyes J-aggregate adsorbed on the tabular and cubic AgBr grains are found to be fitted well by a double-exponential decay function. The fitting curves consist of a fast and a slow component. Because of the large amplitude of the fast component, this fast decay should be attributable mainly to the electron transfer from J-aggregate of dye to a conduction band of AgBr.

  4. Photoinduced electron transfer of chlorophyll in lipid bilayer system

    Indian Academy of Sciences (India)

    D K Lee; K W Seo; Y S Kang

    2002-12-01

    Photoinduced electron transfer from chlorophyll- through the interface of dipalmitoylphosphatidylcholine (DPPC) headgroup of the lipid bilayers was studied with electron magnetic resonance (EMR). The photoproduced radicals were identified with electron spin resonance (ESR) and radical yields of chlorophyll- were determined by double integration ESR spectra. The formation of vesicles was identified by changes in measured max values from diethyl ether solutions to vesicles solutions indirectly, and observed directly with SEM and TEM images. The efficiency of photosynthesis in model system was determined by measuring the amount of chlorophyll-a radical yields which were obtained from integration of ESR spectra.

  5. Ion and electron velocity distributions within flux transfer events

    Science.gov (United States)

    Thomsen, M. F.; Stansberry, J. A.; Bame, S. J.; Fuselier, S. A.; Gosling, J. T.

    1987-01-01

    The detailed nature of the thermal and suprathermal ion and electron distributions within magnetic flux transfer events (FTEs) is examined. Examples of both magnetosheath FTEs and magnetospheric FTEs are discussed. The detailed distributions confirm that FTEs contain a mixture of magnetosheath and magnetospheric plasmas. To lowest order, the distributions are consistent with a simple superposition of the two interpenetrating populations, with no strong interactions between them. To first order, some interesting differences appear, especially in the electron distributions, suggesting that considerable pitch angle scattering and some electron energy diffusion are also occurring. These observations should provide a useful test of analytical and numerical studies of interpenetrating plasmas.

  6. Electron transfer in donor-acceptor systems: Many-particle effects and influence of electronic correlations

    Science.gov (United States)

    Tornow, S.; Tong, N.-H.; Bulla, R.

    2006-03-01

    We investigate electron transfer processes in donor-acceptor systems with a coupling of the electronic degrees of freedom to a common bosonic bath. The model allows to study many-particle effects and the influence of the local Coulomb interaction U between electrons on donor and acceptor sites. Using the non-perturbative numerical renormalization group approach we find distinct differences between the electron transfer characteristics in the single- and two-particle subspaces. We calculate the critical electron-boson coupling αc as a function of U and show results for density-density correlation functions in the whole parameter space. The possibility of many-particle (bipolaronic) and Coulomb-assisted transfer is discussed.

  7. Activation of Electron-Deficient Quinones through Hydrogen-Bond-Donor-Coupled Electron Transfer.

    Science.gov (United States)

    Turek, Amanda K; Hardee, David J; Ullman, Andrew M; Nocera, Daniel G; Jacobsen, Eric N

    2016-01-11

    Quinones are important organic oxidants in a variety of synthetic and biological contexts, and they are susceptible to activation towards electron transfer through hydrogen bonding. Whereas this effect of hydrogen bond donors (HBDs) has been observed for Lewis basic, weakly oxidizing quinones, comparable activation is not readily achieved when more reactive and synthetically useful electron-deficient quinones are used. We have successfully employed HBD-coupled electron transfer as a strategy to activate electron-deficient quinones. A systematic investigation of HBDs has led to the discovery that certain dicationic HBDs have an exceptionally large effect on the rate and thermodynamics of electron transfer. We further demonstrate that these HBDs can be used as catalysts in a quinone-mediated model synthetic transformation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Ultrafast proton coupled electron transfer (PCET dynamics in 9-anthranol-aliphatic amine system

    Directory of Open Access Journals (Sweden)

    Nibbering Erik T. J.

    2013-03-01

    Full Text Available Femtosecond infrared absorption studies strongly suggest that photoexcited 9-anthranol takes part in an ultrafast electron transfer (ET reaction in electron-donating triethylamine solvent, but that ultrafast proton coupled electron transfer (PCET occurs in diethylamine solvent.

  9. Aspects of the physics and chemistry of water radiolysis by fast neutrons and fast electrons in nuclear reactors

    Energy Technology Data Exchange (ETDEWEB)

    McCracken, D.R. [Atomic Energy of Canada Limited, Chalk River, Ontario (Canada); Tsang, K.T. [Atomic Energy of Canada Limited, Mississauga, Ontario (Canada); Laughton, P.J

    1998-09-01

    Detailed radiation physics calculations of energy deposition have been done for the coolant of CANDU reactors and Pressurized Water Reactors (PWRs). The geometry of the CANDU fuel channel was modelled in detail. Fluxes and energy-deposition rates for neutrons, recoil ions, photons, and fast electrons have been calculated using MCNP4B, WIMS-AECL, and specifically derived energy-transfer factors. These factors generate the energy/flux spectra of recoil ions from fast-neutron energy/flux spectra. The energy spectrum was divided into 89 discrete ranges (energy bins).The production of oxidizing species and net coolant radiolysis can be suppressed by the addition of hydrogen to the coolant of nuclear reactors. It is argued that the net dissociation of coolant by gamma rays is suppressed by lower levels of excess hydrogen than when dissociation is by ion recoils. This has consequences for the modelling of coolant radiolysis by homogeneous kinetics. More added hydrogen is required to stop water radiolysis by recoil ions acting alone than if recoil ions and gamma rays acted concurrently in space and time. Homogeneous kinetic models and experimental data suggest that track overlap is very inefficient in providing radicals from gamma-ray tracks to recombine molecular products in ion-recoil tracks. An inhomogeneous chemical model is needed that incorporates ionizing-particle track structure and track overlap. Such a model does not yet exist, but a number of limiting cases using homogeneous kinetics are discussed. There are sufficient uncertainties and contradictions in the data relevant to the radiolysis of reactor coolant that the relatively high CHC's (critical hydrogen concentration) observed in NRU reactor experiments (compared to model predictions) may be explainable by errors in fundamental data and understanding of water radiolysis under reactor conditions. The radiation chemistry program at CRL has been focused to generate quantitative water-radiolysis data in a

  10. Protein dynamics modulated electron transfer kinetics in early stage photosynthesis.

    Science.gov (United States)

    Kundu, Prasanta; Dua, Arti

    2013-01-28

    A recent experiment has probed the electron transfer kinetics in the early stage of photosynthesis in Rhodobacter sphaeroides for the reaction center of wild type and different mutants [Science 316, 747 (2007)]. By monitoring the changes in the transient absorption of the donor-acceptor pair at 280 and 930 nm, both of which show non-exponential temporal decay, the experiment has provided a strong evidence that the initial electron transfer kinetics is modulated by the dynamics of protein backbone. In this work, we present a model where the electron transfer kinetics of the donor-acceptor pair is described along the reaction coordinate associated with the distance fluctuations in a protein backbone. The stochastic evolution of the reaction coordinate is described in terms of a non-Markovian generalized Langevin equation with a memory kernel and Gaussian colored noise, both of which are completely described in terms of the microscopics of the protein normal modes. This model provides excellent fits to the transient absorption signals at 280 and 930 nm associated with protein distance fluctuations and protein dynamics modulated electron transfer reaction, respectively. In contrast to previous models, the present work explains the microscopic origins of the non-exponential decay of the transient absorption curve at 280 nm in terms of multiple time scales of relaxation of the protein normal modes. Dynamic disorder in the reaction pathway due to protein conformational fluctuations which occur on time scales slower than or comparable to the electron transfer kinetics explains the microscopic origin of the non-exponential nature of the transient absorption decay at 930 nm. The theoretical estimates for the relative driving force for five different mutants are in close agreement with the experimental estimates obtained using electrochemical measurements.

  11. A unified diabatic description for electron transfer reactions, isomerization reactions, proton transfer reactions, and aromaticity.

    Science.gov (United States)

    Reimers, Jeffrey R; McKemmish, Laura K; McKenzie, Ross H; Hush, Noel S

    2015-10-14

    While diabatic approaches are ubiquitous for the understanding of electron-transfer reactions and have been mooted as being of general relevance, alternate applications have not been able to unify the same wide range of observed spectroscopic and kinetic properties. The cause of this is identified as the fundamentally different orbital configurations involved: charge-transfer phenomena involve typically either 1 or 3 electrons in two orbitals whereas most reactions are typically closed shell. As a result, two vibrationally coupled electronic states depict charge-transfer scenarios whereas three coupled states arise for closed-shell reactions of non-degenerate molecules and seven states for the reactions implicated in the aromaticity of benzene. Previous diabatic treatments of closed-shell processes have considered only two arbitrarily chosen states as being critical, mapping these states to those for electron transfer. We show that such effective two-state diabatic models are feasible but involve renormalized electronic coupling and vibrational coupling parameters, with this renormalization being property dependent. With this caveat, diabatic models are shown to provide excellent descriptions of the spectroscopy and kinetics of the ammonia inversion reaction, proton transfer in N2H7(+), and aromaticity in benzene. This allows for the development of a single simple theory that can semi-quantitatively describe all of these chemical phenomena, as well as of course electron-transfer reactions. It forms a basis for understanding many technologically relevant aspects of chemical reactions, condensed-matter physics, chemical quantum entanglement, nanotechnology, and natural or artificial solar energy capture and conversion.

  12. Valence-Shell Excitations of Nitrous Oxide Studied by Fast Electron Impact

    Institute of Scientific and Technical Information of China (English)

    LIU Ya-Wei; WANG You-Yan; ZHU Lin-Fan

    2012-01-01

    The valence-shell excitations of nitrous oxide are studied by fast electron energy loss spectroscopy.From the spectra measured at 2.5keV and scattering angles of 3.5°-8.5°,it is found that the asymmetric peak of the transition B 1△ can be well fitted by Haarhoff-Van der Linde function,while the symmetric peaks of the transitions of C1Π and D1∑+ can be well fitted by the Voigt function.The parameters of the peak profiles of B1△,C1Π and D1∑+,i.e.,their energy level positions and linewidths,are determined.With the aid of these parameters,the overlapping spectra measured at the low-energy electron impact can be deconvolved,which provides the possibility to determine the quantitative differential cross sections.The present results also show that the peak profiles of the transitions of B1△,C1Π and D1∑+ are independent of the momentum transfer.%The valence-shell excitations of nitrous oxide are studied by fast electron energy loss spectroscopy. From the spectra measured at 2.5keV and scattering angles of 3.5°-8.5°, it is found that the asymmetric peak of the transition B1A can be well fitted by Haarhoff-Van der Linde function, while the symmetric peaks of the transitions of C1II. And D1∑+ can be well fitted by the Voigt function. The parameters of the peak profiles of B1△, C1II and D1∑+, I.e., their energy level positions and linewidths, are determined. With the aid of these parameters, the overlapping spectra measured at the low-energy electron impact can be deconvolved, which provides the possibility to determine the quantitative differential cross sections. The present results also show that the peak profiles of the transitions of B1△, C1II and D1∑+ are independent of the momentum transfer.

  13. Electromicrobiology: Electron Transfer via Biowires in Nature and Practical Applications

    Directory of Open Access Journals (Sweden)

    Lovley Derek

    2016-01-01

    Full Text Available One of the most exciting developments in the field of electromicrobiology has been the discovery of electrically conductive pili (e-pili in Geobacter species that transport electrons with a metallic-like mechanism. The e-pili are essential for extracellular electron transport to Fe(III oxides and longrange electron transport through the conductive biofilms that form on the anodes of microbial fuel cells. The e-pili also facilitate direct interspecies electron transfer between Geobacter and Methanosaeta or Methanosarcina species. Metatranscriptomic studies have demonstrated that Geobacter/Methanosaeta DIET is an important process in anaerobic digesters converting brewery wastes to methane. Increasing e-pili expression through genetic modification of regulatory systems or adaptive evolution yields strains with enhanced rates of extracellular electron transfer. Measurement of the conductivity of individual e-pili has demonstrated that they have conductivities higher than those of a number of synthetic conducting organic polymers. Multiple lines of evidence have demonstrated that aromatic amino acids play an important role in the electron transport along e-pili, suggesting opportunities to tune e-pili conductivity via genetic manipulation of the amino acid composition of e-pili. It is expected that e-pili will be harnessed to improve microbe-electrode processes such as microbial electrosynthesis and for the development of novel biosensors. Also, e-pili show promise as a sustainable ‘green’ replacement for electronic materials that contain toxic components and/or are produced with harsh chemicals.

  14. Temperature and detection-wavelength dependence of the electron transfer rates in initial stages of photosynthesis.

    Science.gov (United States)

    Kurzynski, Michal; Chelminiak, Przemyslaw

    2013-10-17

    Unusual temperature behavior, observed in the initial electron transfer stages in the photosynthetic reaction centers of the purple bacteria, and a strong probing pulse wavelength dependence of transfer rates, determined in transient absorption spectroscopy, can easily be explained on assuming that the transfer takes place from dynamically unrelaxed states of protein environment. The transitions from the primary special pair (P) to a single bacteriochlorophyll (B) and next to a bacteriopheophytin (H) are controlled by diffusion down the energy value of underdamped vibrational modes of frequency 200 K, probably determining distances between the succeeding cofactors. The subsequent transition to the quinone A (Q) is controlled by diffusion in the position value of an overdamped conformational mode, probably corresponding to the local polarization. From the fit of available experimental data to simple theoretical formulas, the important physical conclusion arises that the very electronic transitions are fast as compared to the relaxation processes and, in the first approximation, only the latter contribute to the overall times of the initial electron transfer stages in photosynthesis.

  15. Syntrophic Growth via Quinone-Mediated Interspecies Electron Transfer

    Directory of Open Access Journals (Sweden)

    Jessica A Smith

    2015-02-01

    Full Text Available The mechanisms by which microbial species exchange electrons are of interest because interspecies electron transfer can expand the metabolic capabilities of microbial communities. Previous studies with the humic substance analog anthraquinone-2,6-disulfonate (AQDS suggested that quinone-mediated interspecies electron transfer (QUIET is feasible, but it was not determined if sufficient energy is available from QUIET to support the growth of both species. Furthermore, there have been no previous studies on the mechanisms for the oxidation of anthrahydroquinone-2,6-disulfonate (AHQDS. A co-culture of Geobacter metallireducens and Geobacter sulfurreducens metabolized ethanol with the reduction of fumarate much faster in the presence of AQDS, and there was an increase in cell protein. G. sulfurreducens was more abundant, consistent with G. sulfurreducens obtaining electrons from acetate that G. metallireducens produced from ethanol, as well as from AHQDS. Cocultures initiated with a citrate synthase-deficient strain of G. sulfurreducens that was unable to use acetate as an electron donor also metabolized ethanol with the reduction of fumarate and cell growth, but acetate accumulated over time. G. sulfurreducens and G. metallireducens were equally abundant in these co-cultures reflecting the inability of the citrate synthase-deficient strain of G. sulfurreducens to metabolize acetate. Evaluation of the mechanisms by which G. sulfurreducens accepts electrons from AHQDS demonstrated that a strain deficient in outer-surface c-type cytochromes that are required for AQDS reduction was as effective at QUIET as the wild-type strain. Deletion of additional genes previously implicated in extracellular electron transfer also had no impact on QUIET. These results demonstrate that QUIET can yield sufficient energy to support the growth of both syntrophic partners, but that the mechanisms by which electrons are derived from extracellular hydroquinones require

  16. Electron-transfer reduction of dinuclear copper peroxo and bis-μ-oxo complexes leading to the catalytic four-electron reduction of dioxygen to water.

    Science.gov (United States)

    Tahsini, Laleh; Kotani, Hiroaki; Lee, Yong-Min; Cho, Jaeheung; Nam, Wonwoo; Karlin, Kenneth D; Fukuzumi, Shunichi

    2012-01-23

    The four-electron reduction of dioxygen by decamethylferrocene (Fc*) to water is efficiently catalyzed by a binuclear copper(II) complex (1) and a mononuclear copper(II) complex (2) in the presence of trifluoroacetic acid in acetone at 298 K. Fast electron transfer from Fc* to 1 and 2 affords the corresponding Cu(I) complexes, which react at low temperature (193 K) with dioxygen to afford the η(2):η(2)-peroxo dicopper(II) (3) and bis-μ-oxo dicopper(III) (4) intermediates, respectively. The rate constants for electron transfer from Fc* and octamethylferrocene (Me(8)Fc) to 1 as well as electron transfer from Fc* and Me(8)Fc to 3 were determined at various temperatures, leading to activation enthalpies and entropies. The activation entropies of electron transfer from Fc* and Me(8)Fc to 1 were determined to be close to zero, as expected for outer-sphere electron-transfer reactions without formation of any intermediates. For electron transfer from Fc* and Me(8)Fc to 3, the activation entropies were also found to be close to zero. Such agreement indicates that the η(2):η(2)-peroxo complex (3) is directly reduced by Fc* rather than via the conversion to the corresponding bis-μ-oxo complex, followed by the electron-transfer reduction by Fc* leading to the four-electron reduction of dioxygen to water. The bis-μ-oxo species (4) is reduced by Fc* with a much faster rate than the η(2):η(2)-peroxo complex (3), but this also leads to the four-electron reduction of dioxygen to water. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Evidence of locally enhanced target heating due to instabilities of counter-streaming fast electron beams

    Energy Technology Data Exchange (ETDEWEB)

    Koester, Petra; Cecchetti, Carlo A. [Intense Laser Irradiation Laboratory at INO, CNR, Pisa (Italy); Booth, Nicola; Woolsey, Nigel [Physics Department, University of York, York (United Kingdom); Chen, Hui [Lawrence Livermore National Laboratory, Livermore, California 94550 (United States); Evans, Roger G. [Imperial College London, London (United Kingdom); Gregori, Gianluca; Li, Bin; Mithen, James; Murphy, Christopher D. [Physics Department, University of Oxford, Oxford (United Kingdom); Labate, Luca; Gizzi, Leonida A. [Intense Laser Irradiation Laboratory at INO, CNR, Pisa (Italy); INFN, Sezione di Pisa, Pisa (Italy); Levato, Tadzio [Intense Laser Irradiation Laboratory at INO, CNR, Pisa (Italy); University of Rome Tor Vergata, Rome (Italy); Makita, Mikako; Riley, David [Physics Department, Queens University Belfast, Belfast (United Kingdom); Notley, Margaret; Pattathil, Rajeev [Rutherford Appleton Laboratory, STFC, Didcot (United Kingdom)

    2015-02-15

    The high-current fast electron beams generated in high-intensity laser-solid interactions require the onset of a balancing return current in order to propagate in the target material. Such a system of counter-streaming electron currents is unstable to a variety of instabilities such as the current-filamentation instability and the two-stream instability. An experimental study aimed at investigating the role of instabilities in a system of symmetrical counter-propagating fast electron beams is presented here for the first time. The fast electron beams are generated by double-sided laser-irradiation of a layered target foil at laser intensities above 10{sup 19 }W/cm{sup 2}. High-resolution X-ray spectroscopy of the emission from the central Ti layer shows that locally enhanced energy deposition is indeed achieved in the case of counter-propagating fast electron beams.

  18. A fast and scalable content transfer protocol (FSCTP) for VANET based architecture

    Science.gov (United States)

    Santamaria, A. F.; Scala, F.; Sottile, C.; Tropea, M.; Raimondo, P.

    2016-05-01

    In the modern Vehicular Ad-hoc Networks (VANET) based systems even more applications require lot of data to be exchanged among vehicles and infrastructure entities. Due to mobility issues and unplanned events that may occurs it is important that contents should be transferred as fast as possible by taking into account consistence of the exchanged data and reliability of the connections. In order to face with these issues, in this work we propose a new transfer data protocol called Fast and Scalable Content Transfer Protocol (FSCTP). This protocol allows a data transfer by using a bidirectional channel among content suppliers and receivers exploiting several cooperative sessions. Each session will be based on User Datagram Protocol (UDP) and Transmission Control Protocol (TCP) to start and manage data transfer. Often in urban area the VANET scenario is composed of several vehicle and infrastructures points. The main idea is to exploit ad-hoc connections between vehicles to reach content suppliers. Moreover, in order to obtain a faster data transfer, more than one session is exploited to achieve a higher transfer rate. Of course it is important to manage data transfer between suppliers to avoid redundancy and resource wastages. The main goal is to instantiate a cooperative multi-session layer efficiently managed in a VANET environment exploiting the wide coverage area and avoiding common issues known in this kind of scenario. High mobility and unstable connections between nodes are some of the most common issues to address, thus a cooperative work between network, transport and application layers needs to be designed.

  19. Sandwiched confinement of quantum dots in graphene matrix for efficient electron transfer and photocurrent production.

    Science.gov (United States)

    Zhu, Nan; Zheng, Kaibo; Karki, Khadga J; Abdellah, Mohamed; Zhu, Qiushi; Carlson, Stefan; Haase, Dörthe; Žídek, Karel; Ulstrup, Jens; Canton, Sophie E; Pullerits, Tõnu; Chi, Qijin

    2015-05-21

    Quantum dots (QDs) and graphene are both promising materials for the development of new-generation optoelectronic devices. Towards this end, synergic assembly of these two building blocks is a key step but remains a challenge. Here, we show a one-step strategy for organizing QDs in a graphene matrix via interfacial self-assembly, leading to the formation of sandwiched hybrid QD-graphene nanofilms. We have explored structural features, electron transfer kinetics and photocurrent generation capacity of such hybrid nanofilms using a wide variety of advanced techniques. Graphene nanosheets interlink QDs and significantly improve electronic coupling, resulting in fast electron transfer from photoexcited QDs to graphene with a rate constant of 1.3 × 10(9) s(-1). Efficient electron transfer dramatically enhances photocurrent generation in a liquid-junction QD-sensitized solar cell where the hybrid nanofilm acts as a photoanode. We thereby demonstrate a cost-effective method to construct large-area QD-graphene hybrid nanofilms with straightforward scale-up potential for optoelectronic applications.

  20. Sandwiched confinement of quantum dots in graphene matrix for efficient electron transfer and photocurrent production

    Science.gov (United States)

    Zhu, Nan; Zheng, Kaibo; Karki, Khadga J.; Abdellah, Mohamed; Zhu, Qiushi; Carlson, Stefan; Haase, Dörthe; Žídek, Karel; Ulstrup, Jens; Canton, Sophie E.; Pullerits, Tõnu; Chi, Qijin

    2015-05-01

    Quantum dots (QDs) and graphene are both promising materials for the development of new-generation optoelectronic devices. Towards this end, synergic assembly of these two building blocks is a key step but remains a challenge. Here, we show a one-step strategy for organizing QDs in a graphene matrix via interfacial self-assembly, leading to the formation of sandwiched hybrid QD-graphene nanofilms. We have explored structural features, electron transfer kinetics and photocurrent generation capacity of such hybrid nanofilms using a wide variety of advanced techniques. Graphene nanosheets interlink QDs and significantly improve electronic coupling, resulting in fast electron transfer from photoexcited QDs to graphene with a rate constant of 1.3 × 109 s-1. Efficient electron transfer dramatically enhances photocurrent generation in a liquid-junction QD-sensitized solar cell where the hybrid nanofilm acts as a photoanode. We thereby demonstrate a cost-effective method to construct large-area QD-graphene hybrid nanofilms with straightforward scale-up potential for optoelectronic applications.

  1. A focusable, convergent fast-electron beam from ultra-high-intensity laser-solid interactions

    CERN Document Server

    Scott, R H H

    2015-01-01

    A novel scheme for the creation of a convergent, or focussing, fast-electron beam generated from ultra-high-intensity laser-solid interactions is described. Self-consistent particle-in-cell simulations are used to demonstrate the efficacy of this scheme in two dimensions. It is shown that a beam of fast-electrons of energy 500 keV - 3 MeV propagates within a solid-density plasma, focussing at depth. The depth of focus of the fast-electron beam is controlled via the target dimensions and focussing optics.

  2. Electron Transfer and Solvent-Mediated Electronic Localization in Molecular Photocatalysis

    DEFF Research Database (Denmark)

    Dohn, Asmus Ougaard; Kjær, Kasper Skov; Harlang, Tobias B.

    2016-01-01

    This work provides a detailed mechanism for electron transfer in a heterodinuclear complex designed as a model system in which to study homogeneous molecular photocatalysis. With efficient Born–Oppenheimer molecular dynamics simulations, we show how intermediate, charge-separated states can mediate...... the electron transfer. We observe how Jahn–Teller distortion effects play out in solution, when the molecule has energetically close-lying states, and how this distortion is averaged out in the thermal sampling. Finally, we demonstrate how the solvent helps stabilize and localize the separated charge....... The information on the electronic configuration and separate states is of key importance for designing next-generation photocatalysts....

  3. Hardwiring microbes via direct interspecies electron transfer: mechanisms and applications.

    Science.gov (United States)

    Cheng, Qiwen; Call, Douglas F

    2016-08-10

    Multicellular microbial communities are important catalysts in engineered systems designed to treat wastewater, remediate contaminated sediments, and produce energy from biomass. Understanding the interspecies interactions within them is therefore essential to design effective processes. The flow of electrons within these communities is especially important in the determination of reaction possibilities (thermodynamics) and rates (kinetics). Conventional models of electron transfer incorporate the diffusion of metabolites generated by one organism and consumed by a second, frequently referred to as mediated interspecies electron transfer (MIET). Evidence has emerged in the last decade that another method, called direct interspecies electron transfer (DIET), may occur between organisms or in conjunction with electrically conductive materials. Recent research has suggested that DIET can be stimulated in engineered systems to improve desired treatment goals and energy recovery in systems such as anaerobic digesters and microbial electrochemical technologies. In this review, we summarize the latest understanding of DIET mechanisms, the associated microorganisms, and the underlying thermodynamics. We also critically examine approaches to stimulate DIET in engineered systems and assess their effectiveness. We find that in most cases attempts to promote DIET in mixed culture systems do not yield the improvements expected based on defined culture studies. Uncertainties of other processes that may be co-occurring in real systems, such as contaminant sorption and biofilm promotion, need to be further investigated. We conclude by identifying areas of future research related to DIET and its application in biological treatment processes.

  4. Modeling Electronic-Nuclear Interactions for Excitation Energy Transfer Processes in Light-Harvesting Complexes.

    Science.gov (United States)

    Lee, Mi Kyung; Coker, David F

    2016-08-18

    An accurate approach for computing intermolecular and intrachromophore contributions to spectral densities to describe the electronic-nuclear interactions relevant for modeling excitation energy transfer processes in light harvesting systems is presented. The approach is based on molecular dynamics (MD) calculations of classical correlation functions of long-range contributions to excitation energy fluctuations and a separate harmonic analysis and single-point gradient quantum calculations for electron-intrachromophore vibrational couplings. A simple model is also presented that enables detailed analysis of the shortcomings of standard MD-based excitation energy fluctuation correlation function approaches. The method introduced here avoids these problems, and its reliability is demonstrated in accurate predictions for bacteriochlorophyll molecules in the Fenna-Matthews-Olson pigment-protein complex, where excellent agreement with experimental spectral densities is found. This efficient approach can provide instantaneous spectral densities for treating the influence of fluctuations in environmental dissipation on fast electronic relaxation.

  5. Alternating electron and proton transfer steps in photosynthetic water oxidation.

    Science.gov (United States)

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-10-02

    Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established.

  6. Photoinduced electron and energy transfer in a new porphyrin-phthalocyanine triad

    Energy Technology Data Exchange (ETDEWEB)

    Ermilov, Eugeny A. [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany)], E-mail: ermilov@physik.hu-berlin.de; Tannert, Sebastian [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany); Werncke, Thomas [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany); Choi, Michael T.M. [Department of Chemistry, Chinese University of Hong Kong, Shatin, N.T., Hong Kong (China); Ng, Dennis K.P. [Department of Chemistry, The Chinese University of Hong Kong, Shatin, N.T., Hong Kong (China)], E-mail: dkpn@cuhk.edu.hk; Roeder, Beate [Institut fuer Physik, Photobiophysik, Humboldt-Universitaet zu Berlin, Newtonstr. 15, D-12489 Berlin (Germany)

    2006-09-29

    Complexes of porphyrins, phthalocyanines, and chlorophylls are well suited for modelling both the electron and energy transfer processes in photosynthetic reaction centers and natural chlorophyll complexes. In the present paper, we report the synthesis and photophysical characterization of a novel tetraphenylporphyrin-silicon(IV) phthalocyanine triad, where two porphyrins are linked to the central silicon atom of a phthalocyanine moiety. It has been found that the photophysical properties of the triad (Tr) are strongly affected by two different types of interactions between the porphyrin (P) and the phthalocyanine (Pc) parts of Tr, namely excitation energy transfer (EET) and photoinduced electron transfer (ET). The first one results in appearance of the Pc fluorescence when the P-part was initially excited and plays dominant role in fast depopulation of the first excited singlet state of the P moiety. Another competitive process in quenching of P-part fluorescence is electron transfer, but the probability of it is six times less compared to that of EET. If the first excited singlet state of the Pc-part is populated (directly or via EET), it undergoes fast depopulation via ET to the charge-separated state. As a result, the fluorescence quantum yield of the Pc-part of Tr is approximately three orders of magnitude less compared to that of silicon(IV) phthalocyanine with two axial poly(ethylene glycol) chains (SiPc) used as a reference. Analysis of transient absorption data has shown that charge-recombination occurs with a decay time of 30 ps directly to the ground state.

  7. Accurate and fast fiber transfer delay measurement based on phase discrimination and frequency measurement

    CERN Document Server

    Dong, J W; Gao, C; Wang, L J

    2016-01-01

    An accurate and fast fiber transfer delay measurement method is demonstrated. As a key technique, a simple ambiguity resolving process based on phase discrimination and frequency measurement is used to overcome the contradiction between measurement accuracy and system complexity. The optimized system achieves a high accuracy of 0.3 ps with a 0.1 ps resolution, and a large dynamic range up to 50 km as well as no dead zone.

  8. Energy deposition of quasi-two temperature relativistic electrons in fast-shock ignition scenario

    Science.gov (United States)

    Ghasemi, Seyed Abolfazl; Farahbod, Amir Hossein

    2016-10-01

    Previous calculations from Solodov et al. (2008) indicate that classical stopping and scattering dominate electrons energy deposition and transport when the electrons reach the dense plasma in FSI inertial confinement fusion concept [1]. Our calculations show that, by using quasi- two temperature electrons energy distribution function [2] in comparison with exponential [3] or monoenergetic distribution function and also increasing fast electrons energy to about 7 MeV, the ratio of beam blooming to straggling definitely decreases. Our analytical analysis shows that for fuel mass more than 1 mg and for fast ignitor wavelength λif > 0.53 μ m, straggling and beam blooming increases. Meanwhile, by reducing fast ignitor wavelength from 0.53 to 0.35 micron, and for fuel mass about 2 mg, electron penetration into the dense fuel slightly increases. Therefore, reduction of scattering (blooming and straggling) of electrons and enhancement of electron penetration into the dense fuel, can be obtained in relativistic regime with high energy fast electrons of the order of 5 Mev and more. Such derivations can be used in theoretical studies of the ignition conditions and PIC simulations of the electron transport in fast ignition scenario.

  9. Electron-Nuclear Spin Transfer in Triple Quantum Dot Networks

    Science.gov (United States)

    Prada, Marta; Toonen, Ryan; Harrison, Paul

    2005-03-01

    We investigate the conductance spectra of coupled quantum dots to study systematically the nuclear spin relaxation of delta- and y-junction networks and observe spin blockade dependence on the electronic configurations. We derive the conductance using the Beenakker approach generalised to an array of quantum dots where we consider the nuclear spin transfer to electrons by hyperfine coupling. This allows us to predict the relevant memory effects on the different electronic states by studying the evolution of the single electron resonances in presence of nuclear spin relaxation. We find that the gradual depolarisation of the nuclear system is imprinted in the conductance spectra of the multidot system. Our calculations of the temporal evolution of the conductance resonance reveal that spin blockade can be lifted by hyperfine coupling.

  10. Electron nuclear spin transfer in quantum-dot networks

    Science.gov (United States)

    Prada, M.; Toonen, R. C.; Blick, R. H.; Harrison, P.

    2005-05-01

    We investigate the conductance spectra of coupled quantum dots to study systematically the nuclear spin relaxation of different geometries of a two-dimensional network of quantum dots and observe spin blockade dependence on the electronic configurations. We derive the conductance using the Beenakker approach generalized to an array of quantum dots where we consider the nuclear spin transfer to electrons by hyperfine coupling. This allows us to predict the relevant memory effects on the different electronic states by studying the evolution of the single electron resonances in the presence of nuclear spin relaxation. We find that the gradual depolarization of the nuclear system is imprinted in the conductance spectra of the multidot system. Our calculations of the temporal evolution of the conductance resonance reveal that spin blockade can be lifted by hyperfine coupling.

  11. A polaron model for electron transfer in globular proteins.

    Science.gov (United States)

    Chuev, G N; Lakhno, V D

    1993-07-07

    Polaron models have been considered for the electron states in protein globules existing in a solvent. These models account for two fundamental effects, viz, polarization interaction of an electron with the conformational vibrations and the heterogeneity of the medium. Equations have been derived to determine the electron state in a protein globule. The parameters of this state show that it is an extended state with an energy of 2 eV. The electron transfer rate for cyt C self-exchange reaction has been calculated in the polaron model. Reorganization energy, tunneling matrix element and the rate constant have also been estimated. The results are compared with experimental data. The influence of model parameters on the significance of the data obtained has been studied. The potentialities of the model are discussed.

  12. The Electron Transfer Reaction between p-Nitrobenzoates and β-N, N-Dimethylaminonaphthalene

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    A few of p-nitrobenzoates were synthesized, and the electron transfer of them with β-N, N-dimethylaminonaphthalene (DMAN) in methanol solution was studied. Steady-state fluore-scence results showed the cyclodextrin moiety in p-nitrobenzoyl-β-cyclodextrin would block the electron transfer pathway from DMAN compared with other electron acceptors, thus, reduced the electron transfer efficiency.

  13. FASTDEF: fast defocus and astigmatism estimation for high-throughput transmission electron microscopy.

    Science.gov (United States)

    Vargas, J; Otón, J; Marabini, R; Jonic, S; de la Rosa-Trevín, J M; Carazo, J M; Sorzano, C O S

    2013-02-01

    In this work we present a fast and automated algorithm for estimating the contrast transfer function (CTF) of a transmission electron microscope. The approach is very suitable for High Throughput work because: (a) it does not require any initial defocus estimation, (b) it is almost an order of magnitude faster than existing approaches, (c) it opens the way to well-defined extensions to the estimation of higher order aberrations, at the same time that provides defocus and astigmatism estimations comparable in accuracy to well established methods, such as Xmipp and CTFFIND3 approaches. The new algorithm is based on obtaining the wrapped modulating phase of the power spectra density pattern by the use of a quadrature filter. This phase is further unwrapped in order to obtain the continuous and smooth absolute phase map; then a Zernike polynomial fitting is performed and the defocus and astigmatism parameters are determined. While the method does not require an initial estimation of the defocus parameters or any non-linear optimization procedure, these approaches can be used if further refinement is desired. Results of the CTF estimation method are presented for standard negative stained images, cryo-electron microscopy images in the absence of carbon support, as well as micrographs with only ice. Additionally, we have also tested the proposed method with micrographs acquired from tilted and untilted samples, obtaining good results. The algorithm is freely available as a part of the Xmipp package [http://xmipp.cnb.csic.es].

  14. Dynamics of Electron Transfer for a Nonsuperexchange Coherent Mechanism. I

    Science.gov (United States)

    1989-10-13

    numerically. One rough but simple analytical result for the latter is also given. tPresent address: Departmento de Quimica , Facultad de Ciencias...With the change of coordinates from (q,, q21, q3) to (x, y, z) it is seen from eqs. (2.9) - (2.11) that the x-motion is identical for all H,’s and so...the geometrical changes . The calculation of the dynamics of the electron transfer starting from electronic configuration 1, i.e., from D*BA, now

  15. Human ceruloplasmin. Intramolecular electron transfer kinetics and equilibration

    DEFF Research Database (Denmark)

    Farver, O; Bendahl, L; Skov, L K

    1999-01-01

    Pulse radiolytic reduction of disulfide bridges in ceruloplasmin yielding RSSR(-) radicals induces a cascade of intramolecular electron transfer (ET) processes. Based on the three-dimensional structure of ceruloplasmin identification of individual kinetically active disulfide groups and type 1 (T1...... and indeed electron equilibration between T1A and the trinuclear copper center in the domain 1-6 interface takes place with a rate constant of 2.9 +/- 0.6 s(-1). The equilibrium constant is 0.17. Following reduction of T1A Cu(II), another ET process takes place between RSSR(-) and T1B copper(II) of domain 4...

  16. Resolution of two distinct electron transfer sites on azurin

    DEFF Research Database (Denmark)

    Farver, O; Blatt, Y; Pecht, I

    1982-01-01

    reaction rates of the Cr(III)-modified protein are attenuated. This decreased reactivity of Cr(III)-labeled azurin toward one of its physiological partners suggests the involvement of the labeled region in the electron transfer reaction with cytochrome c551. Furthermore, the presence of a second active...... in the redox system of the bacterium. The Pseudomonas cytochrome oxidase catalyzed oxidation of reduced native and Cr(III)-labeled azurin by O2 was found to be unaffected by the modification. The kinetics of the electron exchange reaction between native or Cr(III)-labeled azurin and cytochrome c551 were...

  17. Aza-heterocyclic Receptors for Direct Electron Transfer Hemoglobin Biosensor

    Science.gov (United States)

    Kumar, Vinay; Kashyap, D. M. Nikhila; Hebbar, Suraj; Swetha, R.; Prasad, Sujay; Kamala, T.; Srikanta, S. S.; Krishnaswamy, P. R.; Bhat, Navakanta

    2017-01-01

    Direct Electron Transfer biosensors, facilitating direct communication between the biomolecule of interest and electrode surface, are preferable compared to enzymatic and mediator based sensors. Although hemoglobin (Hb) contains four redox active iron centres, direct detection is not possible due to inaccessibility of iron centres and formation of dimers, blocking electron transfer. Through the coordination of iron with aza-heterocyclic receptors - pyridine and imidazole - we report a cost effective, highly sensitive and simple electrochemical Hb sensor using cyclic voltammetry and chronoamperometry. The receptor can be either in the form of liquid micro-droplet mixed with blood or dry chemistry embedded in paper membrane on top of screen printed carbon electrodes. We demonstrate excellent linearity and robustness against interference using clinical samples. A truly point of care technology is demonstrated by integrating disposable test strips with handheld reader, enabling finger prick to result in less than a minute. PMID:28169325

  18. Aza-heterocyclic Receptors for Direct Electron Transfer Hemoglobin Biosensor

    Science.gov (United States)

    Kumar, Vinay; Kashyap, D. M. Nikhila; Hebbar, Suraj; Swetha, R.; Prasad, Sujay; Kamala, T.; Srikanta, S. S.; Krishnaswamy, P. R.; Bhat, Navakanta

    2017-02-01

    Direct Electron Transfer biosensors, facilitating direct communication between the biomolecule of interest and electrode surface, are preferable compared to enzymatic and mediator based sensors. Although hemoglobin (Hb) contains four redox active iron centres, direct detection is not possible due to inaccessibility of iron centres and formation of dimers, blocking electron transfer. Through the coordination of iron with aza-heterocyclic receptors - pyridine and imidazole - we report a cost effective, highly sensitive and simple electrochemical Hb sensor using cyclic voltammetry and chronoamperometry. The receptor can be either in the form of liquid micro-droplet mixed with blood or dry chemistry embedded in paper membrane on top of screen printed carbon electrodes. We demonstrate excellent linearity and robustness against interference using clinical samples. A truly point of care technology is demonstrated by integrating disposable test strips with handheld reader, enabling finger prick to result in less than a minute.

  19. Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Miller, David C; Choi, Gilbert J; Orbe, Hudson S; Knowles, Robert R

    2015-10-28

    Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.

  20. Effect of bremsstrahlung radiation emission on fast electrons in plasmas

    Science.gov (United States)

    Embréus, O.; Stahl, A.; Fülöp, T.

    2016-09-01

    Bremsstrahlung radiation emission is an important energy loss mechanism for energetic electrons in plasmas. In this paper we investigate the effect of spontaneous bremsstrahlung emission on the momentum-space structure of the electron distribution, fully accounting for the emission of finite-energy photons by modeling the bremsstrahlung interactions with a Boltzmann collision operator. We find that electrons accelerated by electric fields can reach significantly higher energies than predicted by the commonly used radiative stopping-power model. Furthermore, we show that the emission of soft photons can contribute significantly to the dynamics of electrons with an anisotropic distribution by causing pitch-angle scattering at a rate that increases with energy.

  1. Effect of bremsstrahlung radiation emission on fast electrons in plasmas

    CERN Document Server

    Embréus, Ola; Fülöp, Tünde

    2016-01-01

    Bremsstrahlung radiation emission is an important energy loss mechanism for energetic electrons in plasmas. In this paper we investigate the effect of spontaneous bremsstrahlung emission on the momentum-space structure of the electron distribution, fully accounting for the emission of finite-energy photons. We find that electrons accelerated by electric fields can reach significantly higher energies than what is expected from energy-loss considerations. Furthermore, we show that the emission of soft photons can contribute significantly to the dynamics of electrons with an anisotropic distribution.

  2. Marcus wins nobel prize in chemistry for electron transfer theory

    Energy Technology Data Exchange (ETDEWEB)

    Levi, B.G.

    1993-01-01

    This article describes the work of Rudolf Marcus of Caltech leading to his receipt of the 1992 Nobel Prize in Chemistry [open quotes]for his contributions to the theory of electron transfer reactions in chemical systems.[close quotes] Applications of Marcus' theory include such diverse phenomena as photosynthesis, electrically conducting polymers, chemiluminescence, and corrosion. Historical aspects of his career are given. 10 refs., 1 fig.

  3. Hetero-cycloreversions Mediated by Photoinduced Electron Transfer

    OpenAIRE

    Pérez Ruiz, Raul; Jiménez Molero, María Consuelo; Miranda Alonso, Miguel Ángel

    2014-01-01

    Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) versi...

  4. Real-time simulations of photoinduced coherent charge transfer and proton-coupled electron transfer.

    Science.gov (United States)

    Eisenmayer, Thomas J; Buda, Francesco

    2014-10-20

    Photoinduced electron transfer (ET) and proton-coupled electron transfer (PCET) are fundamental processes in natural phenomena, most noticeably in photosynthesis. Time-resolved spectroscopic evidence of coherent oscillatory behavior associated with these processes has been reported both in complex biological environments, as well as in biomimetic models for artificial photosynthesis. Here, we consider a few biomimetic models to investigate these processes in real-time simulations based on ab initio molecular dynamics and Ehrenfest dynamics. This allows for a detailed analysis on how photon-to-charge conversion is promoted by a coupling of the electronic excitation with specific vibrational modes and with proton displacements. The ET process shows a characteristic coherence that is linked to the nuclear motion at the interface between donor and acceptor. We also show real-time evidence of PCET in a benzimidazole-phenol redox relay. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. A Simple Transmission Electron Microscopy Method for Fast Thickness Characterization of Suspended Graphene and Graphite Flakes.

    Science.gov (United States)

    Rubino, Stefano; Akhtar, Sultan; Leifer, Klaus

    2016-02-01

    We present a simple, fast method for thickness characterization of suspended graphene/graphite flakes that is based on transmission electron microscopy (TEM). We derive an analytical expression for the intensity of the transmitted electron beam I 0(t), as a function of the specimen thickness t (tgraphene/graphite, the method we propose has the advantage of being simple and fast, requiring only the acquisition of bright-field images.

  6. Fast electron dynamics in lower hybrid current drive experiment on HT-7 tokamak

    Institute of Scientific and Technical Information of China (English)

    Shi Yue-Jiang; Kuang Gang-Li; Li Jian-Gang; HT-7 Team; Wan Bao-Nian; Chen Zhong-Yong; Hu Li-Qun; Lin Shi-Yao; Ruan Huai-Lin; Qian Jin-Ping; Zhen Xiang-Jun; Ding Bo-Jiang

    2005-01-01

    The dynamic behaviour of fast electron in lower hybrid current drive (LHCD) experiments is a crucial issue in the sense of enhancing plasma performance. A new hard x-ray diagnostic system on HT-7 allows the investigation of the lower hybrid wave dynamics. The behaviour of fast electron is studied in several kinds of LHCD experiments, including long pulse discharges, high performance discharges and counter-LHCD experiments.

  7. Ultrafast Photoinduced Electron Transfer in Bimolecular Donor-Acceptor Systems

    KAUST Repository

    Alsulami, Qana A.

    2016-11-30

    The efficiency of photoconversion systems, such as organic photovoltaic (OPV) cells, is largely controlled by a series of fundamental photophysical processes occurring at the interface before carrier collection. A profound understanding of ultrafast interfacial charge transfer (CT), charge separation (CS), and charge recombination (CR) is the key determinant to improving the overall performances of photovoltaic devices. The discussion in this dissertation primarily focuses on the relevant parameters that are involved in photon absorption, exciton separation, carrier transport, carrier recombination and carrier collection in organic photovoltaic devices. A combination of steady-state and femtosecond broadband transient spectroscopies was used to investigate the photoinduced charge carrier dynamics in various donor-acceptor systems. Furthermore, this study was extended to investigate some important factors that influence charge transfer in donor-acceptor systems, such as the morphology, energy band alignment, electronic properties and chemical structure. Interestingly, clear correlations among the steady-state measurements, time-resolved spectroscopy results, grain alignment of the electron transporting layer (ETL), carrier mobility, and device performance are found. In this thesis, we explored the significant impacts of ultrafast charge separation and charge recombination at donor/acceptor (D/A) interfaces on the performance of a conjugated polymer PTB7-Th device with three fullerene acceptors: PC71BM, PC61BM and IC60BA. Time-resolved laser spectroscopy and high-resolution electron microscopy can illustrate the basis for fabricating solar cell devices with improved performances. In addition, we studied the effects of the incorporation of heavy metals into π-conjugated chromophores on electron transfer by monitoring the triplet state lifetime of the oligomer using transient absorption spectroscopy, as understanding the mechanisms controlling intersystem crossing and

  8. Insights into Proton-Coupled Electron Transfer from Computation

    Science.gov (United States)

    Provorse, Makenzie R.

    Proton-coupled electron transfer (PCET) is utilized throughout Nature to facilitate essential biological processes, such as photosynthesis, cellular respiration, and DNA replication and repair. The general approach to studying PCET processes is based on a two-dimensional More O'Ferrall-Jencks diagram in which electron transfer (ET) and proton transfer (PT) occur in a sequential or concerted fashion. Experimentally, it is difficult to discern the contributing factors of concerted PCET mechanisms. Several theoretical approaches have arisen to qualitatively and quantitatively investigate these reactions. Here, we present a multistate density functional theory (MSDFT) method to efficiently and accurately model PCET mechanisms. The MSDFT method is validated against experimental and computational data previously reported on an isoelectronic series of small molecule self-exchange hydrogen atom transfer reactions and a model complex specifically designed to study long-range ET through a hydrogen-bonded salt-bridge interface. Further application of this method to the hydrogen atom abstraction of ascorbate by a nitroxyl radical demonstrates the sensitivity of the thermodynamic and kinetic properties to solvent effects. In particular, the origin of the unusual kinetic isotope effect is investigated. Lastly, the MSDFT is employed in a combined quantum mechanical/molecular mechanical (QM/MM) approach to explicitly model PCET in condensed phases.

  9. An artificial neural network based fast radiative transfer model for simulating infrared sounder radiances

    Indian Academy of Sciences (India)

    Praveen Krishnan; K Srinivasa Ramanujam; C Balaji

    2012-08-01

    The first step in developing any algorithm to retrieve the atmospheric temperature and humidity parameters at various pressure levels is the simulation of the top of the atmosphere radiances that can be measured by the satellite. This study reports the results of radiative transfer simulations for the multichannel infrared sounder of the proposed Indian satellite INSAT-3D due to be launched shortly. Here, the widely used community software k Compressed Atmospheric Radiative Transfer Algorithm (kCARTA) is employed for performing the radiative transfer simulations. Though well established and benchmarked, kCARTA is a line-by-line solver and hence takes enormous computational time and effort for simulating the multispectral radiances for a given atmospheric scene. This necessitates the development of a much faster and at the same time, equally accurate RT model that can drive a real-time retrieval algorithm. In the present study, a fast radiative transfer model using neural networks is proposed to simulate radiances corresponding to the wavenumbers of INSAT-3D. Realistic atmospheric temperature and humidity profiles have been used for training the network. Spectral response functions of GOES-13, a satellite similar in construction, purpose and design and already in use are used. The fast RT model is able to simulate the radiances for 1200 profiles in 18 ms for a 15-channel GOES profile, with a correlation coefficient of over 99%. Finally, the robustness of the model is tested using additional synthetic profiles generated using empirical orthogonal functions (EOF).

  10. Ultrafast energy and electron transfers in structurally well addressable BODIPY-porphyrin-fullerene polyads.

    Science.gov (United States)

    Gao, Di; Aly, Shawkat M; Karsenti, Paul-Ludovic; Brisard, Gessie; Harvey, Pierre D

    2017-01-25

    Two electron transfer polyads built upon [C60]-[ZnP]-[BODIPY] (1) and [ZnP]-[ZnP](-[BODIPY])(-[C60]) (2), where [C60] = N-methyl-2-phenyl-3,4-fulleropyrrolidine, [BODIPY] = boron dipyrromethane, and [ZnP] = zinc(ii) porphyrin, were synthesized along with their corresponding energy transfer polyads [ZnP]-[BODIPY] (1a) and [ZnP]-[ZnP]-[BODIPY] (2a) as well as relevant models. These polyads were studied using cyclic voltammetry, DFT computations, steady state and time-resolved fluorescence spectroscopy, and fs transient absorption spectroscopy. The rates for energy transfer, kET, [BODIPY]* → [ZnP] are ∼2.8 × 10(10) s(-1) for both 1a and 2a, with an efficiency of 99%. Concurrently, the fast appearance of the [C60](-)˙ anion for 1 and 2 indicates that the charge separation occurs on the 20-30 ps timescale with the rates of electron transfer, ket, [ZnP]*/[C60] → [ZnP](+)˙/[C60](-)˙ of ∼0.9 × 10(10) to ∼3.8 × 10(10) s(-1). The latter value is among the fastest for these types of polyads. Conversely, the charge recombination operates on the ns timescale. These rates are comparable to or faster than those reported for other more flexible [C60]-[ZnP]-[BODIPY] polyads, which can be rationalized by the donor-acceptor separations.

  11. The electron transfer system of syntrophically grown Desulfovibrio vulgaris

    Energy Technology Data Exchange (ETDEWEB)

    Walker, C.B.; He, Z.; Yang, Z.K.; Ringbauer, Jr., J.A.; He, Q.; Zhou, J.; Voordouw, G.; Wall, J.D.; Arkin, A.P.; Hazen, T.C.; Stolyar, S.; Stahl, D.A.

    2009-05-01

    Interspecies hydrogen transfer between organisms producing and consuming hydrogen promotes the decomposition of organic matter in most anoxic environments. Although syntrophic couplings between hydrogen producers and consumers are a major feature of the carbon cycle, mechanisms for energy recovery at the extremely low free energies of reactions typical of these anaerobic communities have not been established. In this study, comparative transcriptional analysis of a model sulfate-reducing microbe, Desulfovibrio vulgaris Hildenborough, suggested the use of alternative electron transfer systems dependent upon growth modality. During syntrophic growth on lactate with a hydrogenotrophic methanogen, D. vulgaris up-regulated numerous genes involved in electron transfer and energy generation when compared with sulfate-limited monocultures. In particular, genes coding for the putative membrane-bound Coo hydrogenase, two periplasmic hydrogenases (Hyd and Hyn) and the well-characterized high-molecular weight cytochrome (Hmc) were among the most highly expressed and up-regulated. Additionally, a predicted operon coding for genes involved in lactate transport and oxidation exhibited up-regulation, further suggesting an alternative pathway for electrons derived from lactate oxidation during syntrophic growth. Mutations in a subset of genes coding for Coo, Hmc, Hyd and Hyn impaired or severely limited syntrophic growth but had little affect on growth via sulfate-respiration. These results demonstrate that syntrophic growth and sulfate-respiration use largely independent energy generation pathways and imply that understanding of microbial processes sustaining nutrient cycling must consider lifestyles not captured in pure culture.

  12. The Electron Transfer System of Syntrophically Grown Desulfovibrio vulgaris

    Energy Technology Data Exchange (ETDEWEB)

    PBD; ENIGMA; GTL; VIMSS; Walker, Christopher B.; He, Zhili; Yang, Zamin K.; Ringbauer Jr., Joseph A.; He, Qiang; Zhou, Jizhong; Voordouw, Gerrit; Wall, Judy D.; Arkin, Adam P.; Hazen, Terry C.; Stolyar, Sergey; Stahl, David A.

    2009-06-22

    Interspecies hydrogen transfer between organisms producing and consuming hydrogen promotes the decomposition of organic matter in most anoxic environments. Although syntrophic couplings between hydrogen producers and consumers are a major feature of the carbon cycle, mechanisms for energy recovery at the extremely low free energies of reactions typical of these anaerobic communities have not been established. In this study, comparative transcriptional analysis of a model sulfate-reducing microbe, Desulfovibrio vulgaris Hildenborough, suggested the use of alternative electron transfer systems dependent upon growth modality. During syntrophic growth on lactate with a hydrogenotrophic methanogen, D. vulgaris up-regulated numerous genes involved in electron transfer and energy generation when compared with sulfate-limited monocultures. In particular, genes coding for the putative membrane-bound Coo hydrogenase, two periplasmic hydrogenases (Hyd and Hyn) and the well-characterized high-molecular weight cytochrome (Hmc) were among the most highly expressed and up-regulated. Additionally, a predicted operon coding for genes involved in lactate transport and oxidation exhibited up-regulation, further suggesting an alternative pathway for electrons derived from lactate oxidation during syntrophic growth. Mutations in a subset of genes coding for Coo, Hmc, Hyd and Hyn impaired or severely limited syntrophic growth but had little affect on growth via sulfate-respiration. These results demonstrate that syntrophic growth and sulfate-respiration use largely independent energy generation pathways and imply that understanding of microbial processes sustaining nutrient cycling must consider lifestyles not captured in pure culture.

  13. Fast magnetic and turbulent-wave dynamos in electron magnetohydrodynamics

    NARCIS (Netherlands)

    Lakhin, V. P.; Moiseev, S. S.; Schep, T. J.

    2000-01-01

    The influence of inertia on the spontaneous amplification of large-scale perturbations by electron magnetohydrodynamic (EMHD) turbulence is studied in a 2 1/2 -dimensional(2 1/2 -D) model. It is shown that electron inertia results in the modification of ct-like effects, which are due to the helicity

  14. Ejected-electron spectroscopy of autoionizing resonances of helium excited by fast-electron impact

    Science.gov (United States)

    Zhang, Zhe; Shan, Xu; Wang, Enliang; Chen, Xiangjun

    2012-06-01

    The autoionizing resonances (2s2)1S, (2p2)1D, and (2s2p)1P of helium have been investigated employing ejected-electron spectroscopy by fast-electron impact at incident energies of 250-2000 eV and ejected angles of 26°-116°. Shore parameters of the line shapes for these three resonances have been obtained in such high incident energy regime except at 250 eV. Distinct discrepancies between the present results at 250 eV and those of McDonald and Crowe at 200 eV [D. G. McDonald and A. Crowe, J. Phys. BJPAMA40953-407510.1088/0953-4075/25/9/018 25, 2129 (1992); D. G. McDonald and A. Crowe, J. Phys. BJPAMA40953-407510.1088/0953-4075/25/20/024 25, 4313 (1992)] and Sise at 250 eV [O. Sise, M. Dogan, I. Okur, and A. Crowe, Phys. Rev. APLRAAN1050-294710.1103/PhysRevA.84.022705 84, 022705 (2011)], especially for 1D and 1P states, are also observed.

  15. Transfer of piano practice in fast performance of skilled finger movements.

    Science.gov (United States)

    Furuya, Shinichi; Nakamura, Ayumi; Nagata, Noriko

    2013-11-01

    Transfer of learning facilitates the efficient mastery of various skills without practicing all possible sensory-motor repertoires. The present study assessed whether motor practice at a submaximal speed, which is typical in sports and music performance, results in an increase in a maximum speed of finger movements of trained and untrained skills. Piano practice of sequential finger movements at a submaximal speed over days progressively increased the maximum speed of trained movements. This increased maximum speed of finger movements was maintained two months after the practice. The learning transferred within the hand to some extent, but not across the hands. The present study confirmed facilitation of fast finger movements following a piano practice at a submaximal speed. In addition, the findings indicated the intra-manual transfer effects of piano practice on the maximum speed of skilled finger movements.

  16. Theoretical study on electron transfer in biological systems (Ⅲ)——Intramolecular electron transfer in metal-containing spiro π-electron system

    Institute of Scientific and Technical Information of China (English)

    翟宇峰; 蒋华良; 朱维良; 顾健德; 陈建忠; 陈凯先; 嵇汝运

    1999-01-01

    Intramolecular electron transfer of metal-containing spiro π-electron system was studied by AM1 method in the MOPAC-ET program developed by the present group. The results indicated that with the increasing of the outer electric field F, the activation energy of the reaction decreased. When F reaches a certain threshold value, the activation energy barrier becomes zero and the rate of reaction achieves the largest value. The results also indicated that electron transfer matrix elements VAB and reorganization energy λ were not obviously affected by outer electric field while the exothermicity ΔE was directly proportional to it.

  17. Intermolecular electron transfer from naphthalene derivatives in the higher triplet excited states.

    Science.gov (United States)

    Sakamoto, Masanori; Cai, Xichen; Hara, Michihiro; Fujitsuka, Mamoru; Majima, Tetsuro

    2004-08-11

    Intermolecular electron transfer (ELT) from a series of naphthalene derivatives (NpD) in the higher triplet excited states (T(n)) to carbon tetrachloride (CCl(4)) in Ar-saturated acetonitrile was observed using the two-color two-laser flash photolysis method. The ELT efficiency depended on the driving force of ELT. Since the ELT from the T(n) state occurred competitively with the internal conversion (IC, T(n) --> T(1)) and the triplet energy transfer (ENT), the ELT became apparent only when sufficient free energy change of ELT was attained. On the other hand, ELT from the T(1) state was not observed, although ELT from the T(1) state with sufficiently long lifetime has a slightly exothermic driving force. The fast ELT from the T(n) state and lack of the reactivity of the T(1) state were explained well by the "sticky" dissociative electron-transfer model based on one-electron reductive attachment to CCl(4) leading to the C-Cl bond cleavage.

  18. The electron-transfer reaction between azurin and the cytochrome c oxidase from Pseudomonas aeruginosa.

    Science.gov (United States)

    Parr, S R; Barber, D; Greenwood, C; Brunori, M

    1977-11-01

    A stopped-flow investigation of the electron-transfer reaction between oxidized azurin and reduced Pseudomonas aeruginosa cytochrome c-551 oxidase and between reduced azurin and oxidized Ps. aeruginosa cytochrome c-551 oxidase was performed. Electrons leave and enter the oxidase molecule via its haem c component, with the oxidation and reduction of the haem d1 occurring by internal electron transfer. The reaction mechanism in both directions is complex. In the direction of oxidase oxidation, two phases assigned on the basis of difference spectra to haem c proceed with rate constants of 3.2 X 10(5)M-1-S-1 and 2.0 X 10(4)M-1-S-1, whereas the haem d1 oxidation occurs at 0.35 +/- 0.1S-1. Addition of CO to the reduced enzyme profoundly modifies the rate of haem c oxidation, with the faster process tending towards a rate limit of 200S-1. Reduction of the oxidase was similarly complex, with a fast haem c phase tending to a rate limit of 120S-1, and a slower phase with a second-order rate of 1.5 X 10(4)M-1-S-1; the internal transfer rate in this direction was o.25 +/- 0.1S-1. These results have been applied to a kinetic model originally developed from temperature-jump studies.

  19. First-Principles Calculations of Electron Transfer in Organic Molecules

    Science.gov (United States)

    Pati, Ranjit; Karna, Shashi P.

    2000-03-01

    Suitably tailored organic structures are considered potential candidates as components in molecular electronic devices. A common molecular architecture for electronics consists of an electron donor (D) and an electron acceptor (A) moiety bonded together by a chemically inert bridging moiety, called spacer (S). The D-S-A combination constitutes the basic component equivalent of a solid state capacitor. A useful physical property that determines the applicability of molecular structures in moletronics is the electron transfer (ET) rate, which is related, in a two-state approximation, to the coupling matrix between the two electronic states representing the localization of electrons. In an effort to model potential organic structures, we have calculated the ET coupling matrix elements in a number of D-, S-, and A-type organic molecules with the use of ab initio Hartree-Fock method and two different basis sets, namely an STO-3G and a double zeta plus polarization (DZP). A number of important findings have emerged from this study: (i) The ET coupling matrix strongly depends upon the geometrical arrangement of the molecular fragment(s) in the architecture. (ii) In an oligomeric chain, the ET matrix decreases exponentially with molecular length (number of monomer units). (iii) In cyclic alkanes, the magnitude of the ET coupling matrix decreases with increasing size of fused rings.

  20. Charge-Transfer Emitting Triarylborane π-Electron Systems.

    Science.gov (United States)

    Li, Sheng-Yong; Sun, Zuo-Bang; Zhao, Cui-Hua

    2017-08-07

    Triarylboranes have attracted significantly increasing research interest as a remarkable class of photoelectronic π-electron materials. Because of the presence of vacant p orbital on the B center, the boryl group is a very unique electron acceptor that exhibits not only electron-accepting ability through p-π* conjugation but also high Lewis acidity to coordinate with Lewis bases and steric bulk arising from the aryl substituent on the B center to get enough kinetic stability. Thus, the incorporation of a trivalent B element into π-conjugated systems is an efficient strategy to tune the electronic and stereo structures and thus the photoelectronic properties of π-electron systems. When an electron-donating group, such as amino, is present, triarylboranes would likely display intramolecular charge-transfer transitions. These kinds of molecules are often highly emissive. In addition, the geometry of the molecules has a great impact on the emission properties. In this Forum Article, we herein describe our recent progress on the charge-transfer emitting triarylborane π-electron systems with novel geometries, which include the lateral boryl-substituted π-system with amino groups at the terminal positions, the o,o'-substituted biaryl π-system with boryl and amino groups at the o,o'-positions, a triarylborane-based BODIPY system, and a B,N/S-bridged ladder-type π-system. We mainly put the emphasis on the molecular design concept, structure-property relationships, intriguing emission properties and great applications of the corresponding triarylborane π-systems.

  1. Syntrophic anaerobic photosynthesis via direct interspecies electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Ha, Phuc T.; Lindemann, Stephen R.; Shi, Liang; Dohnalkova, Alice C.; Fredrickson, James K.; Madigan, Michael T.; Beyenal, Haluk

    2017-01-09

    Microbial phototrophs are key primary producers on Earth. Currently known electron donors for microbial photosynthesis include H2O, H2, H2S and other reduced inorganic compounds. We describe a new form of metabolism linking anoxygenic photosynthesis to anaerobic respiration, or “syntrophic anoxygenic photosynthesis.” We show that photoautotrophy in green sulfur bacterium Prosthecochloris aestaurii can be driven not only by electrons from a graphite electrode, but also by acetate oxidation via interspecies electron transfer from heterotrophic partner bacterium Geobacter sulfurreducens. P. aestuarii photosynthetic growth using reductant provided by either an electrode or syntrophy was robust and light-dependent. By contrast, P. aestuarii did not grow in co-culture with a G. sulfurreducens mutant lacking a trans-outer membrane porin-cytochrome protein complex required for direct intercellular electron transfer,. This syntrophic interaction suggests revisitation of global carbon cycling in anoxic environments and lays a foundation for further engineering of phototrophic microbial communities for biotechnological applications, such as waste treatment and bioenergy production.

  2. Time-resolved measurements of fast electron-sourced sheath dynamics

    Science.gov (United States)

    Green, J. S.; Murphy, C. D.; Gray, R. J.; MacLellan, D. A.; McKenna, P.; Dance, R. J.; Ridgers, C. P.; Robinson, A. P. L.; Rusby, D.; Wilson, L.

    2013-10-01

    Here we present unique fast electron generation and transport results from a recent experimental campaign on the Astra Gemini laser facility. Using complementary diagnostics a unique picture is presented of the evolution of electron sheath dynamics, and thus electron transport, in the interaction of an ultra-intense, short pulse (40 fs) laser with a solid target. Targets were irradiated at up to (1021W cm - 2), with a chirped optical probe used to spatially and temporally resolve the rear surface target reflectivity. Clear snapshots of rapid ionisation and fast electron transport at the target rear surface were observed for a range of target and laser parameters. As well as providing a valuable insight into fast electron transport at the rear surface the role of fast electron refluxing inside thin targets was also investigated through the use of thin foils and novel targetry. These studies aim to see how the very earliest stages of the fast electron dynamics directly affect both the sheath evolution and ion acceleration at the rear surface.

  3. Electron Generation and Transport in Intense Relativistic Laser-Plasma Interactions Relevant to Fast Ignition ICF

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Tammy Yee Wing [Univ. of California, San Diego, CA (United States)

    2010-01-01

    The reentrant cone approach to Fast Ignition, an advanced Inertial Confinement Fusion scheme, remains one of the most attractive because of the potential to efficiently collect and guide the laser light into the cone tip and direct energetic electrons into the high density core of the fuel. However, in the presence of a preformed plasma, the laser energy is largely absorbed before it can reach the cone tip. Full scale fast ignition laser systems are envisioned to have prepulses ranging between 100 mJ to 1 J. A few of the imperative issues facing fast ignition, then, are the conversion efficiency with which the laser light is converted to hot electrons, the subsequent transport characteristics of those electrons, and requirements for maximum allowable prepulse this may put on the laser system. This dissertation examines the laser-to-fast electron conversion efficiency scaling with prepulse for cone-guided fast ignition. Work in developing an extreme ultraviolet imager diagnostic for the temperature measurements of electron-heated targets, as well as the validation of the use of a thin wire for simultaneous determination of electron number density and electron temperature will be discussed.

  4. Electron Transfer and Solvent-Mediated Electronic Localization in Molecular Photocatalysis

    DEFF Research Database (Denmark)

    Dohn, Asmus Ougaard; Kjær, Kasper Skov; Harlang, Tobias B.

    2016-01-01

    This work provides a detailed mechanism for electron transfer in a heterodinuclear complex designed as a model system in which to study homogeneous molecular photocatalysis. With efficient Born–Oppenheimer molecular dynamics simulations, we show how intermediate, charge-separated states can mediate...... the electron transfer. We observe how Jahn–Teller distortion effects play out in solution, when the molecule has energetically close-lying states, and how this distortion is averaged out in the thermal sampling. Finally, we demonstrate how the solvent helps stabilize and localize the separated charge...

  5. Mechanisms for control of biological electron transfer reactions.

    Science.gov (United States)

    Williamson, Heather R; Dow, Brian A; Davidson, Victor L

    2014-12-01

    Electron transfer (ET) through and between proteins is a fundamental biological process. The rates and mechanisms of these ET reactions are controlled by the proteins in which the redox centers that donate and accept electrons reside. The protein influences the magnitudes of the ET parameters, the electronic coupling and reorganization energy that are associated with the ET reaction. The protein can regulate the rates of the ET reaction by requiring reaction steps to optimize the system for ET, leading to kinetic mechanisms of gated or coupled ET. Amino acid residues in the segment of the protein through which long range ET occurs can also modulate the ET rate by serving as staging points for hopping mechanisms of ET. Specific examples are presented to illustrate these mechanisms by which proteins control rates of ET reactions. Copyright © 2014 Elsevier Inc. All rights reserved.

  6. Noise-assisted quantum electron transfer in photosynthetic complexes

    CERN Document Server

    Nesterov, Alexander I; Martínez, José Manuel Sánchez; Sayre, Richard T

    2013-01-01

    Electron transfer (ET) between primary electron donors and acceptors is modeled in the photosystem II reaction center (RC). Our model includes (i) two discrete energy levels associated with donor and acceptor, interacting through a dipole-type matrix element and (ii) two continuum manifolds of electron energy levels ("sinks"), which interact directly with the donor and acceptor. Namely, two discrete energy levels of the donor and acceptor are embedded in their independent sinks through the corresponding interaction matrix elements. We also introduce classical (external) noise which acts simultaneously on the donor and acceptor (collective interaction). We derive a closed system of integro-differential equations which describes the non-Markovian quantum dynamics of the ET. A region of parameters is found in which the ET dynamics can be simplified, and described by coupled ordinary differential equations. Using these simplified equations, both sharp and flat redox potentials are analyzed. We analytically and nu...

  7. Electron transfer, ionization, and excitation in atomic collisions

    Energy Technology Data Exchange (ETDEWEB)

    Winter, T.G.; Alston, S.G.

    1992-01-01

    The research being carried out at Penn State by Winter and Alston addresses the fundamental processes of electron transfer, ionization, and excitation in ion-atom (and ion-ion) collisions. The focus is on intermediate- and higher-energy collisions, corresponding to proton energies of about 25 kilo-electron-volts (keV) or larger. At intermediate energies, where the transition probabilities are not small, many states must be coupled in a large calculation, while at higher energies, perturbative approaches may be used. Several studies have been carried out in the current three-year period; most of these treat systems with only one or two electrons, so that fewer approximations need be made and the basic collisional mechanisms can be more clearly described.

  8. General purpose pulse shape analysis for fast scintillators implemented in digital readout electronics

    Science.gov (United States)

    Asztalos, Stephen J.; Hennig, Wolfgang; Warburton, William K.

    2016-01-01

    Pulse shape discrimination applied to certain fast scintillators is usually performed offline. In sufficiently high-event rate environments data transfer and storage become problematic, which suggests a different analysis approach. In response, we have implemented a general purpose pulse shape analysis algorithm in the XIA Pixie-500 and Pixie-500 Express digital spectrometers. In this implementation waveforms are processed in real time, reducing the pulse characteristics to a few pulse shape analysis parameters and eliminating time-consuming waveform transfer and storage. We discuss implementation of these features, their advantages, necessary trade-offs and performance. Measurements from bench top and experimental setups using fast scintillators and XIA processors are presented.

  9. ELECTRON TRANSFER MECHANISM AT THE SOLID-LIQUID INTERFACE OF PHYLLOSILICATES

    Science.gov (United States)

    Interfacial electron transfer processes on clay minerals have significant impact in natural environments and geochemical systems. Nitrobenzene was used as molecular probes to study the electron transfer mechanism at the solid-water interfaces of Fe-containing phyllosicates. For...

  10. Application of Electron-Transfer Theory to Several Systems of Biological Interest

    Science.gov (United States)

    Marcus, R. A.; Sutin, N.

    1985-03-23

    Electron-transfer reaction rates are compared with theoretically calculated values for several reactions in the bacterial photosynthetic reaction center. A second aspect of the theory, the cross-relation, is illustrated using protein-protein electron transfers.

  11. Direct observation of the ultrafast electron transfer process in a polymer/fullerene blend

    NARCIS (Netherlands)

    Cerullo, G.; Lanzani, G.; Silvestri, S. De; Brabec, Ch.J.; Zerza, G.; Sariciftci, N.S.; Hummelen, J.C.

    2000-01-01

    Photoinduced electron transfer in organic molecules is an extensively investigated topic both because of fundamental interest in the photophysics and for applications to artificial photosynthesis. Highly efficient ultrafast electron transfer from photoexcited conjugated polymers to C60 has been

  12. Simulations of electron transport for fast ignition using Lisp

    Energy Technology Data Exchange (ETDEWEB)

    Town, R.P.J. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States)]. E-mail: town2@llnl.gov; Chen, C. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Cottrill, L.A. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Key, M.H. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Kruer, W.L. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Langdon, A.B. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Lasinski, B.F. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Snavely, R.A. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Still, C.H. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Tabak, M. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States); Welch, D.R. [Mission Research Corp., 5001 Indian School Rd NE, Albuquerque, NM 87110-3946 (United States); Wilks, S.C. [Lawrence Livermore National Laboratory, University of California, 7000 East Avenue, Livermore, CA 94550-9234 (United States)

    2005-05-21

    A crucial issue for the viability of the fast ignition approach to inertial fusion energy is the transport of the ignition pulse energy from the critical surface to the high-density compressed fuel. Experiments have characterized this transport through the interaction of short pulse, high intensity lasers with solid-density targets containing thin K{alpha} fluorescence layers. These experiments show a reasonably well-collimated beam, although with a significantly larger radius than the incident laser beam. We report on LSP calculations of these experiments, which show reasonable agreement with the experimental observations.

  13. Fast-ignition design transport studies: realistic electron source, integrated PIC-hydrodynamics, imposed magnetic fields

    CERN Document Server

    Strozzi, D J; Larson, D J; Divol, L; Kemp, A J; Bellei, C; Marinak, M M; Key, M H

    2012-01-01

    Transport modeling of idealized, cone-guided fast ignition targets indicates the severe challenge posed by fast-electron source divergence. The hybrid particle-in-cell [PIC] code Zuma is run in tandem with the radiation-hydrodynamics code Hydra to model fast-electron propagation, fuel heating, and thermonuclear burn. The fast electron source is based on a 3D explicit-PIC laser-plasma simulation with the PSC code. This shows a quasi two-temperature energy spectrum, and a divergent angle spectrum (average velocity-space polar angle of 52 degrees). Transport simulations with the PIC-based divergence do not ignite for > 1 MJ of fast-electron energy, for a modest 70 micron standoff distance from fast-electron injection to the dense fuel. However, artificially collimating the source gives an ignition energy of 132 kJ. To mitigate the divergence, we consider imposed axial magnetic fields. Uniform fields ~50 MG are sufficient to recover the artificially collimated ignition energy. Experiments at the Omega laser facil...

  14. Retrieving ice cloud properties by using a fast infrared radiative transfer model

    Science.gov (United States)

    Wang, C.; Yang, P.; Heidinger, A. K.; Platnick, S. E.; Baum, B. A.

    2010-12-01

    A new fast infrared radiative transfer (RT) model based on pre-computed look-up tables (LUTs) including the LUTs for emissivity function and cloud effective temperature is proposed. This model can be applied to the simulation of upward radiance (or brightness temperature) at 8.5, 11.0 and 12.0 μm at the top of the atmosphere (TOA) under cloudy-sky conditions. Optical depths of Atmospheric layers resulting from gaseous absorption are derived from the correlated-K distribution (CKD) method. The cloud reflection and transmission functions are computed from the discrete ordinates radiative transfer model (DISORT). In addition to the LUTs of reflection and transmission functions of cloud in traditional RT models, the LUTs of emissivity and effective temperature are also included to improve the accuracy. Generally speaking, for an atmosphere containing a single ice cloud layer with small optical thickness (i.e., less than 5.0), the brightness temperature differences (BTDs) between the fast model and DISORT results are approximately less than 0.1K, whereas the BTDs are less than 0.02K when the ice cloud optical thickness is larger than 5.0. Moreover, with the fast RT model, cloud optical and microphysical properties of ice clouds are retrieved from MODIS and CALIPSO observations and the MERRA reanalysis data. The present retrievals are compared with the MODIS operational cloud products (MYD06).

  15. Reduced density matrix hybrid approach: application to electronic energy transfer.

    Science.gov (United States)

    Berkelbach, Timothy C; Markland, Thomas E; Reichman, David R

    2012-02-28

    Electronic energy transfer in the condensed phase, such as that occurring in photosynthetic complexes, frequently occurs in regimes where the energy scales of the system and environment are similar. This situation provides a challenge to theoretical investigation since most approaches are accurate only when a certain energetic parameter is small compared to others in the problem. Here we show that in these difficult regimes, the Ehrenfest approach provides a good starting point for a dynamical description of the energy transfer process due to its ability to accurately treat coupling to slow environmental modes. To further improve on the accuracy of the Ehrenfest approach, we use our reduced density matrix hybrid framework to treat the faster environmental modes quantum mechanically, at the level of a perturbative master equation. This combined approach is shown to provide an efficient and quantitative description of electronic energy transfer in a model dimer and the Fenna-Matthews-Olson complex and is used to investigate the effect of environmental preparation on the resulting dynamics.

  16. Overpotential-induced lability of the electronic overlap factor in long-range electrochemical electron transfer: charge and distance dependence

    DEFF Research Database (Denmark)

    Kornyshev, A. A.; Kuznetsov, A. M.; Nielsen, Jens Ulrik;

    2000-01-01

    Long-distance electrochemical electron transfer exhibits approximately exponential dependence on the electron transfer distance. On the basis of a jellium model of the metal surface we show that the slope of the logarithm of the current vs. the transfer distance also depends strongly...

  17. Gas hydrate fast nucleation from melting ice and quiescent growth along vertical heat transfer tube

    Institute of Scientific and Technical Information of China (English)

    XIE; Yingming; GUO; Kaihua; LIANG; Deqing; FAN; Shuanshi

    2005-01-01

    During the observation of HCFC141b gas hydrate growth processes outside a vertical heat transfer tube, two exciting phenomena were found: fast nucleation of gas hydrate from melting ice, and the spontaneous permeation of water into the guest phases along the surface of heat transfer tube to form gas hydrate continuously. These two phenomena were explained with Zhou & Sloan's hypothesis and the theory of surface free energy respectively, and a novel method of gas hydrate formation was presented--gas hydrate fast nucleation from melting ice and quiescent growth along heat transfer tube. There is no mechanic stirring in this method, the formed gas hydrates are compact, the ratio of unreacted interstitial water is little, which overcome the drawback of high energy cost and high ratio of unreacted interstitial water among the formed gas hydrates in the system with mechanic stirring. This finding will benefit the gas hydrate application technologies such as natural gas storage technology or cool storage technology with gas hydrate.

  18. Optically monitoring voltage in neurons by photo-induced electron transfer through molecular wires.

    Science.gov (United States)

    Miller, Evan W; Lin, John Y; Frady, E Paxon; Steinbach, Paul A; Kristan, William B; Tsien, Roger Y

    2012-02-07

    Fluorescence imaging is an attractive method for monitoring neuronal activity. A key challenge for optically monitoring voltage is development of sensors that can give large and fast responses to changes in transmembrane potential. We now present fluorescent sensors that detect voltage changes in neurons by modulation of photo-induced electron transfer (PeT) from an electron donor through a synthetic molecular wire to a fluorophore. These dyes give bigger responses to voltage than electrochromic dyes, yet have much faster kinetics and much less added capacitance than existing sensors based on hydrophobic anions or voltage-sensitive ion channels. These features enable single-trial detection of synaptic and action potentials in cultured hippocampal neurons and intact leech ganglia. Voltage-dependent PeT should be amenable to much further optimization, but the existing probes are already valuable indicators of neuronal activity.

  19. Triple differential cross sections for the ionization of atomic hydrogen by fast electrons

    Science.gov (United States)

    Byron, F. W.; Joachain, C. J.; Piraux, B.

    1983-12-01

    The triple differential cross section for the ionization of atomic hydrogen by fast electrons is analyzed in the case of a coplanar, asymmetric geometry by using the eikonal Born series theory. Our calculations are in good agreement with recent measurements performed at an incident electron energy of 250 eV.

  20. Studies of Electron Transport and Isochoric Heating and Their Applicability to Fast Ignition

    Energy Technology Data Exchange (ETDEWEB)

    Key, M H; Amiranoff, F; Andersen, C; Batani, D; Baton, S D; Cowan, T; Fisch, N; Freeman, R; Gremillet, L; Hall, T; Hatchett, S; Hill, J; King, J; Kodama, R; Koch, J; Koenig, M; Lasinski, B; Langdon, B; MacKinnon, A; Martinolli, E; Norreys, P; Parks, P; Perrelli-Cippo, E; Rabec Le Gloahec, M; Rosenbluth, M; Rousseaux, C; Santon, J J; Scianitti, F; Snavely, R; Tabak, M; Tanaka, K; Town, R; Tsutumi, T; Stephens, R

    2003-10-30

    Experimental measurements of electron transport and isochoric heating in 100 J, 1 ps laser irradiation of solid A1 targets are presented. Modeling with a hybrid PIC code is compared with the data and good agreement is obtained using a heuristic model for the electron injection. The relevance for fast ignition is discussed.

  1. Hetero-cycloreversions mediated by photoinduced electron transfer.

    Science.gov (United States)

    Pérez-Ruiz, Raúl; Jiménez, M Consuelo; Miranda, Miguel A

    2014-04-15

    Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest. In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies. In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited. In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the

  2. Polyoxometalate-mediated electron transfer-oxygen transfer oxidation of cellulose and hemicellulose to synthesis gas.

    Science.gov (United States)

    Sarma, Bidyut Bikash; Neumann, Ronny

    2014-08-01

    Terrestrial plants contain ~70% hemicellulose and cellulose that are a significant renewable bioresource with potential as an alternative to petroleum feedstock for carbon-based fuels. The efficient and selective deconstruction of carbohydrates to their basic components, carbon monoxide and hydrogen, so called synthesis gas, is an important key step towards the realization of this potential, because the formation of liquid hydrocarbon fuels from synthesis gas are known technologies. Here we show that by using a polyoxometalate as an electron transfer-oxygen transfer catalyst, carbon monoxide is formed by cleavage of all the carbon-carbon bonds through dehydration of initially formed formic acid. In this oxidation-reduction reaction, the hydrogen atoms are stored on the polyoxometalate as protons and electrons, and can be electrochemically released from the polyoxometalate as hydrogen. Together, synthesis gas is formed. In a hydrogen economy scenario, this method can also be used to convert carbon monoxide to hydrogen.

  3. Bremsstrahlung measurements for characterization of intense short-pulse, laser produced fast electrons with OMEGA EP

    Science.gov (United States)

    Daykin, Tyler; Sawada, Hiroshi; Sentoku, Yasuhiko; Pandit, Rishi; Chen, Cliff; Beg, Farhat; Chen, Hui; McLean, Harry; Patel, Pravesh; Tommasini, Riccardo

    2016-10-01

    Understanding relativistic fast electron generation and transport inside solids is important for applications such as generation of high energy x-ray sources and fast ignition. An experiment was carried out to study the scaling of the fast electron spectrum and bremsstrahlung generation in multi-pico second laser interactions using 1 ps and 10 ps OMEGA EP short-pulse beam to generate fast electrons at a similar peak intensity of 5x1018 W/cm2. The bremsstrahlung produced by collisions of the fast electrons with background ions was recorded using differential filter stacked spectrometers. A preliminary analysis with a Monte Carlo Code ITS shows that the electrons injection having an electron slope 1.8 MeV matched well with the high energy component of the 1 ps and 10 ps bremsstrahlung measurements. Details of the data analysis and modeling with Monte Carlo and a hybrid particle-in-cell codes will be presented at the conference. Work supported by the UNR Office of the Provost and by DOE/OFES under Contract No. DE-SC0008827. This collaborative work was partially supported under the auspices of the US DOE by LLNL under Contracts No. DE-AC52-07NA27344 and No. DE-FG-02-05ER54834.

  4. Characteristics of the fast electron emission produced during the cleavage of crystals

    Indian Academy of Sciences (India)

    B P Chandra; N L Patel; S S Rahangdale; R P Patel; V K Patle

    2003-01-01

    The present paper reports the fast electron emission produced during the cleavage of alkali halide crystals and models the dynamics of the process. The mechano-emission arises as a result of the ionization of surface traps at the expense of the energy which is released in the annihilation of the defects which are formed during cleavage. The slow electrons which appear upon the ionization of surface traps are subsequently accelerated in the field of negatively charged segment of the freshly cleaved surface. Considering the basic mechanism of fast electron emission, expressions are derived which are able to explain satisfactorily the temporal, thermal, charge, surface, coloration, water adsorption and other characteristics of the fast electron emission produced during the cleavage of crystals. The decay time of the charges on the newly created surfaces, and the velocity of cracks can be determined from the measurements of fast electron emission produced during the cleavage of crystals. It is shown that two types of diffusing centres are responsible for the charge relaxation and thereby for the emission of fast electrons produced during the cleavage of alkali halide crystals.

  5. Local operator partitioning of electronic energy for electronic energy transfer: An efficient algorithm

    CERN Document Server

    Nagesh, Jayashree; Brumer, Paul

    2013-01-01

    An efficient computational algorithm to implement a local operator approach to partitioning electronic energy in general molecular systems is presented. This approach, which rigorously defines the electronic energy on any subsystem within a molecule, gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. We apply the technique to the $9-$(($1-$naphthyl)$-$methyl)-anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH$_2-$naphthyl groups as subsystems, and examine their electronic energies and populations for several excited states using Configuration Interaction Singles method. The implemented approach shows a wide variety of different behaviors amongst these excited electronic states.

  6. Measurement of fast electrons spectra generated by interaction between solid target and peta watt laser

    Energy Technology Data Exchange (ETDEWEB)

    Tanimoto, T; Habara, H; Tanaka, K A; Kodama, R [Graduate School of Engineering, Osaka University, 2-6 Yamada-oka, Suita, Osaka 565-0871 (Japan); Nakatsutsumi, M [Laboratoire pour l' Utilisation des Laser Intenses (LULI), CNRS, Ecole Polytechnique, Route de Saclay, 91128 Palaiseau, Cedex F 91128 (France); Lancaster, K L; Green, J S; Scott, R H H; Sherlock, M; Norreys, P A [STFC Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0QX (United Kingdom); Evans, R G; Haines, M G [Department of Physics, Imperial College London, Blackett Laboratory, Prince Consort Road, London SW7 2BZ (United Kingdom); Kar, S; Zepf, M [Centre for Plasma Physics, School of Mathematics and Physics, Queens University Belfast, University Road, Belfast BT7 1NN (United Kingdom); King, J; Ma, T; Wei, M S; Yabuuchi, T; Beg, F N [Department of Mechanical and Aerospace Engineering, UC San Diego, 9500 Gillman Drive 0411, La Jolla, California 92093-0411, United States of America (United States); Key, M H, E-mail: tanimoto@ile.osaka-u.ac.j [Lawrence Livermore National Laboratory, PO Box 808, Livermore, California 94550, United States of America (United States)

    2010-08-01

    Fast electron energy spectra have been measured for a range of intensities between 10{sup 18} Wcm{sup -2} and 10{sup 21} Wcm{sup -2} and for different target materials using electron spectrometers. Several experimental campaigns were conducted on peta watt laser facilities at the Rutherford Appleton Laboratory and Osaka University. In these experimental campaigns, the pulse duration was varied from 0.5 ps to 5 ps. The laser incident angle was also changed from normal incidence to 40{sup 0} in p-polarized. The results show a reduction from the ponderomotive scaling on fast electrons over 10{sup 20} Wcm{sup -2}.

  7. Gunn effect and transferred electron devices. Citations from the NTIS data base

    Science.gov (United States)

    Reed, W. E.

    1980-06-01

    A bibliography containing 99 abstracts addressing the Gunn effect and transferred electron devices is presented. The application of Gunn effect and transferred electron devices to microwave generation, amplification, and control is included. The Gunn effect in semiconductors is dicussed along with the design, fabrication, and properties of Gunn diodes and transferred electron devices.

  8. Mechanisms of bridge-mediated electron transfer: a TDDFT electronic dynamics study.

    Science.gov (United States)

    Ding, Feizhi; Chapman, Craig T; Liang, Wenkel; Li, Xiaosong

    2012-12-14

    We present a time-dependent density functional theory approach for probing the dynamics of electron transfer on a donor-bridge-acceptor polyene dye scaffold. Two kinds of mechanisms, namely, the superexchange mechanism and the sequential mechanism, may be involved in the electron transfer process. In this work, we have focused on the crossover between these two charge transfer mechanisms on a series of donor-bridge-acceptor polyene dye systems with varying lengths of conjugated bridges. A number of methods and quantities are used to assist in the analysis, including the phase relationship of charge evolution and frequency domain spectra of the time-dependent dipole. Our simulations show that the superexchange mechanism plays a dominant role in the electron transfer from donor to acceptor when the bridge length is small, and the sequential mechanism becomes more important as the polyene bridge is lengthened. Full Ehrenfest dynamics with nuclear motion show that molecular vibrations play a very small role in such ultrafast charge transfer processes.

  9. MATHEMATICAL MODELING OF EXTRACELLULAR ELECTRON TRANSFER IN BIOFILMS

    Energy Technology Data Exchange (ETDEWEB)

    Renslow, Ryan S.; Babauta, Jerome T.; Kuprat, Andrew P.; Schenk, Jim; Ivory, Cornelius; Fredrickson, Jim K.; Beyenal, Haluk

    2015-09-12

    Electrochemically active biofilms have a unique form of respiration in which they utilize solid external materials as terminal electron acceptors for their metabolism. Currently, two primary mechanisms have been identified for long-range extracellular electron transfer (EET): a diffusion- and a conduction-based mechanism. Evidence in the literature suggests that some biofilms, particularly Shewanella oneidensis, produce the requisite components for both mechanisms. In this study, a generic model is presented that incorporates the diffusion- and the conduction-based mechanisms and allows electrochemically active biofilms to utilize both simultaneously. The model was applied to S. oneidensis and Geobacter sulfurreducens biofilms using experimentally generated data found in the literature. Our simulation results show that 1) biofilms having both mechanisms available, especially if they can interact, may have a metabolic advantage over biofilms that can use only a single mechanism; 2) the thickness of G. sulfurreducens biofilms is likely not limited by conductivity; 3) accurate intrabiofilm diffusion coefficient values are critical for current generation predictions; and 4) the local biofilm potential and redox potential are two distinct parameters and cannot be assumed to have identical values. Finally, we determined that simulated cyclic and squarewave voltammetry based on our model are currently not capable of determining the specific percentages of extracellular electron transfer mechanisms in a biofilm. The developed model will be a critical tool for designing experiments to explain EET mechanisms.

  10. Controlling time scales for electron transfer through proteins

    Directory of Open Access Journals (Sweden)

    Scot Wherland

    2015-12-01

    Full Text Available Electron transfer processes within proteins constitute key elements in biological energy conversion processes as well as in a wide variety of biochemical transformations. Pursuit of the parameters that control the rates of these processes is driven by the great interest in the latter reactions. Here, we review a considerable body of results emerging from investigation of intramolecular electron transfer (ET reactions in two types of proteins, all done by the use of the pulse-radiolysis method: first are described results of extensive studies of a model system, the bacterial electron mediating protein azurin, where an internal ET between the disulfide radical ion and the Cu(II is induced. Impact of specific structural changes introduced into azurin on the reaction rates and the parameters controlling it are discussed. Then, the presentation is extended to results of investigations of intra-protein ET reactions that are part of catalytic cycles of multi-copper containing enzymes. Again, the rates and the parameters controlling them are presented and discussed in the context of their efficacy and possible constraints set on their evolution.

  11. Modeling biofilms with dual extracellular electron transfer mechanisms

    Science.gov (United States)

    Renslow, Ryan; Babauta, Jerome; Kuprat, Andrew; Schenk, Jim; Ivory, Cornelius; Fredrickson, Jim; Beyenal, Haluk

    2013-01-01

    Electrochemically active biofilms have a unique form of respiration in which they utilize solid external materials as terminal electron acceptors for their metabolism. Currently, two primary mechanisms have been identified for long-range extracellular electron transfer (EET): a diffusion- and a conduction-based mechanism. Evidence in the literature suggests that some biofilms, particularly Shewanella oneidensis, produce the requisite components for both mechanisms. In this study, a generic model is presented that incorporates the diffusion- and the conduction-based mechanisms and allows electrochemically active biofilms to utilize both simultaneously. The model was applied to S. oneidensis and Geobacter sulfurreducens biofilms using experimentally generated data found in the literature. Our simulation results show that 1) biofilms having both mechanisms available, especially if they can interact, may have a metabolic advantage over biofilms that can use only a single mechanism; 2) the thickness of G. sulfurreducens biofilms is likely not limited by conductivity; 3) accurate intrabiofilm diffusion coefficient values are critical for current generation predictions; and 4) the local biofilm potential and redox potential are two distinct parameters and cannot be assumed to have identical values. Finally, we determined that simulated cyclic and squarewave voltammetry based on our model are currently not capable of determining the specific percentages of extracellular electron transfer mechanisms in a biofilm. The developed model will be a critical tool for designing experiments to explain EET mechanisms. PMID:24113651

  12. Microbial extracellular electron transfer and its relevance to iron corrosion.

    Science.gov (United States)

    Kato, Souichiro

    2016-03-01

    Extracellular electron transfer (EET) is a microbial metabolism that enables efficient electron transfer between microbial cells and extracellular solid materials. Microorganisms harbouring EET abilities have received considerable attention for their various biotechnological applications, including bioleaching and bioelectrochemical systems. On the other hand, recent research revealed that microbial EET potentially induces corrosion of iron structures. It has been well known that corrosion of iron occurring under anoxic conditions is mostly caused by microbial activities, which is termed as microbiologically influenced corrosion (MIC). Among diverse MIC mechanisms, microbial EET activity that enhances corrosion via direct uptake of electrons from metallic iron, specifically termed as electrical MIC (EMIC), has been regarded as one of the major causative factors. The EMIC-inducing microorganisms initially identified were certain sulfate-reducing bacteria and methanogenic archaea isolated from marine environments. Subsequently, abilities to induce EMIC were also demonstrated in diverse anaerobic microorganisms in freshwater environments and oil fields, including acetogenic bacteria and nitrate-reducing bacteria. Abilities of EET and EMIC are now regarded as microbial traits more widespread among diverse microbial clades than was thought previously. In this review, basic understandings of microbial EET and recent progresses in the EMIC research are introduced.

  13. Fast Electron Repulsion Integrals for Molecular Coulomb Sturmians

    DEFF Research Database (Denmark)

    Avery, James Emil

    2013-01-01

    of hyperspherical harmonics. A rudimentary software library has been implemented and preliminary benchmarks indicate very good performance: On average 40 ns, or approximately 80 clock cycles, per electron repulsion integral. This makes molecular Coulomb Sturmians competitive with Gaussian type orbitals in terms...

  14. Effects of Laser Parameters on Fast Electron Generation in a Multihole Array Target

    Institute of Scientific and Technical Information of China (English)

    JI Yan-Ling; DUAN Tao; JIANG Gang; WU Wei-Doug; TANG Yong-Jian

    2011-01-01

    The effects of laser parameters on the production of fast electrons from laser-multihole array target interaction are investigated theoretically via two-dimensional particle-in-cell simulations. The results show that the fast electron temperature is scaled by I1/2(λ)2 with I and(λ) being the laser intensity and wavelength. When the laser intensity reaches 2.14 × 10(20) W.cm-2, a typical bi-Maxwellian energy distribution is observed. The slope temperature of the low-energy component fits the linear scaling Th~I1/2 well. The high-energy component has an increased slope temperature comparable to ponderomotive potential scaling law. In addition, the electron temperature rises linearly with the pulse duration, Th~△t. The divergence angle of the fast electrons increases with laser intensity and pulse duration, but is independent of laser wavelength.

  15. Controlling fast electron beam divergence via temporal shaping of the laser intensity envelope

    CERN Document Server

    Scott, R H H; Beaucourt, C; Markey, K; Lancaster, K L; Brenner, C M; Gray, R J; Musgrave, I O; Robinson, A P L; Li, K; Pasley, J; Notley, M M; Davies, J R; Baton, S D; Santos, J J; McKenna, P; Neely, D; Rose, S J; Norreys, P A

    2010-01-01

    A new experimental technique is described which uses two relativistically intense laser pulses to control and enhance the properties of the MeV electron beam generated during the interaction of an ultra-high-intensity laser pulse with a solid target. Both thermal and Cu K$_{\\alpha}$ x-ray imaging diagnostics show reduced emission size, increased peak emission, increased total emission, and reduced shot-to-shot variability with respect to a single high-contrast pulse. This evidences reduced fast electron divergence, increased fast electron current density and increased energy absorption into the target via fast electrons. The observed characteristics are attributed to magnetic field generation within the target and alterations to the plasma density scale length.

  16. Electron transfer processes occurring on platinum neural stimulating electrodes: a tutorial on the i(V e) profile

    Science.gov (United States)

    Kumsa, Doe W.; Bhadra, Narendra; Hudak, Eric M.; Kelley, Shawn C.; Untereker, Darrel F.; Mortimer, J. Thomas

    2016-10-01

    The aim of this tutorial is to encourage members of the neuroprosthesis community to incorporate electron transfer processes into their thinking and provide them with the tools to do so when they design and work with neurostimulating devices. The focus of this article is on platinum because it is the most used electrode metal for devices in commercial use. The i(V e) profile or cyclic voltammogram contains information about electron transfer processes that can occur when the electrode-electrolyte interface, V e, is at a specific potential, and assumed to be near steady-state conditions. For the engineer/designer this means that if the potential is not in the range of a specific electron transfer process, that process cannot occur. An i(V e) profile, recorded at sweep rates greater than 0.1 mVs-1, approximates steady-state conditions. Rapid transient potential excursions, like that seen with neural stimulation pulses, may be too fast for the reaction to occur, however, this means that if the potential is in the range of a specific electron transfer process it may occur and should be considered. The approach described here can be used to describe the thermodynamic electron transfer processes on other candidate electrode metals, e.g. stainless steel, iridium, carbon-based, etc.

  17. Electron transfer processes occurring on platinum neural stimulating electrodes: a tutorial on the i(V e) profile.

    Science.gov (United States)

    Kumsa, Doe W; Bhadra, Narendra; Hudak, Eric M; Kelley, Shawn C; Untereker, Darrel F; Mortimer, J Thomas

    2016-10-01

    The aim of this tutorial is to encourage members of the neuroprosthesis community to incorporate electron transfer processes into their thinking and provide them with the tools to do so when they design and work with neurostimulating devices. The focus of this article is on platinum because it is the most used electrode metal for devices in commercial use. The i(V e) profile or cyclic voltammogram contains information about electron transfer processes that can occur when the electrode-electrolyte interface, V e, is at a specific potential, and assumed to be near steady-state conditions. For the engineer/designer this means that if the potential is not in the range of a specific electron transfer process, that process cannot occur. An i(V e) profile, recorded at sweep rates greater than 0.1 mVs(-1), approximates steady-state conditions. Rapid transient potential excursions, like that seen with neural stimulation pulses, may be too fast for the reaction to occur, however, this means that if the potential is in the range of a specific electron transfer process it may occur and should be considered. The approach described here can be used to describe the thermodynamic electron transfer processes on other candidate electrode metals, e.g. stainless steel, iridium, carbon-based, etc.

  18. Comparative analysis of using natural and radiogenic lead as heat-transfer agent in fast reactors

    Science.gov (United States)

    Laas, R. A.; Gizbrekht, R. V.; Komarov, P. A.; Nesterov, V. N.

    2016-06-01

    Fast reactors with lead coolant have several advantages over analogues. Performance can be further improved by replacement of natural composition lead with radiogenic one. Thus, two main issues need to be addressed: induced radioactivity in coolant and efficient neutron multiplication factor in the core will be changed and need to be estimated. To address these issues analysis of the scheme of the nuclear transformations in the lead heat-transfer agent in the process of radiation was carried out. Induced radioactivity of radiogenic and natural lead has been studied. It is shown that replacement of lead affects multiplication factor in a certain way. Application of radiogenic lead can significantly affect reactor operation.

  19. Mass Transfer of Corrosion Products in the Nonisothermal Sodium Loop of a Fast Reactor

    Science.gov (United States)

    Varseev, E. V.; Alekseev, V. V.

    2014-11-01

    The mass transfer of the products of corrosion of the steel surface of the sodium loop of a fast nuclear power reactor was investigated for the purpose of optimization of its parameters. The problem of deposition of the corrosion products on the surface of the heat-exchange unit of the indicated loop was considered. Experimental data on the rate of accumulation of deposits in the channel of this unit and results of the dispersion analysis of the suspensions contained in the sodium coolant are presented.

  20. Adsorption and Interfacial Electron Transfer of Saccharomyces Cerevisiae

    DEFF Research Database (Denmark)

    Andersen, Jens Enevold Thanulov

    2003-01-01

    We have studied the adsorption and electron-transfer dynamics of Saccharomyces cerevisiae (yeast) iso-l-cytochrome c adsorbed on Au(lll) electrodes in aqueous phosphate buffer media. This cytochrome possesses a thiol group dos e to the protein surface (Cysl02) suitable for linking the protein...... negative ofthe equilibrium potential of YCC, where the protein is electrochemically functional. The MCS data show tensile differential stress signals when YCC is adsorbed on a gold-coate d MCS, with distinguishable adsorption phases in the time range from

  1. Fast electron current density profile and diffusion studies during LHCD in PBX-M

    Energy Technology Data Exchange (ETDEWEB)

    Jones, S.E.; Kesner, J.; Luckhardt, S.; Paoletti, F. [Massachusetts Inst. of Tech., Cambridge, MA (United States). Plasma Fusion Center; von Goeler, S.; Bernabei, S.; Kaita, R. [Princeton Univ., NJ (United States). Plasma Physics Lab.; Rimini, F. [JET Joint Undertaking, Abingdon (United Kingdom)

    1993-08-01

    Successful current profile control experiments using lower hybrid current drive (LCHD) clearly require knowledge of (1) the location of the driven fast electrons and (2) the ability to maintain that location from spreading due to radial diffusion. These issues can be addressed by examining the data from the hard x-ray camera on PBX-M, a unique diagnostic producing two-dimensional, time resolved tangential images of fast electron bremsstrahlung. Using modeling, these line-of-sight images are inverted to extract a radial fast electron current density profile. We note that ``hollow`` profiles have been observed, indicative of off-axis current drive. These profiles can then be used to calculate an upper bound for an effective fast electron diffusion constant: assuming an extremely radially narrow lower hybrid absorption profile and a transport model based on Rax and Moreau, a model fast electron current density profile is calculated and compared to the experimentally derived profile. The model diffusion constant is adjusted until a good match is found. Applied to steady-state quiescent modes on PBX-M, we obtain an upper limit for an effective diffusion constant of about D*=1.1 m{sup 2}/sec.

  2. The electronic transfer of information and aerospace knowledge diffusion

    Science.gov (United States)

    Pinelli, Thomas E.; Bishop, Ann P.; Barclay, Rebecca O.; Kennedy, John M.

    1992-01-01

    Increasing reliance on and investment in information technology and electronic networking systems presupposes that computing and information technology will play a motor role in the diffusion of aerospace knowledge. Little is known, however, about actual information technology needs, uses, and problems within the aerospace knowledge diffusion process. The authors state that the potential contributions of information technology to increased productivity and competitiveness will be diminished unless empirically derived knowledge regarding the information-seeking behavior of the members of the social system - those who are producing, transferring, and using scientific and technical information - is incorporated into a new technology policy framework. Research into the use of information technology and electronic networks by U.S. aerospace engineers and scientists, collected as part of a research project designed to study aerospace knowledge diffusion, is presented in support of this assertion.

  3. Electron transfer pathway analysis in bacterial photosynthetic reaction center

    CERN Document Server

    Kitoh-Nishioka, Hirotaka

    2016-01-01

    A new computational scheme to analyze electron transfer (ET) pathways in large biomolecules is presented with applications to ETs in bacterial photosynthetic reaction center. It consists of a linear combination of fragment molecular orbitals and an electron tunneling current analysis, which enables an efficient first-principles analysis of ET pathways in large biomolecules. The scheme has been applied to the ET from menaquinone to ubiquinone via nonheme iron complex in bacterial photosynthetic reaction center. It has revealed that not only the central Fe$^{2+}$ ion but also particular histidine ligands are involved in the ET pathways in such a way to mitigate perturbations that can be caused by metal ion substitution and depletion, which elucidates the experimentally observed insensitivity of the ET rate to these perturbations.

  4. Molecular Models for Conductance in Junctions and Electrochemical Electron Transfer

    Science.gov (United States)

    Mazinani, Shobeir Khezr Seddigh

    This thesis develops molecular models for electron transport in molecular junctions and intra-molecular electron transfer. The goal is to identify molecular descriptors that afford a substantial simplification of these electronic processes. First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon's tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer. Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed. Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of

  5. Current drive with combined electron cyclotron wave and high harmonic fast wave in tokamak plasmas

    Science.gov (United States)

    Li, J. C.; Gong, X. Y.; Dong, J. Q.; Wang, J.; Zhang, N.; Zheng, P. W.; Yin, C. Y.

    2016-12-01

    The current driven by combined electron cyclotron wave (ECW) and high harmonic fast wave is investigated using the GENRAY/CQL3D package. It is shown that no significant synergetic current is found in a range of cases with a combined ECW and fast wave (FW). This result is consistent with a previous study [Harvey et al., in Proceedings of IAEA TCM on Fast Wave Current Drive in Reactor Scale Tokamaks (Synergy and Complimentarily with LHCD and ECRH), Arles, France, IAEA, Vienna, 1991]. However, a positive synergy effect does appear with the FW in the lower hybrid range of frequencies. This positive synergy effect can be explained using a picture of the electron distribution function induced by the ECW and a very high harmonic fast wave (helicon). The dependence of the synergy effect on the radial position of the power deposition, the wave power, the wave frequency, and the parallel refractive index is also analyzed, both numerically and physically.

  6. Characterization of intense laser-produced fast electrons using hard x-rays via bremsstrahlung

    Science.gov (United States)

    Sawada, H.; Sentoku, Y.; Bass, A.; Griffin, B.; Pandit, R.; Beg, F.; Chen, H.; McLean, H.; Link, A. J.; Patel, P. K.; Ping, Y.

    2015-11-01

    Energy distribution of high-power, short-pulse laser produced fast electrons was experimentally and numerically studied using high-energy bremsstrahlung x-rays. The hard x-ray photons and escaping electrons from various metal foils, irradiated by the 50 TW Leopard laser at Nevada Terawatt Facility, were recorded with a differential filter stack spectrometer that is sensitive to photons produced by mainly 0.5-2 MeV electrons and an electron spectrometer measuring >2 MeV electrons. The experimental bremsstrahlung and the slope of the measured escaped electrons were compared with an analytic calculation using an input electron spectrum estimated with the ponderomotive scaling. The result shows that the electron spectrum entering a Cu foil could be continuous single slope with the slope temperature of ˜1.5 MeV in the detector range. The experiment and analytic calculation were then compared with a 2D particle-in-cell code, PICLS, including a newly developed radiation transport module. The simulation shows that a two-temperature electron distribution is generated at the laser interaction region, but only the hot component of the fast electrons flow into the target during the interaction because the low energy electron component is trapped by self-generated magnetic field in the preformed plasma. A significant amount of the photons less than 100 keV observed in the experiment could be attributed to the low energy electrons entering the foil a few picoseconds later after the gating field disappears.

  7. In situ Regeneration of NADH via Lipoamide Dehydrogenase-catalyzed Electron Transfer Reaction Evidenced by Spectroelectrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Tam, Tsz Kin; Chen, Baowei; Lei, Chenghong; Liu, Jun

    2012-08-01

    NAD/NADH is a coenzyme found in all living cells, carrying electrons from one reaction to another. We report on characterizations of in situ regeneration of NADH via lipoamide dehydrogenase (LD)-catalyzed electron transfer reaction to regenerate NADH using UV-vis spectroelectrochemistry. The Michaelis-Menten constant (Km) and maximum velocity (Vmax) of NADH regeneration were measured as 0.80 {+-} 0.15 mM and 1.91 {+-} 0.09 {micro}M s-1 in a 1-mm thin-layer spectroelectrochemical cell using gold gauze as the working electrode at the applied potential -0.75 V (vs. Ag/AgCl). The electrocatalytic reduction of the NAD system was further coupled with the enzymatic conversion of pyruvate to lactate by lactate dehydrogenase to examine the coenzymatic activity of the regenerated NADH. Although the reproducible electrocatalytic reduction of NAD into NADH is known to be difficult compared to the electrocatalytic oxidation of NADH, our spectroelectrochemical results indicate that the in situ regeneration of NADH via LD-catalyzed electron transfer reaction is fast and sustainable and can be potentially applied to many NAD/NADH-dependent enzyme systems.

  8. Thermodynamics of electron transfer in oxygenic photosynthetic reaction centers: volume change, enthalpy, and entropy of electron-transfer reactions in manganese-depleted photosystem II core complexes.

    Science.gov (United States)

    Hou, J M; Boichenko, V A; Diner, B A; Mauzerall, D

    2001-06-19

    We have previously reported the thermodynamic data of electron transfer in photosystem I using pulsed time-resolved photoacoustics [Hou et al. (2001) Biochemistry 40, 7109-7116]. In the present work, using preparations of purified manganese-depleted photosystem II (PS II) core complexes from Synechocystis sp. PCC 6803, we have measured the DeltaV, DeltaH, and estimated TDeltaS of electron transfer on the time scale of 1 micros. At pH 6.0, the volume contraction of PS II was determined to be -9 +/- 1 A3. The thermal efficiency was found to be 52 +/- 5%, which corresponds to an enthalpy change of -0.9 +/- 0.1 eV for the formation of the state P680+Q(A-) from P680*. An unexpected volume expansion on pulse saturation of PS II was observed, which is reversible in the dark. At pH 9.0, the volume contraction, the thermal efficiency, and the enthalpy change were -3.4 +/- 0.5 A3, 37 +/- 7%, and -1.15 +/- 0.13 eV, respectively. The DeltaV of PS II, smaller than that of PS I and bacterial centers, is assigned to electrostriction and analyzed using the Drude-Nernst equation. To explain the small DeltaV for the formation of P680+Q(A-) or Y(Z*)Q(A-), we propose that fast proton transfer into a polar region is involved in this reaction. Taking the free energy of charge separation of PS II as the difference between the energy of the excited-state P680* and the difference in the redox potentials of the donor and acceptor, the apparent entropy change (TDeltaS) for charge separation of PS II is calculated to be negative, -0.1 +/- 0.1 eV at pH 6.0 (P680+Q(A-)) and -0.2 +/- 0.15 eV at pH 9.0 (Y(Z*)Q(A-)). The thermodynamic properties of electron transfer in PS II core reaction centers thus differ considerably from those of bacterial and PS I reaction centers, which have DeltaV of approximately -27 A3, DeltaH of approximately -0.4 eV, and TDeltaS of approximately +0.4 eV.

  9. Electromagnetic field generation by ATP-induced reverse electron transfer.

    Science.gov (United States)

    Steele, Richard H

    2003-03-01

    This paper describes a mechanism to explain low-level light emission in biology. A biological analog of the electrical circuitry, modeled on the parallel plate capacitor, traversed by a helical structure, required to generate electromagnetic radiation in the optical spectral range, is described. The charge carrier required for the emissions is determined to be an accelerating electron driven by an ATP-induced reverse electron transfer. The radial velocity component, the emission trajectory, of the moving charges traversing helical protein structures in a cyclotron-type mechanism is proposed to be imposed by the ferromagnetic field components of the iron in the iron-sulfur proteins. The redox systems NADH, riboflavin, and chlorophyll were examined with their long-wavelength absorption maxima determining the energetic parameters for the calculations. Potentials calculated from the axial velocity components for the riboflavin and NADH systems were found to equal the standard redox potentials of these systems as measured electrochemically and enzymatically. The mechanics for the three systems determined the magnetic moments, the angular momenta, and the orbital magnetic fluxes to be adiabatic invariant parameters. The De Broglie dual wave-particle equation, the fundamental equation of wave mechanics, and the key idea of quantum mechanics, establishes the wavelengths for accelerating electrons which, divided into a given radial velocity, gives its respective emission frequency. Electrons propelled through helical structures, traversed by biologically available electric and magnetic fields, make accessible to the internal environment the optical spectral frequency range that the solar spectrum provides to the external environment.

  10. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

    DEFF Research Database (Denmark)

    Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane;

    2015-01-01

    cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...... new light on how oxidative enzymes present in plant degraders may act in concert....

  11. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer

    DEFF Research Database (Denmark)

    Westereng, Bjorge; Cannella, David; Wittrup Agger, Jane;

    2015-01-01

    cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds...

  12. Determination of the electronics transfer function for current transient measurements

    CERN Document Server

    Scharf, Christian

    2014-01-01

    We describe a straight-forward method for determining the transfer function of the readout of a sensor for the situation in which the current transient of the sensor can be precisely simulated. The method relies on the convolution theorem of Fourier transforms. The specific example is a planar silicon pad diode connected with a 50 $\\Omega $ cable to an amplifier followed by a 5 GS/s sampling oscilloscope. The charge carriers in the sensor were produced by picosecond lasers with light of wavelengths of 675 and 1060 nm. The transfer function is determined from the 1060 nm data with the pad diode biased at 1000 V. It is shown that the simulated sensor response convoluted with this transfer function provides an excellent description of the measured transients for the laser light of both wavelengths, at voltages 50 V above the depletion voltage of about 90 V up to the maximum applied voltage of 1000 V. The method has been developed for the precise measurement of the dependence of the drift velocity of electrons an...

  13. MD studies of electron transfer at ambient and elevated pressures

    Science.gov (United States)

    Giles, Alex; Spooner, Jacob; Weinberg, Noham

    2013-06-01

    The effect of pressure on the rate constants of outer-sphere electron transfer reactions has often been described using the Marcus-Hush theory. This theory agrees well with experiment when internal reorganization of the ionic system is negligible, however it does not offer a recipe for calculation of the effects that result from significant solute restructuring. We have recently developed a molecular dynamics technique that accurately describes structural dependence of molecular volumes in non-polar and weakly polar systems. We are now extending this approach to the case of highly polar ionic systems where both solvent and solute restructuring components are important. For this purpose we construct pressure-dependent two-dimensional surfaces for electron transfer reactions in coordinate system composed of interionic distance and Marcus-type solvent polarization coordinate, and use these surfaces to describe pressure effects on reaction kinetics. R.A. Marcus. J. Chem. Phys. 24, 966 (1956); 24, 979 (1956); 26, 867 (1957). Discuss. Faraday Soc. 29, 21 (1960). Faraday Discuss. Chem. Soc. 74, 7 (1982); N.S. Hush. Trans. Faraday Soc. 57, 557 (1961).

  14. Promoting direct interspecies electron transfer with activated carbon

    DEFF Research Database (Denmark)

    Liu, Fanghua; Rotaru, Amelia-Elena; Shrestha, Pravin M.

    2012-01-01

    Granular activated carbon (GAC) is added to methanogenic digesters to enhance conversion of wastes to methane, but the mechanism(s) for GAC’s stimulatory effect are poorly understood. GAC has high electrical conductivity and thus it was hypothesized that one mechanism for GAC stimulation of metha......Granular activated carbon (GAC) is added to methanogenic digesters to enhance conversion of wastes to methane, but the mechanism(s) for GAC’s stimulatory effect are poorly understood. GAC has high electrical conductivity and thus it was hypothesized that one mechanism for GAC stimulation...... of methanogenesis might be to facilitate direct interspecies electron transfer (DIET) between bacteria and methanogens. Metabolism was substantially accelerated when GAC was added to co-cultures of Geobacter metallireducens and Geobacter sulfurreducens grown under conditions previously shown to require DIET. Cells...... were attached to GAC, but did not aggregate as they do when making biological electrical connections between cells. Studies with a series of gene deletion mutants eliminated the possibility that GAC promoted electron exchange via interspecies hydrogen or formate transfer and demonstrated that DIET...

  15. Vibrational dynamics in photoinduced electron transfer. Progress report, December 1, 1992--November 30, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Spears, K.G.

    1993-09-08

    Objective is to perform a new type of measurement for optically excited electron transfer processes that can provide unique experimental insight into the molecular mechanism of electron transfer. Measurements of optically excited electron transfer are done with picosecond infrared (IR) absorption spectroscopy to monitor the vibrational motions of the molecules immediately after electron transfer. Theory and experiment suggest that molecular vibrations and distortions are important controlling elements for electron transfer, and direct information has yet to be obtained on these elements of electron transfer mechanisms. The second period of funding has been dedicated to finishing technique development and performing studies of electron transfer in ion pair systems to identify if vibrational dependent electron transfer rates are present in this system. We have succeeded in measuring, for the first time, electron transfer rates as a function of vibrational state in an ion pair complex in solution. In a different area of electron transfer research we have proposed a new mechanism of solvent gated electron transfer.

  16. Destabilization of fast particle stabilized sawteeth in ASDEX Upgrade with electron cyclotron current drive

    DEFF Research Database (Denmark)

    Igochine, V.; Chapman, I.T.; Bobkov, V.

    2011-01-01

    It is often observed that large sawteeth trigger the neoclassical tearing mode well below the usual threshold for this instability. At the same time, fast particles in the plasma core stabilize sawteeth and provide these large crashes. The paper presents results of first experiments in ASDEX...... Upgrade for destabilization of fast particle stabilized sawteeth with electron cyclotron current drive (ECCD). It is shown that moderate ECCD from a single gyrotron is able to destabilize the fast particle stabilized sawteeth. A reduction in sawtooth period by about 40% was achieved in first experiments...

  17. Linear energy relationships in ground state proton transfer and excited state proton-coupled electron transfer.

    Science.gov (United States)

    Gamiz-Hernandez, Ana P; Magomedov, Artiom; Hummer, Gerhard; Kaila, Ville R I

    2015-02-12

    Proton-coupled electron transfer (PCET) processes are elementary chemical reactions involved in a broad range of radical and redox reactions. Elucidating fundamental PCET reaction mechanisms are thus of central importance for chemical and biochemical research. Here we use quantum chemical density functional theory (DFT), time-dependent density functional theory (TDDFT), and the algebraic diagrammatic-construction through second-order (ADC(2)) to study the mechanism, thermodynamic driving force effects, and reaction barriers of both ground state proton transfer (pT) and photoinduced proton-coupled electron transfer (PCET) between nitrosylated phenyl-phenol compounds and hydrogen-bonded t-butylamine as an external base. We show that the obtained reaction barriers for the ground state pT reactions depend linearly on the thermodynamic driving force, with a Brønsted slope of 1 or 0. Photoexcitation leads to a PCET reaction, for which we find that the excited state reaction barrier depends on the thermodynamic driving force with a Brønsted slope of 1/2. To support the mechanistic picture arising from the static potential energy surfaces, we perform additional molecular dynamics simulations on the excited state energy surface, in which we observe a spontaneous PCET between the donor and the acceptor groups. Our findings suggest that a Brønsted analysis may distinguish the ground state pT and excited state PCET processes.

  18. Helium Leak Detection of Vessels in Fuel Transfer Cell (FTC) of Prototype Fast Breeder Reactor (PFBR)

    Science.gov (United States)

    Dutta, N. G.

    2012-11-01

    Bharatiya Nabhikiya Vidyut Nigam (BHAVINI) is engaged in construction of 500MW Prototype Fast Breeder Reactor (PFBR) at Kalpak am, Chennai. In this very important and prestigious national programme Special Product Division (SPD) of M/s Kay Bouvet Engg.pvt. ltd. (M/s KBEPL) Satara is contributing in a major way by supplying many important sub-assemblies like- Under Water trolley (UWT), Airlocks (PAL, EAL) Container and Storage Rack (CSR) Vessels in Fuel Transfer Cell (FTC) etc for PFBR. SPD of KBEPL caters to the requirements of Government departments like - Department of Atomic Energy (DAE), BARC, Defense, and Government undertakings like NPCIL, BHAVINI, BHEL etc. and other precision Heavy Engg. Industries. SPD is equipped with large size Horizontal Boring Machines, Vertical Boring Machines, Planno milling, Vertical Turret Lathe (VTL) & Radial drilling Machine, different types of welding machines etc. PFBR is 500 MWE sodium cooled pool type reactor in which energy is produced by fissions of mixed oxides of Uranium and Plutonium pellets by fast neutrons and it also breeds uranium by conversion of thorium, put along with fuel rod in the reactor. In the long run, the breeder reactor produces more fuel then it consumes. India has taken the lead to go ahead with Fast Breeder Reactor Programme to produce electricity primarily because India has large reserve of Thorium. To use Thorium as further fuel in future, thorium has to be converted in Uranium by PFBR Technology.

  19. Preliminary Measurement of the Transfer Matrix of a TESLA-type Cavity at FAST

    Energy Technology Data Exchange (ETDEWEB)

    Halavanau, Aliaksei [NICADD, DeKalb; Eddy, Nathan [Fermilab; Edstrom, Dean [Fermilab; Lunin, Andrei [Fermilab; Piot, Philippe [NICADD, DeKalb; Ruan, Jinhao [Fermilab; Santucci, James [Fermilab; Solyak, Nikolay [Fermilab

    2016-06-01

    Superconducting linacs are capable of producing intense, ultra-stable, high-quality electron beams that have widespread application in Science and Industry. Many current and planned projects employ 1.3-GHz 9-cell superconducting cavities of the TESLA design*. In the present paper we discuss the transverse-focusing properties of such a cavity and non-ideal transverse-map effects introduced by field asymmetries in the vicinity of the input and high-order-mode radiofrequency (RF) couplers**. We especially consider the case of a cavity located downstream of an RF-gun in a setup similar to the photoinjector of the Fermilab Accelerator Science and Technology (FAST) facility. Preliminary experimental measurements of the CC2 cavity transverse matrix were carried out at the FAST facility. The results are discussed and compared with analytical and numerical simulations.

  20. HT-FRTC: a fast radiative transfer code using kernel regression

    Science.gov (United States)

    Thelen, Jean-Claude; Havemann, Stephan; Lewis, Warren

    2016-09-01

    The HT-FRTC is a principal component based fast radiative transfer code that can be used across the electromagnetic spectrum from the microwave through to the ultraviolet to calculate transmittance, radiance and flux spectra. The principal components cover the spectrum at a very high spectral resolution, which allows very fast line-by-line, hyperspectral and broadband simulations for satellite-based, airborne and ground-based sensors. The principal components are derived during a code training phase from line-by-line simulations for a diverse set of atmosphere and surface conditions. The derived principal components are sensor independent, i.e. no extra training is required to include additional sensors. During the training phase we also derive the predictors which are required by the fast radiative transfer code to determine the principal component scores from the monochromatic radiances (or fluxes, transmittances). These predictors are calculated for each training profile at a small number of frequencies, which are selected by a k-means cluster algorithm during the training phase. Until recently the predictors were calculated using a linear regression. However, during a recent rewrite of the code the linear regression was replaced by a Gaussian Process (GP) regression which resulted in a significant increase in accuracy when compared to the linear regression. The HT-FRTC has been trained with a large variety of gases, surface properties and scatterers. Rayleigh scattering as well as scattering by frozen/liquid clouds, hydrometeors and aerosols have all been included. The scattering phase function can be fully accounted for by an integrated line-by-line version of the Edwards-Slingo spherical harmonics radiation code or approximately by a modification to the extinction (Chou scaling).

  1. XCO2 Retrieval Errors from a PCA-based Approach to Fast Radiative Transfer

    Science.gov (United States)

    Somkuti, Peter; Boesch, Hartmut; Natraj, Vijay; Kopparla, Pushkar

    2017-04-01

    Multiple-scattering radiative transfer (RT) calculations are an integral part of forward models used to infer greenhouse gas concentrations in the shortwave-infrared spectral range from satellite missions such as GOSAT or OCO-2. Such calculations are, however, computationally expensive and, combined with the recent growth in data volume, necessitate the use of acceleration methods in order to make retrievals feasible on an operational level. The principle component analysis (PCA)-based approach to fast radiative transfer introduced by Natraj et al. 2005 is a spectral binning method, in which the many line-by-line monochromatic calculations are replaced by a small set of representative ones. From the PCA performed on the optical layer properties for a scene-dependent atmosphere, the results of the representative calculations are mapped onto all spectral points in the given band. Since this RT scheme is an approximation, the computed top-of-atmosphere radiances exhibit errors compared to the "full" line-by-line calculation. These errors ultimately propagate into the final retrieved greenhouse gas concentrations, and their magnitude depends on scene-dependent parameters such as aerosol loadings or viewing geometry. An advantage of this method is the ability to choose the degree of accuracy by increasing or decreasing the number of empirical orthogonal functions used for the reconstruction of the radiances. We have performed a large set of global simulations based on real GOSAT scenes and assess the retrieval errors induced by the fast RT approximation through linear error analysis. We find that across a wide range of geophysical parameters, the errors are for the most part smaller than ± 0.2 ppm and ± 0.06 ppm (out of roughly 400 ppm) for ocean and land scenes respectively. A fast RT scheme that produces low errors is important, since regional biases in XCO2 even in the low sub-ppm range can cause significant changes in carbon fluxes obtained from inversions

  2. ATP-induced electron transfer by redox-selective partner recognition.

    Science.gov (United States)

    Hennig, Sandra E; Goetzl, Sebastian; Jeoung, Jae-Hun; Bommer, Martin; Lendzian, Friedhelm; Hildebrandt, Peter; Dobbek, Holger

    2014-08-11

    Thermodynamically unfavourable electron transfers are enabled by coupling to an energy-supplying reaction. How the energy is transduced from the exergonic to the endergonic process is largely unknown. Here we provide the structural basis for an energy transduction process in the reductive activation of B12-dependent methyltransferases. The transfer of one electron from an activating enzyme to the cobalamin cofactor is energetically uphill and relies on coupling to an ATPase reaction. Our results demonstrate that the key to coupling is, besides the oxidation state-dependent complex formation, the conformational gating of the electron transfer. Complex formation induces a substitution of the ligand at the electron-accepting Co ion. Addition of ATP initiates electron transfer by provoking conformational changes that destabilize the complex. We show how remodelling of the electron-accepting Co(2+) promotes ATP-dependent electron transfer; an efficient strategy not seen in other electron-transferring ATPases.

  3. Mitochondrial nitric oxide production supported by reverse electron transfer.

    Science.gov (United States)

    Bombicino, Silvina S; Iglesias, Darío E; Zaobornyj, Tamara; Boveris, Alberto; Valdez, Laura B

    2016-10-01

    Heart phosphorylating electron transfer particles (ETPH) produced NO at 1.2 ± 0.1 nmol NO. min(-1) mg protein(-1) by the mtNOS catalyzed reaction. These particles showed a NAD(+) reductase activity of 64 ± 3 nmol min(-1) mg protein(-1) sustained by reverse electron transfer (RET) at expenses of ATP and succinate. The same particles, without NADPH and in conditions of RET produced 0.97 ± 0.07 nmol NO. min(-1) mg protein(-1). Rotenone inhibited NO production supported by RET measured in ETPH and in coupled mitochondria, but did not reduce the activity of recombinant nNOS, indicating that the inhibitory effect of rotenone on NO production is due to an electron flow inhibition and not to a direct action on mtNOS structure. NO production sustained by RET corresponds to 20% of the total amount of NO released from heart coupled mitochondria. A mitochondrial fraction enriched in complex I produced 1.7 ± 0.2 nmol NO. min(-1) mg protein(-1) and reacted with anti-75 kDa complex I subunit and anti-nNOS antibodies, suggesting that complex I and mtNOS are located contiguously. These data show that mitochondrial NO production can be supported by RET, and suggest that mtNOS is next to complex I, reaffirming the idea of a functional association between these proteins.

  4. Control of Electron Beam Using Strong Magnetic Field for Efficient Core Heating in Fast Ignition

    CERN Document Server

    Johzaki, T; Sentoku, Y; Sunahara, A; Nagatomo, H; Sakagami, H; Mima, K; Fujioka, S; Shiraga, H

    2014-01-01

    For enhancing the core heating efficiency in electron-driven fast ignition, we proposed the fast electron beam guiding using externally applied longitudinal magnetic fields. Based on the PIC simulations for the FIREX-class experiments, we demonstrated the sufficient beam guiding performance in the collisional dense plasma by kT-class external magnetic fields for the case with moderate mirror ratio (~<10 ). Boring of the mirror field was found through the formation of magnetic pipe structure due to the resistive effects, which indicates a possibility of beam guiding in high mirror field for higher laser intensity and/or longer pulse duration.

  5. Transport of fast electrons in a nanowire array with collisional effects included

    Energy Technology Data Exchange (ETDEWEB)

    Li, Boyuan; Zhang, Zhimeng; Wang, Jian; Zhang, Bo; Zhao, Zongqing; Shan, Lianqiang; Zhou, Weimin; Zhang, Baohan [Science and Technology on Plasma Physics Laboratory, Laser Fusion Research Center, China Academy of Engineering Physics, 621900 Mianyang (China); Cao, Lihua [Center for Applied physics and Technology, HEDPs, Peking University, Beijing 100871 (China); Gu, Yuqiu, E-mail: yqgu@caep.ac.cn [Science and Technology on Plasma Physics Laboratory, Laser Fusion Research Center, China Academy of Engineering Physics, 621900 Mianyang (China); Center for Applied physics and Technology, HEDPs, Peking University, Beijing 100871 (China)

    2015-12-15

    The transport of picosecond laser generated fast electrons in a nanowire array is studied with two-dimensional particle-in-cell simulations. Our simulations show that a fast electron beam is initially guided and collimated by strong magnetic filaments in the array. Subsequently, after the decomposition of the structure of nanowire array due to plasma expansion, the beam is still collimated by the resistive magnetic field. An analytical model is established to give a criterion for long-term beam collimation in a nanowire array; it indicates that the nanowire cell should be wide enough to keep the beam collimated in picosecond scale.

  6. Fast Polarization Switching Demonstration Using Crossed-Planar Undulator in a Seeded Free Electron Laser

    CERN Document Server

    Deng, Haixiao; Feng, Lie; Feng, Chao; Chen, Jianhui; Liu, Bo; Wang, Xingtao; Lan, Taihe; Wang, Guanglei; Zhang, Wenyan; Liu, Xiaoqing; Zhang, Meng; Lin, Guoqiang; Zhang, Miao; Wang, Dong; Zhao, Zhentang

    2013-01-01

    Fast polarization switching of light sources is required over a wide spectral range to investigate the symmetry of matter. In this Letter, we report the first experimental demonstration of the crossed-planar undulator technique at a seeded free-electron laser, which holds great promise for the full control and fast switching of the polarization of short-wavelength radiation. In the experiment, the polarization state of the coherent radiation at the 2nd harmonic of the seed laser is switched successfully. The experiment results confirm the theory, and pave the way for applying the crossed-planar undulator technique for the seeded X-ray free electron lasers.

  7. Effect of laser wavelength and intensity on the divergence of hot electrons in fast ignition

    Science.gov (United States)

    Li, Boyuan; Tian, Chao; Zhang, Zhimeng; Zhang, Feng; Shan, Lianqiang; Zhang, Bo; Zhou, Weimin; Zhang, Baohan; Gu, Yuqiu

    2016-09-01

    Recently, the short wavelength laser is believed to have a promising prospect in fast ignition for reducing the conflict between laser energy requirement and electron stopping range. Here we investigate the influence of laser wavelength and intensity in the angular dispersion of hot electrons. Both our theoretical model and numerical simulations show that the angular dispersion would increase rapidly with the shortening of laser wavelength due to the Weibel instability, while the laser intensity has little effect on it. These results have important implications for fast ignition.

  8. Density matrix treatment of non-adiabatic photoinduced electron transfer at a semiconductor surface.

    Science.gov (United States)

    Micha, David A

    2012-12-14

    Photoinduced electron transfer at a nanostructured surface leads to localized transitions and involves three different types of non-adiabatic couplings: vertical electronic transitions induced by light absorption emission, coupling of electronic states by the momentum of atomic motions, and their coupling due to interactions with electronic density fluctuations and vibrational motions in the substrate. These phenomena are described in a unified way by a reduced density matrix (RDM) satisfying an equation of motion that contains dissipative rates. The RDM treatment is used here to distinguish non-adiabatic phenomena that are localized from those due to interaction with a medium. The fast decay of localized state populations due to electronic density fluctuations in the medium has been treated within the Lindblad formulation of rates. The formulation is developed introducing vibronic states constructed from electron orbitals available from density functional calculations, and from vibrational states describing local atomic displacements. Related ab initio molecular dynamics calculations have provided diabatic momentum couplings between excited electronic states. This has been done in detail for an indirect photoexcitation mechanism of the surface Ag(3)Si(111):H, which leads to long lasting electronic charge separation. The resulting coupled density matrix equations are solved numerically to obtain the population of the final charge-separated state as it changes over time, for several values of the diabatic momentum coupling. New insight and unexpected results are presented here which can be understood in terms of photoinduced non-adiabatic transitions involving many vibronic states. It is found that the population of long lasting charge separation states is larger for smaller momentum coupling, and that their population grows faster for smaller coupling.

  9. Challenges of Remote Sensing and Spatial Information Education and Technology Transfer in a Fast Developing Industry

    Science.gov (United States)

    Tsai, F.; Chen, L.-C.

    2014-04-01

    During the past decade, Taiwan has experienced an unusual and fast growing in the industry of mapping, remote sensing, spatial information and related markets. A successful space program and dozens of advanced airborne and ground-based remote sensing instruments as well as mobile mapping systems have been implemented and put into operation to support the vast demands of geospatial data acquisition. Moreover, in addition to the government agencies and research institutes, there are also tens of companies in the private sector providing geo-spatial data and services. However, the fast developing industry is also posing a great challenge to the education sector in Taiwan, especially the higher education for geo-spatial information. Facing this fast developing industry, the demands of skilled professionals and new technologies in order to address diversified needs are indubitably high. Consequently, while delighting in the expanding and prospering benefitted from the fast growing industry, how to fulfill these demands has become a challenge for the remote sensing and spatial information disciplines in the higher education institutes in Taiwan. This paper provides a brief insight into the status of the remote sensing and spatial information industry in Taiwan as well as the challenges of the education and technology transfer to support the increasing demands and to ensure the continuous development of the industry. In addition to the report of the current status of the remote sensing and spatial information related courses and programs in the colleges and universities, current and potential threatening issues and possible resolutions are also discussed in different points of view.

  10. Fabrication and single-electron-transfer operation of a triple-dot single-electron transistor

    Energy Technology Data Exchange (ETDEWEB)

    Jo, Mingyu, E-mail: mingyujo@eis.hokudai.ac.jp; Uchida, Takafumi; Tsurumaki-Fukuchi, Atsushi; Arita, Masashi; Takahashi, Yasuo [Graduate School of Information Science and Technology, Hokkaido University, Sapporo 060-0814 (Japan); Fujiwara, Akira; Nishiguchi, Katsuhiko [NTT Basic Research Laboratories, NTT Corporation, 3-1 Morinosato Wakamiya, Atsugi 243-0198 (Japan); Ono, Yukinori [Graduate School of Science and Engineering, University of Toyama, 3190 Gofuku, Toyama 930-8555 (Japan); Inokawa, Hiroshi [Research Institute of Electronics, Shizuoka University, 3-5-1, Johoku, Hamamatsu 432-8011 (Japan)

    2015-12-07

    A triple-dot single-electron transistor was fabricated on silicon-on-insulator wafer using pattern-dependent oxidation. A specially designed one-dimensional silicon wire having small constrictions at both ends was converted to a triple-dot single-electron transistor by means of pattern-dependent oxidation. The fabrication of the center dot involved quantum size effects and stress-induced band gap reduction, whereas that of the two side dots involved thickness modulation because of the complex edge structure of two-dimensional silicon. Single-electron turnstile operation was confirmed at 8 K when a 100-mV, 1-MHz square wave was applied. Monte Carlo simulations indicated that such a device with inhomogeneous tunnel and gate capacitances can exhibit single-electron transfer.

  11. Photoinduced Bimolecular Electron Transfer from Cyano Anions in Ionic Liquids.

    Science.gov (United States)

    Wu, Boning; Liang, Min; Maroncelli, Mark; Castner, Edward W

    2015-11-19

    Ionic liquids with electron-donating anions are used to investigate rates and mechanisms of photoinduced bimolecular electron transfer to the photoexcited acceptor 9,10-dicyanoanthracene (9,10-DCNA). The set of five cyano anion ILs studied comprises the 1-ethyl-3-methylimidazolium cation paired with each of these five anions: selenocyanate, thiocyanate, dicyanamide, tricyanomethanide, and tetracyanoborate. Measurements with these anions dilute in acetonitrile and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide show that the selenocyanate and tricyanomethanide anions are strong quenchers of the 9,10-DCNA fluorescence, thiocyanate is a moderately strong quencher, dicyanamide is a weak quencher, and no quenching is observed for tetracyanoborate. Quenching rates are obtained from both time-resolved fluorescence transients and time-integrated spectra. Application of a Smoluchowski diffusion-and-reaction model showed that the complex kinetics observed can be fit using only two adjustable parameters, D and V0, where D is the relative diffusion coefficient between donor and acceptor and V0 is the value of the electronic coupling at donor-acceptor contact.

  12. Intramolecular electron transfer in Pseudomonas aeruginosa cd(1) nitrite reductase

    DEFF Research Database (Denmark)

    Farver, Ole; Brunori, Maurizio; Cutruzzolà, Francesca

    2009-01-01

    nitrite reductase has been determined in both fully oxidized and reduced states. Intramolecular electron transfer (ET), between c and d(1) hemes is an essential step in the catalytic cycle. In earlier studies of the Pseudomonas stutzeri enzyme, we observed that a marked negative cooperativity......The cd(1) nitrite reductases, which catalyze the reduction of nitrite to nitric oxide, are homodimers of 60 kDa subunits, each containing one heme-c and one heme-d(1). Heme-c is the electron entry site, whereas heme-d(1) constitutes the catalytic center. The 3D structure of Pseudomonas aeruginosa......-controlled bimolecular process, followed by unimolecular electron equilibration between the c and d(1) hemes (k(ET) = 4.3 s(-1) and K = 1.4 at 298 K, pH 7.0). In the case of the mutant, the latter ET rate was faster by almost one order of magnitude. Moreover, the internal ET rate dropped (by approximately 30-fold...

  13. Mechanically Controlled Electron Transfer in a Single-Polypeptide Transistor

    Science.gov (United States)

    Sheu, Sheh-Yi; Yang, Dah-Yen

    2017-01-01

    Proteins are of interest in nano-bio electronic devices due to their versatile structures, exquisite functionality and specificity. However, quantum transport measurements produce conflicting results due to technical limitations whereby it is difficult to precisely determine molecular orientation, the nature of the moieties, the presence of the surroundings and the temperature; in such circumstances a better understanding of the protein electron transfer (ET) pathway and the mechanism remains a considerable challenge. Here, we report an approach to mechanically drive polypeptide flip-flop motion to achieve a logic gate with ON and OFF states during protein ET. We have calculated the transmission spectra of the peptide-based molecular junctions and observed the hallmarks of electrical current and conductance. The results indicate that peptide ET follows an NC asymmetric process and depends on the amino acid chirality and α-helical handedness. Electron transmission decreases as the number of water molecules increases, and the ET efficiency and its pathway depend on the type of water-bridged H-bonds. Our results provide a rational mechanism for peptide ET and new perspectives on polypeptides as potential candidates in logic nano devices.

  14. Carboxylate shifts steer interquinone electron transfer in photosynthesis.

    Science.gov (United States)

    Chernev, Petko; Zaharieva, Ivelina; Dau, Holger; Haumann, Michael

    2011-02-18

    Understanding the mechanisms of electron transfer (ET) in photosynthetic reaction centers (RCs) may inspire novel catalysts for sunlight-driven fuel production. The electron exit pathway of type II RCs comprises two quinone molecules working in series and in between a non-heme iron atom with a carboxyl ligand (bicarbonate in photosystem II (PSII), glutamate in bacterial RCs). For decades, the functional role of the iron has remained enigmatic. We tracked the iron site using microsecond-resolution x-ray absorption spectroscopy after laser-flash excitation of PSII. After formation of the reduced primary quinone, Q(A)(-), the x-ray spectral changes revealed a transition (t½ ≈ 150 μs) from a bidentate to a monodentate coordination of the bicarbonate at the Fe(II) (carboxylate shift), which reverted concomitantly with the slower ET to the secondary quinone Q(B). A redox change of the iron during the ET was excluded. Density-functional theory calculations corroborated the carboxylate shift both in PSII and bacterial RCs and disclosed underlying changes in electronic configuration. We propose that the iron-carboxyl complex facilitates the first interquinone ET by optimizing charge distribution and hydrogen bonding within the Q(A)FeQ(B) triad for high yield Q(B) reduction. Formation of a specific priming intermediate by nuclear rearrangements, setting the stage for subsequent ET, may be a common motif in reactions of biological redox cofactors.

  15. Photo-induced electron transfer in the strong coupling regime: Waveguide-plasmon polaritons

    CERN Document Server

    Zeng, Peng; Chakraborty, Debadi; Smith, Trevor A; Roberts, Ann; Sader, John E; Davis, Timothy J; Gomez, Daniel E

    2015-01-01

    Reversible exchange of photons between a material and an optical cavity can lead to the formation of hybrid light--matter states where material properties such as the work function\\cite{Hutchison_AM2013a}, chemical reactivity\\cite{Hutchison_ACIE2012a}, ultra--fast energy relaxation \\cite{Salomon_ACIE2009a,Gomez_TJOPCB2012a} and electrical conductivity\\cite{Orgiu_NM2015a} of matter differ significantly to those of the same material in the absence of strong interactions with the electromagnetic fields. Here we show that strong light--matter coupling between confined photons on a semiconductor waveguide and localised plasmon resonances on metal nanowires modifies the efficiency of the photo--induced charge--transfer rate of plasmonic derived (hot) electrons into accepting states in the semiconductor material. Ultra--fast spectroscopy measurements reveal a strong correlation between the amplitude of the transient signals, attributed to electrons residing in the semiconductor, and the hybridization of waveguide an...

  16. Study of fast electrons from hard-X radiation; Etude des electrons rapides a partir du rayonnement X-dur

    Energy Technology Data Exchange (ETDEWEB)

    Arslanbekov, R.

    1995-12-19

    The goal of this thesis is the study of fast electron dynamics by means of the hard X-ray diagnosis installed in TORE SUPRA and numerical simulations. Fast electrons are generated in the plasma in the presence of the injected lower hybrid (LH) waves. Two aspects are studied in detail: the lower hybrid wave propagation and absorption in a periodically perturbed media and 2-D Fokker-Planck modelling of the fast electron dynamics in the presence of the LH power. Ripple effects on lower hybrid wave propagation and absorption are investigated using the ray tracing technique. A cylindrical equilibrium is first studied and a strong modification of the ray dynamics is predicted. Calculations are carried out in a real toroidal geometry corresponding to TORE SUPRA. It is shown that the lack of toroidal axisymmetry of the magnetic field may result in a modification of the ray evolution even if the global ray evolution is governed by the larger poloidal inhomogeneity. Simulation of LH experiments are performed for TORE SUPRA tokamak which has a large magnetic ripple (7% at the plasma edge). By considering ripple perturbation in LH current drive simulations, a better agreement is found with experimental results, in particular with the hard-X spectra and the current density profiles. In the second part of the thesis, a 2-D modeling of the fast electron dynamics in the velocity phase space is considered, based on the 2-D relativistic electron Fokker-Planck equation. Electron distribution functions obtained are used to calculate non-thermal Bremsstrahlung emission for different TORE SUPRA shots in a wide range of experimental conditions. (J.S.). 168 refs., 93 figs., 1 tab., 3 appendix.

  17. Exogenous electron shuttle-mediated extracellular electron transfer of Shewanella putrefaciens 200: electrochemical parameters and thermodynamics.

    Science.gov (United States)

    Wu, Yundang; Liu, Tongxu; Li, Xiaomin; Li, Fangbai

    2014-08-19

    Despite the importance of exogenous electron shuttles (ESs) in extracellular electron transfer (EET), a lack of understanding of the key properties of ESs is a concern given their different influences on EET processes. Here, the ES-mediated EET capacity of Shewanella putrefaciens 200 (SP200) was evaluated by examining the electricity generated in a microbial fuel cell. The results indicated that all the ESs substantially accelerated the current generation compared to only SP200. The current and polarization parameters were linearly correlated with both the standard redox potential (E(ES)(0)) and the electron accepting capacity (EAC) of the ESs. A thermodynamic analysis of the electron transfer from the electron donor to the electrode suggested that the EET from c-type cytochromes (c-Cyts) to ESs is a crucial step causing the differences in EET capacities among various ESs. Based on the derived equations, both E(ES)(0) and EAC can quantitatively determine potential losses (ΔE) that reflect the potential loss of the ES-mediated EET. In situ spectral kinetic analysis of ES reduction by c-Cyts in a living SP200 suspension was first investigated with the E(ES), E(c-Cyt), and ΔE values being calculated. This study can provide a comprehensive understanding of the role of ESs in EET.

  18. Studies on photooxidation (VIII)——Electron transfer photooxygenation mechanism of acenaphthenone as electron donor

    Institute of Scientific and Technical Information of China (English)

    吴树屏; 刘继峰; 江致勤

    1996-01-01

    The photooxidation and its electron transfer (ET) mechanism of acenaphthenone (ANO) sensitized by 9,10-dicyanoanthracence (DCA) are investigated. It has been found that the reaction with a stepwise manner led to the formation of 1,8- (3’-hydroxy)-β-naphthalene lactone and 1,8-naphthalenedicarboxylic anhydride. By cyclic voltammetry, fluorescence quenching, exciplex emission, co-sensitbation of biphenyl/DCA as well as CIDNP studies, it is verified that ANO can behave as an electron donor to undergo ET reaction with singlet DCA which is a thermodynamically-favored process.

  19. Electronic shift register memory based on molecular electron-transfer reactions

    Science.gov (United States)

    Hopfield, J. J.; Onuchic, Jose Nelson; Beratan, David N.

    1989-01-01

    The design of a shift register memory at the molecular level is described in detail. The memory elements are based on a chain of electron-transfer molecules incorporated on a very large scale integrated (VLSI) substrate, and the information is shifted by photoinduced electron-transfer reactions. The design requirements for such a system are discussed, and several realistic strategies for synthesizing these systems are presented. The immediate advantage of such a hybrid molecular/VLSI device would arise from the possible information storage density. The prospect of considerable savings of energy per bit processed also exists. This molecular shift register memory element design solves the conceptual problems associated with integrating molecular size components with larger (micron) size features on a chip.

  20. Fast electronic relaxation in metal nanoclusters via excitation of coherent shape deformations: Circumventing a bottleneck

    CERN Document Server

    Kresin, V V; Kresin, Vitaly V.; Ovchinnikov, Yu. N.

    2006-01-01

    Electron-phonon relaxation in size-quantized systems may become inhibited when the spacing of discrete electron energy levels exceeds the magnitude of the phonon frequency. We show, however, that nanoclusters can support a fast nonradiative relaxation channel which derives from their distinctive ability to undergo Jahn-Teller shape deformations. Such a deformation represents a collective and coherent vibrational excitation and enables electronic transitions to occur without a multiphonon bottleneck. We analyze this mechanism for a metal cluster within the analytical framework of a three-dimensional potential well undergoing a spheroidal distortion. An expression for the time evolution of the distortion parameter is derived, the electronic level crossing condition formulated, and the probability of electronic transition at a level crossing is evaluated. An application to electron-hole recombination in a closed-shell aluminum cluster with 40 electrons shows that the short (~250 fs) excitation lifetime observed ...

  1. Electrochemical Electron Transfer and Proton-Coupled Electron Transfer: Effects of Double Layer and Ionic Environment on Solvent Reorganization Energies

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Soumya; Soudackov, Alexander; Hammes-Schiffer, Sharon

    2016-06-14

    Electron transfer and proton coupled electron transfer (PCET) reactions at electrochemical interfaces play an essential role in a broad range of energy conversion processes. The reorganization energy, which is a measure of the free energy change associated with solute and solvent rearrangements, is a key quantity for calculating rate constants for these reactions. We present a computational method for including the effects of the double layer and ionic environment of the diffuse layer in calculations of electrochemical solvent reorganization energies. This approach incorporates an accurate electronic charge distribution of the solute within a molecular-shaped cavity in conjunction with a dielectric continuum treatment of the solvent, ions, and electrode using the integral equations formalism polarizable continuum model. The molecule-solvent boundary is treated explicitly, but the effects of the electrode-double layer and double layer-diffuse layer boundaries, as well as the effects of the ionic strength of the solvent, are included through an external Green’s function. The calculated total reorganization energies agree well with experimentally measured values for a series of electrochemical systems, and the effects of including both the double layer and ionic environment are found to be very small. This general approach was also extended to electrochemical PCET and produced total reorganization energies in close agreement with experimental values for two experimentally studied PCET systems. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  2. Transfer of optical orbital angular momentum to a bound electron

    Science.gov (United States)

    Schmiegelow, Christian T.; Schulz, Jonas; Kaufmann, Henning; Ruster, Thomas; Poschinger, Ulrich G.; Schmidt-Kaler, Ferdinand

    2016-10-01

    Photons can carry angular momentum, not only due to their spin, but also due to their spatial structure. This extra twist has been used, for example, to drive circular motion of microscopic particles in optical tweezers as well as to create vortices in quantum gases. Here we excite an atomic transition with a vortex laser beam and demonstrate the transfer of optical orbital angular momentum to the valence electron of a single trapped ion. We observe strongly modified selection rules showing that an atom can absorb two quanta of angular momentum from a single photon: one from the spin and another from the spatial structure of the beam. Furthermore, we show that parasitic ac-Stark shifts from off-resonant transitions are suppressed in the dark centre of vortex beams. These results show how light's spatial structure can determine the characteristics of light-matter interaction and pave the way for its application and observation in other systems.

  3. Electron Transfer Reactions: Generalized Spin-Boson Approach

    CERN Document Server

    Merkli, Marco

    2012-01-01

    We introduce a mathematically rigorous analysis of a generalized spin-boson system for the treatment of a donor-acceptor (reactant-product) quantum system coupled to a thermal quantum noise. The donor/acceptor probability dynamics describes transport reactions in chemical processes in presence of a noisy environment -- such as the electron transfer in a photosynthetic reaction center. Besides being rigorous, our analysis has the advantages over previous ones that (1) we include a general, non energy-conserving system-environment interaction, and that (2) we allow for the donor or acceptor to consist of multiple energy levels lying closely together. We establish explicit expressions for the rates and the efficiency (final donor-acceptor population difference) of the reaction. In particular, we show that the rate increases for a multi-level acceptor, but the efficiency does not.

  4. On the Hopping Efficiency of Nanoparticles in the Electron Transfer across Self‐Assembled Monolayers

    DEFF Research Database (Denmark)

    Liu, Feng; Khan, Kamran; Liang, Jing‐Hong

    2013-01-01

    Redox reactions of solvated molecular species at gold‐electrode surfaces modified by electrochemically inactive self‐assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au–alkanedithiol–NP–molecule hy......Redox reactions of solvated molecular species at gold‐electrode surfaces modified by electrochemically inactive self‐assembled molecular monolayers (SAMs) are found to be activated by introducing Au nanoparticles (NPs) covalently bound to the SAM to form a reactive Au......–alkanedithiol–NP–molecule hybrid entity. The NP appears to relay long‐range electron transfer (ET) so that the rate of the redox reaction may be as efficient as directly on a bare Au electrode, even though the ET distance is increased by several nanometers. In this study, we have employed a fast redox reaction of surface...

  5. Thermalisation and hard X-ray bremsstrahlung efficiency of self-interacting solar flare fast electrons

    CERN Document Server

    Galloway, R K; MacKinnon, A L; Brown, J C

    2010-01-01

    Most theoretical descriptions of the production of solar flare bremsstrahlung radiation assume the collision of dilute accelerated particles with a cold, dense target plasma, neglecting interactions of the fast particles with each other. This is inadequate for situations where collisions with this background plasma are not completely dominant, as may be the case in, for example, low-density coronal sources. We aim to formulate a model of a self-interacting, entirely fast electron population in the absence of a dense background plasma, to investigate its implications for observed bremsstrahlung spectra and the flare energy budget. We derive approximate expressions for the time-dependent distribution function of the fast electrons using a Fokker-Planck approach. We use these expressions to generate synthetic bremsstrahlung X-ray spectra as would be seen from a corresponding coronal source. We find that our model qualitatively reproduces the observed behaviour of some flares. As the flare progresses, the model's...

  6. Redox induced electron transfer in doublet azo-anion diradical rhenium(II) complexes. Characterization of complete electron transfer series.

    Science.gov (United States)

    Paul, Nandadulal; Samanta, Subhas; Goswami, Sreebrata

    2010-03-15

    Reactions of dirhenium decacarbonyl with the two azoaromatic ligands, L(a) = (2-phenylazo)pyridine and L(b) = (4-chloro-2-phenylazo)pyridine (general abbreviation of the ligands is L) afford paramagnetic rhenium(II) complexes, [Re(II)(L(*-))(2)(CO)(2)] (1) (S = 1/2 ground state) with two one-electron reduced azo-anion radical ligands in an octahedral geometrical arrangement. At room temperature (300 K) the complexes 1a-b, showed magnetic moments (mu(eff)) close to 1.94 mu(B), which is suggestive of the existence of strong antiferromagnetic interactions in the complexes. The results of magnetic measurements on one of the complexes, 1b, in the temperature range 2-300 K are reported. The above complexes showed two cathodic and two anodic responses in cyclic voltammetry where one-electron oxidation leads to an unusual redox event involving simultaneous reduction of the rhenium(II) and oxidation of the second ligand via intramolecular electron transfer. The oxidized complexes 1a(+) and 1b(+) are air stable and were isolated as crystalline solids as their tri-iodide (I(3)(-)) salts. The structures of the two representative complexes, 1b and [1b]I(3), as determined by X-ray crystallography, are compared. The anionic complexes, [1](-) and [1](2-) were characterized in solution by their spectral properties.

  7. FAST

    DEFF Research Database (Denmark)

    Zuidmeer-Jongejan, Laurian; Fernandez-Rivas, Montserrat; Poulsen, Lars K.

    2012-01-01

    ABSTRACT: The FAST project (Food Allergy Specific Immunotherapy) aims at the development of safe and effective treatment of food allergies, targeting prevalent, persistent and severe allergy to fish and peach. Classical allergen-specific immunotherapy (SIT), using subcutaneous injections with aqu......ABSTRACT: The FAST project (Food Allergy Specific Immunotherapy) aims at the development of safe and effective treatment of food allergies, targeting prevalent, persistent and severe allergy to fish and peach. Classical allergen-specific immunotherapy (SIT), using subcutaneous injections...... with aqueous food extracts may be effective but has proven to be accompanied by too many anaphylactic side-effects. FAST aims to develop a safe alternative by replacing food extracts with hypoallergenic recombinant major allergens as the active ingredients of SIT. Both severe fish and peach allergy are caused...... in depth serological and cellular immune analyses will be performed, allowing identification of novel biomarkers for monitoring treatment efficacy. FAST aims at improving the quality of life of food allergic patients by providing a safe and effective treatment that will significantly lower their threshold...

  8. Three dimensional filamentary structures of a relativistic electron beam in Fast Ignition plasmas

    CERN Document Server

    Karmakar, Anupam; Pukhov, Alexander

    2008-01-01

    The filamentary structures and associated electromagnetic fields of a relativistic electron beam have been studied by three dimensional particle-in-cell (PIC) simulations in the context of Fast Ignition fusion. The simulations explicitly include collisions in return plasma current and distinctly examine the effects of beam temperature and collisions on the growth of filamentary structures generated.

  9. Generation of fast electrons by breaking of a laser-induced plasma wave

    NARCIS (Netherlands)

    Trines, Rmgm; Goloviznin, V. V.; Kamp, L. P. J.; Schep, T. J.

    2001-01-01

    A one-dimensional model for fast electron generation by an intense, nonevolving laser pulse propagating through an underdense plasma has been developed. Plasma wave breaking is considered to be the dominant mechanism behind this process, and wave breaking both in front of and behind the laser pulse

  10. ELECTRON TRANSFER COLLISION OF NEON IONS WITH Ne IN A RF ION TRAP

    Institute of Scientific and Technical Information of China (English)

    满宝元; 王象泰; 等

    1995-01-01

    The pulsed electron beam rf ion stroage system is used to study neon ions electron transfer,The rate coefficients for electron transfer of the neon ions with the neon gas are measured.the results are better than those in other ion storage system.

  11. Machine Learning for Silver Nanoparticle Electron Transfer Property Prediction.

    Science.gov (United States)

    Sun, Baichuan; Fernandez, Michael; Barnard, Amanda S

    2017-09-22

    Nanoparticles exhibit diverse structural and morphological features that are often inter-connected, making the correlation of structure/property relationships challenging. In this study a multi-structure/single-property relationship of silver nanoparticles is developed for the energy of Fermi level, which can be tuned to improve the transfer of electrons in a variety of applications. By combining different machine learning analytical algorithms, including k-mean, logistic regression and random forest with electronic structure simulations, we find that the degree of twinning (characterised by the fraction of hexagonal closed packed atoms) and the population of {111} facet (characterized by a surface coordination number of 9) are strongly correlated to the Fermi energy of silver nanoparticles. A concise 3 layer artificial neural network together with principal component analysis is built to predict this property, with reduced geometrical, structural and topological features, making the method ideal for efficient and accurate high-throughput screening of large-scale virtual nanoparticles libraries, and the creation of single-structure/single-property, multi-structure/single-property and single-structure/multi-property relationships in the near future.

  12. Enhanced electron transfer dissociation through fixed charge derivatization of cysteines.

    Science.gov (United States)

    Vasicek, Lisa; Brodbelt, Jennifer S

    2009-10-01

    Electron transfer dissociation (ETD) has proven to be a promising new ion activation method for proteomics applications due to its ability to generate c- and z-type fragment ions in comparison to the y- and b-type ions produced upon the more conventional collisional activation of peptides. However, low precursor charge states hinder the success of electron-based activation methods due to competition from nondissociative charge reduction and incomplete sequence coverage. In the present report, the reduction and alkylation of disulfide bonds prior to ETD analysis is evaluated by comparison of three derivatization reagents: iodoacetamide (IAM), N,N-dimethyl-2-chloro-ethylamine (DML), and (3-acrylamidopropyl)-trimethyl ammonium chloride (APTA). While both the DML and APTA modifications lead to an increase in the charge states of peptides, the APTA-peptides provided the most significant improvement in percent fragmentation and sequence coverage for all peptides upon ETD, including formation of diagnostic ions that allow characterization of both the C- and N-termini. In addition, the formation of product ions in multiple charge states upon ETD is minimized for the APTA-modified peptides.

  13. A Fast, Accurate and Robust Algorithm For Transferring Radiation in Three-Dimensional Space

    CERN Document Server

    Cen, R

    2002-01-01

    We have developed an algorithm for transferring radiation in three-dimensional space. The algorithm computes radiation source and sink terms using the Fast Fourier Transform (FFT) method, based on a formulation in which the integral of any quantity (such as emissivity or opacity) over any volume may be written in the classic convolution form. The algorithm is fast with the computational time scaling as N (log N)^2, where N is the number of grid points of a simulation box, independent of the number of radiation sources. Furthermore, in this formulation one can naturally account for both local radiation sources and diffuse background as well as any extra external sources, all in a completely self-consistent fashion. Finally, the algorithm is completely stable and robust. While the algorithm is generally applicable, we test it on a set of problems that encompass a wide range of situations in cosmological applications, demonstrating that the algorithm is accurate. These tests show that the algorithm produces resu...

  14. Dry-cured ham tissue characterization by fast field cycling NMR relaxometry and quantitative magnetization transfer.

    Science.gov (United States)

    Bajd, Franci; Gradišek, Anton; Apih, Tomaž; Serša, Igor

    2016-05-31

    Fast field cycling (FFC) and quantitative magnetization transfer (qMT) NMR methods are two powerful tools in NMR analysis of biological tissues. The qMT method is well established in biomedical NMR applications, while the FFC method is often used in investigations of molecular dynamics on which longitudinal NMR relaxation times of the investigated material critically depend. Despite their proven analytical potential, these two methods were rarely used in NMR studies of food, especially when combined together. In our study, we demonstrate the feasibility of a combined FFC/qMT-NMR approach for the fast and nondestructive characterization of dry-curing ham tissues differing by protein content. The characterization is based on quantifying the pure quadrupolar peak area (area under the quadrupolar contribution of dispersion curve obtained by FFC-NMR) and the restricted magnetization pool size (obtained by qMT-NMR). Both quantities correlate well with concentration of partially immobilized, nitrogen-containing and proton magnetization exchanging muscle proteins. Therefore, these two quantities could serve as potential markers for dry-curing process monitoring. Copyright © 2016 John Wiley & Sons, Ltd.

  15. A new model for electron flow during anaerobic digestion: direct interspecies electron transfer to Methanosaeta for the reduction of carbon dioxide to methane

    DEFF Research Database (Denmark)

    Rotaru, Amelia-Elena; Shrestha, Pravin M.; Liu, Fanghua

    2013-01-01

    , the most abundant bacteria in the aggregates, highly expressed genes for ethanol metabolism and for extracellular electron transfer via electrically conductive pili, suggesting that Geobacter and Methanosaeta species were exchanging electrons via direct interspecies electron transfer (DIET...

  16. Charge and Energy Dependences of Ionization and Transfer for Helium in Collisions with Fast Charged Projectiles

    Institute of Scientific and Technical Information of China (English)

    FU Hong-Bin; WANG Bao-Hong; DING Bao-Wei; LIU Zhao-Yuan

    2009-01-01

    The classical method within the independent electron model is employed to investigate (i) charge dependences of single and double ionization for helium by various charged ions Aq+ (q = 1 - 8) at impact energies of 0.64 and 1.44 MeV/u, respectively, (ii) energy dependences of transfer ionization for helium by 0.5-3 MeV/u A8,9+ ions impact. The Lenz-Jensen model of the atom is applied instead of the Bohr model of the atom, and the impact-parameter dependences are also introduced into the calculations. Satisfactory agreement is found between theoretical and experimental data.

  17. Intramolecular Electron Transfer in Bis(tetraalkyl Hydrazine) and Bis(hydrazyl) Radical Cations.

    Science.gov (United States)

    Chang, Hao

    A series of multicyclic bis(hydrazine) and bis(diazenium) compounds connected by relatively rigid hydrocarbon frameworks were prepared for the study of intramolecular electron transfer. The thermodynamics of electron removal of these compounds was investigated by cyclic voltammetry. The difference between the first and second oxidation potentials for the 4 sigma-bonded species was found to be larger for the bis(hydrazyl) radical systems than for the bis(hydrazines) by ca. 0.2 V (4.6 kcal/mol). This indicates a greater degree of interaction between the two nitrogen moieties for the hydrazyl systems, which is consistent with a greater degree of electronic coupling (H _{rm AB}) in these systems. The ESR spectra of the 4 sigma -bonded bis(hydrazine) radical cations indicate localized radical cations, which corresponds to slow intramolecular electron transfer on the ESR timescale. Conversely, the ESR spectra of the corresponding bis(hydrazyl) radical cation systems show nitrogen hyperfine splittings of a(4N) of ca. 4.5 G. This indicates that intramolecular electron transfer between the two nitrogen moieties is fast on the ESR timescale; the rate of exchange, k_ {rm ex} was estimated to be well above 1.9 times 10^8 s^{-1}. The contrast in exchange rates is consistent with the large geometry change upon oxidation which is characteristic of hydrazines. The hydrazyls undergo a smaller geometry change upon oxidation, and thus are expected to exhibit smaller inner-sphere reorganization energies. The optical spectra of these radical species was investigated in hopes of observing absorption bands corresponding to intramolecular electron transfer, as predicted by Hush theory. A broad absorption band was observed in the near IR region for the saturated bis(hydrazyl) radical cation system at 1060 nm (9420 cm^{-1} ) in acetonitrile at room temperature, and was accompanied by a narrower band at 1430 nm (6993 cm^ {-1}). The width of this band was estimated to be 545 nm (6496 cm^{-1

  18. An electron/ion spectrometer with the ability of low energy electron measurement for fast ignition experiments

    Energy Technology Data Exchange (ETDEWEB)

    Ozaki, T.; Sakagami, H. [National Institute for Fusion Science, 322-6, Oroshi, Toki, Gifu 509-5292 (Japan); Kojima, S.; Arikawa, Y.; Shiraga, H.; Fujioka, S. [Institute of Laser Engineering, Osaka University, 2-6, Yamada-oka, Suita, Osaka 565-0871 (Japan); Kato, R., E-mail: ozaki@nifs.ac.jp [Institute of Scientific and Industrial Research, Osaka University, 8-1, Mihogaoka, Ibaraki, Osaka 567-0047 (Japan)

    2014-11-15

    An electron energy spectrometer (ESM) is one of the most fundamental diagnostics in the fast ignition experiment. It is necessary to observe the spectra down to a low energy range in order to obtain the accurate deposition efficiency toward the core. Here, we realize the suitable ESM by using a ferrite magnet with a moderate magnetic field of 0.3 T and a rectangular magnetic circuit covered with a steel plate in the inlet side.

  19. Design of an MeV ultra-fast electron diffraction experiment at Tsinghua university

    Institute of Scientific and Technical Information of China (English)

    LI Ren-Kai; TANG Chuan-Xiang; HUANG Wen-Hui; DU Ying-Chao; SHI Jia-Ru; YAN Li-Xin

    2009-01-01

    Time-resolved MeV ultra-fast electron difiraction(UED)is a powerful tool for structure dynamics studies.In this paper.we present a design of a MeV UED facility based on a photocathode RF gun at Tsinghua University.Electron beam qualities are optimized with numerical simulations,indicating that resolutions of 250 fs and 0.01 A.and bunch charge exceeding 105 electrons are expected with technically achievable machine parameters.Status of experiment preparation is also presented.

  20. Modular electron transfer circuits for synthetic biology: Insulation of an engineered biohydrogen pathway

    OpenAIRE

    Agapakis, Christina M; Silver, Pamela A

    2010-01-01

    Electron transfer is central to a wide range of essential metabolic pathways, from photosynthesis to fermentation. The evolutionary diversity and conservation of proteins that transfer electrons makes these pathways a valuable platform for engineered metabolic circuits in synthetic biology. Rational engineering of electron transfer pathways containing hydrogenases has the potential to lead to industrial scale production of hydrogen as an alternative source of clean fuel and experimental assay...

  1. Interfacial Electron Transfer and Transient Photoconductivity Studied with Terahertz Spectroscopy

    Science.gov (United States)

    Milot, Rebecca Lee

    Terahertz spectroscopy is distinguished from other far infrared and millimeter wave spectroscopies by its inherent phase sensitivity and sub-picosecond time resolution making it a versatile technique to study a wide range of physical phenomena. As THz spectroscopy is still a relatively new field, many aspects of THz generation mechanisms have not been fully examined. Using terahertz emission spectroscopy (TES), THz emission from ZnTe(110) was analyzed and found to be limited by two-photon absorption and free-carrier generation at high excitation fluences. Due to concerns about the continued use of fossil fuels, solar energy has been widely investigated as a promising source of renewable energy. Dye-sensitized solar cells (DSSCs) have been developed as a low-cost alternative to conventional photovoltaic solar cells. To solve the issues of the intermittency and inefficient transport associated with solar energy, researchers are attempting to adapt DSSCs for water oxidation and chemical fuel production. Both device designs incorporate sensitizer molecules covalently bound to metal oxide nanoparticles. The sensitizer, which is comprised of a chromophore and anchoring group, absorbs light and transfers an electron from its excited state to the conduction band of the metal oxide, producing an electric current. Using time-resolved THz spectroscopy (TRTS), an optical pump/THz probe technique, the efficiency and dynamics of electron injection from sensitizers to metal oxides was evaluated as a function of the chromophore, its anchoring group, and the metal oxide identity. Experiments for studying fully functioning DSSCs and water oxidation devices are also described. Bio-inspired pentafluorophenyl porphyrin chromophores have been designed and synthesized for use in photoelectrochemical water oxidation cells. Influences on the efficiency and dynamics of electron injection from the chromophores into TiO2 and SnO2 nanoparticles due to changes in both the central substituent to

  2. Syntrophic growth with direct interspecies electron transfer as the primary mechanism for energy exchange

    DEFF Research Database (Denmark)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Aklujkar, Muktak

    2013-01-01

    Direct interspecies electron transfer (DIET) through biological electrical connections is an alternative to interspecies H2 transfer as a mechanism for electron exchange in syntrophic cultures. However, it has not previously been determined whether electrons received via DIET yield energy...... dehydrogenase, the pilus-associated c-type cytochrome OmcS and pili consistent with electron transfer via DIET. These results suggest that electrons transferred via DIET can serve as the sole energy source to support anaerobic respiration....... to support cell growth. In order to investigate this, co-cultures of Geobacter metallireducens, which can transfer electrons to wild-type G. sulfurreducens via DIET, were established with a citrate synthase-deficient G. sulfurreducens strain that can receive electrons for respiration through DIET only...

  3. Control of Electron Transfer from Lead-Salt Nanocrystals to TiO 2

    KAUST Repository

    Hyun, Byung-Ryool

    2011-05-11

    The roles of solvent reorganization energy and electronic coupling strength on the transfer of photoexcited electrons from PbS nanocrystals to TiO 2 nanoparticles are investigated. We find that the electron transfer depends only weakly on the solvent, in contrast to the strong dependence in the nanocrystal-molecule system. This is ascribed to the larger size of the acceptor in this system, and is accounted for by Marcus theory. The electronic coupling of the PbS and TiO 2 is varied by changing the length, aliphatic and aromatic structure, and anchor groups of the linker molecules. Shorter linker molecules consistently lead to faster electron transfer. Surprisingly, linker molecules of the same length but distinct chemical structures yield similar electron transfer rates. In contrast, the electron transfer rate can vary dramatically with different anchor groups. © 2011 American Chemical Society.

  4. Fast radiative transfer parameterisation for assessing the surface solar irradiance: The Heliosat‑4 method

    Directory of Open Access Journals (Sweden)

    Zhipeng Qu

    2017-02-01

    Full Text Available The new Heliosat‑4 method estimates the downwelling shortwave irradiance received at ground level in all sky conditions. It provides the global irradiance and its direct and diffuse components on a horizontal plane and the direct irradiance for a plane normal to sun rays. It is a fully physical model using a fast, but still accurate approximation of radiative transfer modelling and is therefore well suited for geostationary satellite retrievals. It can also be used as a fast radiative transfer model in numerical weather prediction models. It is composed of two models based on abaci, also called look-up tables: the already-published McClear model calculating the irradiance under cloud-free conditions and the new McCloud model calculating the extinction of irradiance due to clouds. Both have been realized by using the libRadtran radiative transfer model. The main inputs to Heliosat‑4 are aerosol properties, total column water vapour and ozone content as provided by the Copernicus Atmosphere Monitoring Service (CAMS every 3 h. Cloud properties are derived from images of the Meteosat Second Generation (MSG satellites in their 15 min temporal resolution using an adapted APOLLO (AVHRR Processing scheme Over cLouds, Land and Ocean scheme. The 15 min means of irradiance estimated by Heliosat‑4 are compared to corresponding measurements made at 13 stations within the Baseline Surface Radiation Network and being located in the field of view of MSG and in various climates. The bias for global irradiance is comprised between 2 and 32 W m−2. The root mean square error (RMSE ranges between 74 and 94 W m−2. Relative RMSE values range between 15 % and 20 % of the mean observed irradiance for stations in desert and Mediterranean climates, and between 26 % and 43 % for rainy climates with mild winters. Correlation coefficients between 0.91 and 0.97 are found. The bias for the direct irradiance at normal incidence is comprised

  5. Neutron, electron and photon transport in ICF tragets in direct and fast ignition

    Directory of Open Access Journals (Sweden)

    A. Parvazian

    2005-12-01

    Full Text Available Fusion energy due to inertial confinement has progressed in the last few decades. In order to increase energy efficiency in this method various designs have been presented. The standard scheme for direct ignition and fast ignition fuel targets are considered. Neutrons, electrons and photons transport in targets containing different combinations of Li and Be are calculated in both direct and fast ignition schemes. To compress spherical multilayer targets having fuel in the central part, they are irradiated by laser or heavy ion beams. Neutrons energy deposition in the target is considered using Monte Carlo method code MCNP. A significant amount of neutrons energy is deposited in the target which resulted in growing fusion reactions rates. It is found that Beryllium compared to Lithium is more important. In an introductory consideration of relativistic electron beam transport into central part of a fast ignition target, we have calculated electron energy deposition in highly dense D-T fuel and Beryllium layer of the target. It has been concluded that a fast ignition scheme is preferred to direct ignition because of the absence of hydrodynamic instability.

  6. Spectrum of fast electrons in a dense gas in the presence of a nonuniform pulsed field

    Science.gov (United States)

    Tkachev, A. N.; Yakovlenko, S. I.

    2007-01-01

    The problems of gas preionization in discharges related to laser physics are considered. The propagation of fast electrons injected from the cathode in the presence of a nonuniform nonstationary field and the motion of multiplying electrons at the edge of the avalanche in the presence of a nonuniform nonstationary field are simulated. The effect of the voltage pulse steepness and the field nonuniformity on the mean propagation velocity of fast electrons and their energy distribution is demonstrated. At certain combinations of the voltage pulse rise time and amplitude and at a certain time interval, the center of gravity of the electron cloud can move in the opposite direction relative to the direction of force acting upon electrons. It is also demonstrated that the number of hard particles (and, hence, the hard component of the x-ray bremsstrahlung) increases with both an increase in the voltage amplitude and a decrease in the pulse rise time. For nonoptimal conditions of the picosecond voltage pulse, an assumption is formulated: an electron beam in gas is formed due to the electrons at the edge of the avalanche rather than the background multiplication wave approaching the anode.

  7. Hydrated Electron Transfer to Nucleobases in Aqueous Solutions Revealed by Ab Initio Molecular Dynamics Simulations.

    Science.gov (United States)

    Zhao, Jing; Wang, Mei; Fu, Aiyun; Yang, Hongfang; Bu, Yuxiang

    2015-08-03

    We present an ab initio molecular dynamics (AIMD) simulation study into the transfer dynamics of an excess electron from its cavity-shaped hydrated electron state to a hydrated nucleobase (NB)-bound state. In contrast to the traditional view that electron localization at NBs (G/A/C/T), which is the first step for electron-induced DNA damage, is related only to dry or prehydrated electrons, and a fully hydrated electron no longer transfers to NBs, our AIMD simulations indicate that a fully hydrated electron can still transfer to NBs. We monitored the transfer dynamics of fully hydrated electrons towards hydrated NBs in aqueous solutions by using AIMD simulations and found that due to solution-structure fluctuation and attraction of NBs, a fully hydrated electron can transfer to a NB gradually over time. Concurrently, the hydrated electron cavity gradually reorganizes, distorts, and even breaks. The transfer could be completed in about 120-200 fs in four aqueous NB solutions, depending on the electron-binding ability of hydrated NBs and the structural fluctuation of the solution. The transferring electron resides in the π*-type lowest unoccupied molecular orbital of the NB, which leads to a hydrated NB anion. Clearly, the observed transfer of hydrated electrons can be attributed to the strong electron-binding ability of hydrated NBs over the hydrated electron cavity, which is the driving force, and the transfer dynamics is structure-fluctuation controlled. This work provides new insights into the evolution dynamics of hydrated electrons and provides some helpful information for understanding the DNA-damage mechanism in solution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Thermodynamic, kinetic and electronic structure aspects of a charge-transfer active bichromophoric organofullerene

    Indian Academy of Sciences (India)

    K Senthil Kumar; Archita Patnaik

    2013-03-01

    Our recent work on charge transfer in the electronically push-pull dimethylaminoazobenzene-fullerene C60 donor-bridge-acceptor dyad through orbital picture revealed charge displacement from the n(N=N) (non-bonding) and (N=N) type orbitals centred on the donor part to the purely fullerene centred LUMOs and (LUMO+n) orbitals, delocalized over the entire molecule. Consequently, this investigation centres around the kinetic and thermodynamic parameters involved in the solvent polarity dependent intramolecular photo-induced electron transfer processes in the dyad, indispensable for artificial photosynthetic systems. A quasi-reversible electron transfer pathway was elucidated with electrode-specific heterogeneous electron transfer rate constants.

  9. Type IV pili of Acidithiobacillus ferrooxidans can transfer electrons from extracellular electron donors.

    Science.gov (United States)

    Li, Yongquan; Li, Hongyu

    2014-03-01

    Studies on Acidithiobacillus ferrooxidans accepting electrons from Fe(II) have previously focused on cytochrome c. However, we have discovered that, besides cytochrome c, type IV pili (Tfp) can transfer electrons. Here, we report conduction by Tfp of A. ferrooxidans analyzed with a conducting-probe atomic force microscope (AFM). The results indicate that the Tfp of A. ferrooxidans are highly conductive. The genome sequence of A. ferrooxidans ATCC 23270 contains two genes, pilV and pilW, which code for pilin domain proteins with the conserved amino acids characteristic of Tfp. Multiple alignment analysis of the PilV and PilW (pilin) proteins indicated that pilV is the adhesin gene while pilW codes for the major protein element of Tfp. The likely function of Tfp is to complete the circuit between the cell surface and Fe(II) oxides. These results indicate that Tfp of A. ferrooxidans might serve as biological nanowires transferring electrons from the surface of Fe(II) oxides to the cell surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Vibrational and Electronic Energy Transfer and Dissociation of Diatomic Molecules by Electron Collisions

    Science.gov (United States)

    Huo, Winifred M.; Langhoff, Stephen R. (Technical Monitor)

    1995-01-01

    At high altitudes and velocities equal to or greater than the geosynchronous return velocity (10 kilometers per second), the shock layer of a hypersonic flight will be in thermochemical nonequilibrium and partially ionized. The amount of ionization is determined by the velocity. For a trans atmospheric flight of 10 kilometers per second and at an altitude of 80 kilometers, a maximum of 1% ionization is expected. At a velocity of 12 - 17 kilometer per second, such as a Mars return mission, up to 30% of the atoms and molecules in the flow field will be ionized. Under those circumstances, electrons play an important role in determining the internal states of atoms and molecules in the flow field and hence the amount of radiative heat load and the distance it takes for the flow field to re-establish equilibrium. Electron collisions provide an effective means of transferring energy even when the electron number density is as low as 1%. Because the mass of an electron is 12,760 times smaller than the reduced mass of N2, its average speed, and hence its average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron-molecule collisions is equal to or larger than that of molecule-molecule collisions, an important consideration in the low density part of the atmosphere. Three electron-molecule collision processes relevant to hypersonic flows will be considered: (1) vibrational excitation/de-excitation of a diatomic molecule by electron impact, (2) electronic excitation/de-excitation, and (3) dissociative recombination in electron-diatomic ion collisions. A review of available data, both theory and experiment, will be given. Particular attention will be paid to tailoring the molecular physics to the condition of hypersonic flows. For example, the high rotational temperatures in a hypersonic flow field means that most experimental data carried out under room temperatures are not applicable. Also

  11. Electron transfer reactions of macrocyclic compounds of cobalt

    Energy Technology Data Exchange (ETDEWEB)

    Heckman, R.A.

    1978-08-01

    The kinetics and mechanisms of reduction of H/sub 2/O/sub 2/, Br/sub 2/, and I/sub 2/ by various macrocyclic tetraaza complexes of cobalt(II), including Vitamin B/sub 12r/, were studied. The synthetic macrocycles studied were all 14-membered rings which varied in the degree of unsaturation,substitution of methyl groups on the periphery of the ring, and substitution within the ring itself. Scavenging experiments demonstrated that the reductions of H/sub 2/O/sub 2/ produce free hydroxyl radicals only in the case of Co((14)ane)/sup 2 +/ but with none of the others. In the latter instances apparently H/sub 2/O/sub 2/ simultaneously oxidizes the metal center and the ligand. The reductions of Br/sub 2/ and I/sub 2/ produce an aquohalocobalt(III) product for all reductants (except B/sub 12r/ + Br/sub 2/, which was complicated by bromination of the corrin ring). The mechanism of halogen reduction was found to involve rate-limiting inner-sphere electron transfer from cobalt to halogen to produce a dihalide anion coordinated to the cobalt center. This intermediate subsequently decomposes in rapid reactions to halocobalt(III) and halogen atom species or reacts with another cobalt(II) center to give two molecules of halocobalt(III). The reductions of halomethylcobaloximes and related compounds and diamminecobaloxime by Cr/sup 2 +/ were also studied. The reaction was found to be biphasic in all cases with the reaction products being halomethane (for the halomethylcobaloximes), Co/sup 2 +/ (in less than 100 percent yield), a Cr(III)-dimethylglyoxime species, a small amount of free dmgH/sub 2/, and a highly-charged species containing both cobalt and chromium. The first-stage reaction occurs with a stoichiometry of 1:1 producing an intermediate with an absorption maximum at 460 nm for all starting reagents. The results were interpreted in terms of inner-sphere coordination of the cobaloxime to the Cr(II) and electron transfer through the oxime N-O bond.

  12. Fast electron generation by Coulomb scattering on spatially correlated ions in a strong laser field

    CERN Document Server

    Bauch, S

    2009-01-01

    Electrons colliding with spatially fixed ions in strong laser fields are investigated by solving the time-dependent Schr\\"odinger equation. Considering first simple one-dimensional model systems, the mechanisms and energy spectra of fast electrons are analyzed, starting from collisions on a single ion. By using these electrons as projectiles for a second and third collision, the maximum possible energy obtained can be significantly increased. We then generalize the analysis to 2D systems where additional angular degrees of freedom lead to a drastic loss of efficiency. This problem can be overcome by introducing external confinements, which allow to focus the electrons and increase the intensity of high-energy electrons.

  13. Thermal transfer structures coupling electronics card(s) to coolant-cooled structure(s)

    Science.gov (United States)

    David, Milnes P; Graybill, David P; Iyengar, Madhusudan K; Kamath, Vinod; Kochuparambil, Bejoy J; Parida, Pritish R; Schmidt, Roger R

    2014-12-16

    Cooling apparatuses and coolant-cooled electronic systems are provided which include thermal transfer structures configured to engage with a spring force one or more electronics cards with docking of the electronics card(s) within a respective socket(s) of the electronic system. A thermal transfer structure of the cooling apparatus includes a thermal spreader having a first thermal conduction surface, and a thermally conductive spring assembly coupled to the conduction surface of the thermal spreader and positioned and configured to reside between and physically couple a first surface of an electronics card to the first surface of the thermal spreader with docking of the electronics card within a socket of the electronic system. The thermal transfer structure is, in one embodiment, metallurgically bonded to a coolant-cooled structure and facilitates transfer of heat from the electronics card to coolant flowing through the coolant-cooled structure.

  14. DETERMINATION OF HETEROGENEOUS ELECTRON TRANSFER RATE CONSTANTS AT MICROFABRICATED IRIDIUM ELECTRODES. (R825511C022)

    Science.gov (United States)

    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  15. [Theory of long-distance electron transfer in nanoscale biological structures].

    Science.gov (United States)

    Krasil'nikov, P M

    2011-01-01

    Macromolecular biological systems accomplishing the directed electron transfer are nano-sized structures. The distance between carrier molecules (cofactors), which represent practically isolated electron localization centers, reaches tens of angstroms. The electron transfer theory based on the concept of delocalized electron states, which is conventionally used in biophysics, is unable to adequately interpret the results of concrete observations in many cases. On the basis of the theory of electronic transitions in the case of localized states, developed in the physics of disorder matter, a mechanism of long distance electron transfer in biological systems is suggested. The molecular relaxation of the microenvironment of electron localization centers that accompanies the electron transfer process is also considered.

  16. DETERMINATION OF HETEROGENEOUS ELECTRON TRANSFER RATE CONSTANTS AT MICROFABRICATED IRIDIUM ELECTRODES. (R825511C022)

    Science.gov (United States)

    There has been an increasing use of both solid metal and microfabricated iridium electrodes as substrates for various types of electroanalysis. However, investigations to determine heterogeneous electron transfer rate constants on iridium, especially at an electron beam evapor...

  17. Concept of a Fast and Simple Atmospheric Radiative Transfer Model for Aerosol Retrieval

    Science.gov (United States)

    Seidel, Felix; Kokhanovsky, Alexander A.

    2010-05-01

    Radiative transfer modelling (RTM) is an indispensable tool for a number of applications, including astrophysics, climate studies and quantitative remote sensing. It simulates the attenuation of light through a translucent medium. Here, we look at the scattering and absorption of solar light on its way to the Earth's surface and back to space or back into a remote sensing instrument. RTM is regularly used in the framework of the so-called atmospheric correction to find properties of the surface. Further, RTM can be inverted to retrieve features of the atmosphere, such as the aerosol optical depth (AOD), for instance. Present-day RTM, such as 6S, MODTRAN, SHARM, RT3, SCIATRAN or RTMOM have errors of only a few percent, however they are rather slow and often not easy to use. We present here a concept for a fast and simple RTM model in the visible spectral range. It is using a blend of different existing RTM approaches with a special emphasis on fast approximative analytical equations and parametrizations. This concept may be helpful for efficient retrieval algorithms, which do not have to rely on the classic look-up-tables (LUT) approach. For example, it can be used to retrieve AOD without complex inversion procedures including multiple iterations. Naturally, there is always a trade-off between speed and modelling accuracy. The code can be run therefore in two different modes. The regular mode provides a reasonable ratio between speed and accuracy, while the optional mode is very fast but less accurate. The normal mode approximates the diffuse scattered light by calculating the first (single scattering) and second order of scattering according to the classical method of successive orders of scattering. The very fast mode calculates only the single scattering approximation, which does not need any slow numerical integration procedure, and uses a simple correction factor to account for multiple scattering. This factor is a parametrization of MODTRAN results, which

  18. Direct electron transfer from glucose oxidase immobilized on a nano-porous glassy carbon electrode

    Energy Technology Data Exchange (ETDEWEB)

    Haghighi, Behzad, E-mail: haghighi@iasbs.ac.ir [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Gava Zang, Zanjan (Iran, Islamic Republic of); Tabrizi, Mahmoud Amouzadeh [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, P.O. Box 45195-1159, Gava Zang, Zanjan (Iran, Islamic Republic of)

    2011-11-30

    Highlights: > A direct electron transfer reaction of glucose oxidase was observed on the surface of a nano-porous glassy carbon electrode. > A pair of well-defined and reversible redox peaks was observed at the formal potential of approximately -0.439 V. > The apparent electron transfer rate constant was measured to be 5.27 s{sup -1}. > A mechanism for the observed direct electron transfer reaction was proposed, which consists of a two-electron and a two-proton transfer. - Abstract: A pair of well-defined and reversible redox peaks was observed for the direct electron transfer (DET) reaction of an immobilized glucose oxidase (GOx) on the surface of a nano-porous glassy carbon electrode at the formal potential (E{sup o}') of -0.439 V versus Ag/AgCl/saturated KCl. The electron transfer rate constant (k{sub s}) was calculated to be 5.27 s{sup -1}. The dependence of E{sup o}' on pH indicated that the direct electron transfer of the GOx was a two-electron transfer process, coupled with two-proton transfer. The results clearly demonstrate that the nano-porous glassy carbon electrode is a cost-effective and ready-to-use scaffold for the fabrication of a glucose biosensor.

  19. [Mechanisms of electron transfer to insoluble terminal acceptors in chemoorganotrophic bacteria].

    Science.gov (United States)

    Samarukha, I A

    2014-01-01

    The mechanisms of electron transfer of association of chemoorganotrophic bacteria to the anode in microbial fuel cells are summarized in the survey. These mechanisms are not mutually exclusive and are divided into the mechanisms of mediator electron transfer, mechanisms of electron transfer with intermediate products of bacterial metabolism and mechanism of direct transfer of electrons from the cell surface. Thus, electron transfer mediators are artificial or synthesized by bacteria riboflavins and phenazine derivatives, which also determine the ability of bacteria to antagonism. The microorganisms with hydrolytic and exoelectrogenic activity are involved in electron transfer mechanisms that are mediated by intermediate metabolic products, which are low molecular carboxylic acids, alcohols, hydrogen etc. The direct transfer of electrons to insoluble anode is possible due to membrane structures (cytochromes, pili, etc.). Association of microorganisms, and thus the biochemical mechanisms of electron transfer depend on the origin of the inoculum, substrate composition, mass transfer, conditions of aeration, potentials and location of electrodes and others, that are defined by technological and design parameters.

  20. Stereoselectivity in electron-transfer reactions in chiral media.

    Science.gov (United States)

    Olmstead, Deborah; Hua, Xaio; Osvath, Peter; Lappin, A Graham

    2010-02-07

    The oxidation of [Co(edta)](2-) by [IrCl(6)](2-) proceeds by both inner-sphere and outer-sphere electron-transfer pathways. In the presence of added [Co(en)(3)](3+), the outer-sphere pathway is enhanced. When optically active [Co(en)(3)](3+) is used, the [Co(edta)](-) formed is optically active, reflecting a 1.5% DeltaLambda selectivity. It is proposed that the selectivity arises from preferential formation and reactivity of the DeltaLambda ion pair, {[Co(edta)](2-),[Co(en)(3)](3+)}. Direct reaction of [Co(edta)](-) with [Co(en)(3)](2+) has also been investigated in the optically active solvent, (S)-(-)-1,2-propylene carbonate. The induction is small, forming 0.75% Delta-[Co(en)(3)](3+), consistent with the important role for hydrogen bonding in determining the precursor stereoselectivity to the exclusion of solvent.

  1. Proton-Coupled Electron Transfer: Moving Together and Charging Forward

    Energy Technology Data Exchange (ETDEWEB)

    Hammes-Schiffer, Sharon

    2015-07-22

    Proton-coupled electron transfer (PCET) is ubiquitous throughout chemistry and biology. This Perspective discusses recent advances and current challenges in the field of PCET, with an emphasis on the role of theory and computation. The fundamental theoretical concepts are summarized, and expressions for rate constants and kinetic isotope effects are provided. Computational methods for calculating reduction potentials and pKa’s for molecular electrocatalysts, as well as methods for simulating the nonadiabatic dynamics of photoinduced processes, are also described. Representative applications to PCET in solution, proteins, electrochemistry, and photoinduced processes are presented, highlighting the interplay between theoretical and experimental studies. The current challenges and suggested future directions are outlined for each type of application, concluding with an overall view to the future. The work described herein was supported by National Science Foundation Grant CHE-13-61293 (theory development), National Institutes of Health Grant GM056207 (soybean lipoxygenase), Center for Chemical Innovation of the National Science Foundation Solar Fuels Grant CHE-1305124 (cobalt catalysts), Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (nickel catalysts), and Air Force Office of Scientific Research Award No. FA9550-14-1-0295 (photoinduced PCET).

  2. Revisiting direct electron transfer in nanostructured carbon laccase oxygen cathodes.

    Science.gov (United States)

    Adam, Catherine; Scodeller, Pablo; Grattieri, Matteo; Villalba, Matías; Calvo, Ernesto J

    2016-06-01

    The biocatalytic electroreduction of oxygen has been studied on large surface area graphite and Vulcan® carbon electrodes with adsorbed Trametes trogii laccase. The electrokinetics of the O2 reduction reaction (ORR) was studied at different electrode potentials, O2 partial pressures and concentrations of hydrogen peroxide. Even though the overpotential at 0.25 mA·cm(-2) for the ORR at T1Cu of the adsorbed laccase on carbon is 0.8 V lower than for Pt of similar geometric area, the rate of the reaction and thus the operative current density is limited by the enzyme reaction rate at the T2/T3 cluster site for the adsorbed enzyme. The transition potential for the rate determining step from the direct electron transfer (DET) to the enzyme reaction shifts to higher potentials at higher oxygen partial pressure. Hydrogen peroxide produced by the ORR on bare carbon support participates in an inhibition mechanism, with uncompetitive predominance at high H2O2 concentration, non-competitive contribution can be detected at low inhibitor concentration.

  3. Electron transfer precedes ATP hydrolysis during nitrogenase catalysis

    Science.gov (United States)

    Duval, Simon; Danyal, Karamatullah; Shaw, Sudipta; Lytle, Anna K.; Dean, Dennis R.; Hoffman, Brian M.; Antony, Edwin; Seefeldt, Lance C.

    2013-01-01

    The biological reduction of N2 to NH3 catalyzed by Mo-dependent nitrogenase requires at least eight rounds of a complex cycle of events associated with ATP-driven electron transfer (ET) from the Fe protein to the catalytic MoFe protein, with each ET coupled to the hydrolysis of two ATP molecules. Although steps within this cycle have been studied for decades, the nature of the coupling between ATP hydrolysis and ET, in particular the order of ET and ATP hydrolysis, has been elusive. Here, we have measured first-order rate constants for each key step in the reaction sequence, including direct measurement of the ATP hydrolysis rate constant: kATP = 70 s−1, 25 °C. Comparison of the rate constants establishes that the reaction sequence involves four sequential steps: (i) conformationally gated ET (kET = 140 s−1, 25 °C), (ii) ATP hydrolysis (kATP = 70 s−1, 25 °C), (iii) Phosphate release (kPi = 16 s−1, 25 °C), and (iv) Fe protein dissociation from the MoFe protein (kdiss = 6 s−1, 25 °C). These findings allow completion of the thermodynamic cycle undergone by the Fe protein, showing that the energy of ATP binding and protein–protein association drive ET, with subsequent ATP hydrolysis and Pi release causing dissociation of the complex between the Feox(ADP)2 protein and the reduced MoFe protein. PMID:24062462

  4. Effects of quantum coherence in metalloprotein electron transfer

    Science.gov (United States)

    Dorner, Ross; Goold, John; Heaney, Libby; Farrow, Tristan; Vedral, Vlatko

    2012-09-01

    Many intramolecular electron transfer (ET) reactions in biology are mediated by metal centers in proteins. This process is commonly described by a model of diffusive hopping according to the semiclassical theories of Marcus and Hopfield. However, recent studies have raised the possibility that nontrivial quantum mechanical effects play a functioning role in certain biomolecular processes. Here, we investigate the potential effects of quantum coherence in biological ET by extending the semiclassical model to allow for the possibility of quantum coherent phenomena using a quantum master equation based on the Holstein Hamiltonian. We test the model on the structurally defined chain of seven iron-sulfur clusters in nicotinamide adenine dinucleotide plus hydrogen:ubiquinone oxidoreductase (complex I), a crucial respiratory enzyme and one of the longest chains of metal centers in biology. Using experimental parameters where possible, we find that, in limited circumstances, a small quantum mechanical contribution can provide a marked increase in the ET rate above the semiclassical diffusive-hopping rate. Under typical biological conditions, our model reduces to well-known diffusive behavior.

  5. Synthetic Applications of Proton-Coupled Electron Transfer.

    Science.gov (United States)

    Gentry, Emily C; Knowles, Robert R

    2016-08-16

    Redox events in which an electron and proton are exchanged in a concerted elementary step are commonly referred to as proton-coupled electron transfers (PCETs). PCETs are known to operate in numerous important biological redox processes, as well as recent inorganic technologies for small molecule activation. These studies suggest that PCET catalysis might also function as a general mode of substrate activation in organic synthesis. Over the past three years, our group has worked to advance this hypothesis and to demonstrate the synthetic utility of PCET through the development of novel catalytic radical chemistries. The central aim of these efforts has been to demonstrate the ability of PCET to homolytically activate a wide variety of common organic functional groups that are energetically inaccessible using known molecular H atom transfer catalysts. To do so, we made use of a simple formalism first introduced by Mayer and co-workers that allowed us to predict the thermodynamic capacity of any oxidant/base or reductant/acid pair to formally add or remove H· from a given substrate. With this insight, we were able to rationally select catalyst combinations thermodynamically competent to homolyze the extraordinarily strong E-H σ-bonds found in many common protic functional groups (BDFEs > 100 kcal/mol) or to form unusually weak bonds to hydrogen via the reductive action of common organic π-systems (BDFEs < 35 kcal/mol). These ideas were reduced to practice through the development of new catalyst systems for reductive PCET activations of ketones and oxidative PCET activation of amide N-H bonds to directly furnish reactive ketyl and amidyl radicals, respectively. In both systems, the reaction outcomes were found to be successfully predicted using the effective bond strength formalism, suggesting that these simple thermochemical considerations can provide useful and actionable insights into PCET reaction design. The ability of PCET catalysis to control

  6. Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S.

    2016-07-01

    electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

  7. Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators.

    Science.gov (United States)

    Badalyan, Artavazd; Stahl, Shannon S

    2016-07-21

    electron-proton-transfer mediators, such as TEMPO, may be used in combination with first-row transition metals, such as copper, to achieve efficient two-electron electrochemical processes, thereby introducing a new concept for the development of non-precious-metal electrocatalysts.

  8. Ab initio quantum mechanical/molecular mechanical simulation of electron transfer process: fractional electron approach.

    Science.gov (United States)

    Zeng, Xiancheng; Hu, Hao; Hu, Xiangqian; Cohen, Aron J; Yang, Weitao

    2008-03-28

    Electron transfer (ET) reactions are one of the most important processes in chemistry and biology. Because of the quantum nature of the processes and the complicated roles of the solvent, theoretical study of ET processes is challenging. To simulate ET processes at the electronic level, we have developed an efficient density functional theory (DFT) quantum mechanical (QM)/molecular mechanical (MM) approach that uses the fractional number of electrons as the order parameter to calculate the redox free energy of ET reactions in solution. We applied this method to study the ET reactions of the aqueous metal complexes Fe(H(2)O)(6)(2+/3+) and Ru(H(2)O)(6)(2+/3+). The calculated oxidation potentials, 5.82 eV for Fe(II/III) and 5.14 eV for Ru(II/III), agree well with the experimental data, 5.50 and 4.96 eV, for iron and ruthenium, respectively. Furthermore, we have constructed the diabatic free energy surfaces from histogram analysis based on the molecular dynamics trajectories. The resulting reorganization energy and the diabatic activation energy also show good agreement with experimental data. Our calculations show that using the fractional number of electrons (FNE) as the order parameter in the thermodynamic integration process leads to efficient sampling and validate the ab initio QM/MM approach in the calculation of redox free energies.

  9. Quantum non-equilibrium approach for fast electron transport in open systems: photosynthetic reaction centers

    CERN Document Server

    Pudlak, M; Nazmitdinov, R G; Pincak, R

    2011-01-01

    Creation of electron or exciton by external fields in a system with initially statistically independent unrelaxed vibrational modes leads to an initial condition term. The contribution of this term in the time convolution generalized master equation approach is studied in second order of the perturbation theory for electron-phonon coupling in the parth integral formalism. The developed approach, applied for analysis of dynamics in the photosynthetic reaction center, exhibits the key role of the initial condition term at the primary stage of electron transfer.

  10. Fast calculation of two-electron-repulsion integrals: a numerical approach

    CERN Document Server

    Lopes, Pedro E M

    2016-01-01

    An alternative methodology to evaluate two-electron-repulsion integrals based on numerical approximation is proposed. Computational chemistry has branched into two major fields with methodologies based on quantum mechanics and classical force fields. However, there are significant shadowy areas not covered by any of the available methods. Many relevant systems are often too big for traditional quantum chemical methods while being chemically too complex for classical force fields. Examples include systems in nanomedicine, studies of metalloproteins, etc. There is an urgent need to develop fast quantum chemical methods able to study large and complex systems. This work is a proof-of-concept on the numerical techniques required to develop accurate and computationally efficient algorithms for the fast calculation of electron-repulsion integrals, one of the most significant bottlenecks in the extension of quantum chemistry to large systems. All concepts and calculations were developed for the three-center integral...

  11. Effect of horizontal fast electron beam position feedback on the performance of ESRF beamlines

    CERN Document Server

    Pascarelli, S

    2001-01-01

    ESRF is a state of the art third generation synchrotron light source optimized to produce very bright and collimated hard X-ray beams using insertion devices. Instabilities of the electron beam, resulting in source point transverse displacements, spoil these outstanding beam qualities. At the beginning of operation a fast active feedback system was installed to damp the transverse motion of the electron beam in the vertical plane. Recently it became evident that also the relatively smaller horizontal instabilities may have specific detrimental effects on the operation of particularly sensitive beamlines. The dispersive XAS beamline (ID24) was the first to benefit from the activation of a local horizontal feedback. Optimized to perform time-resolved studies and high-pressure experiments, its operation was strongly perturbed. This paper briefly describes the work carried out to identify and solve these problems, presenting the outcome of the implementation of a fast orbit feedback on this beamline.

  12. A fast high-order method to calculate wakefield forces in an electron beam

    CERN Document Server

    Qiang, Ji; Ryne, Robert D

    2012-01-01

    In this paper we report on a high-order fast method to numerically calculate wakefield forces in an electron beam given a wake function model. This method is based on a Newton-Cotes quadrature rule for integral approximation and an FFT method for discrete summation that results in an $O(Nlog(N))$ computational cost, where $N$ is the number of grid points. Using the Simpson quadrature rule with an accuracy of $O(h^4)$, where $h$ is the grid size, we present numerical calculation of the wakefields from a resonator wake function model and from a one-dimensional coherent synchrotron radiation (CSR) wake model. Besides the fast speed and high numerical accuracy, the calculation using the direct line density instead of the first derivative of the line density avoids numerical filtering of the electron density function for computing the CSR wakefield force.

  13. Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles.

    Science.gov (United States)

    Tvrdy, Kevin; Frantsuzov, Pavel A; Kamat, Prashant V

    2011-01-04

    Quantum dot-metal oxide junctions are an integral part of next-generation solar cells, light emitting diodes, and nanostructured electronic arrays. Here we present a comprehensive examination of electron transfer at these junctions, using a series of CdSe quantum dot donors (sizes 2.8, 3.3, 4.0, and 4.2 nm in diameter) and metal oxide nanoparticle acceptors (SnO(2), TiO(2), and ZnO). Apparent electron transfer rate constants showed strong dependence on change in system free energy, exhibiting a sharp rise at small driving forces followed by a modest rise further away from the characteristic reorganization energy. The observed trend mimics the predicted behavior of electron transfer from a single quantum state to a continuum of electron accepting states, such as those present in the conduction band of a metal oxide nanoparticle. In contrast with dye-sensitized metal oxide electron transfer studies, our systems did not exhibit unthermalized hot-electron injection due to relatively large ratios of electron cooling rate to electron transfer rate. To investigate the implications of these findings in photovoltaic cells, quantum dot-metal oxide working electrodes were constructed in an identical fashion to the films used for the electron transfer portion of the study. Interestingly, the films which exhibited the fastest electron transfer rates (SnO(2)) were not the same as those which showed the highest photocurrent (TiO(2)). These findings suggest that, in addition to electron transfer at the quantum dot-metal oxide interface, other electron transfer reactions play key roles in the determination of overall device efficiency.

  14. Enzymatic cellulose oxidation is linked to lignin by long-range electron transfer.

    Science.gov (United States)

    Westereng, Bjørge; Cannella, David; Wittrup Agger, Jane; Jørgensen, Henning; Larsen Andersen, Mogens; Eijsink, Vincent G H; Felby, Claus

    2015-12-21

    Enzymatic oxidation of cell wall polysaccharides by lytic polysaccharide monooxygenases (LPMOs) plays a pivotal role in the degradation of plant biomass. While experiments have shown that LPMOs are copper dependent enzymes requiring an electron donor, the mechanism and origin of the electron supply in biological systems are only partly understood. We show here that insoluble high molecular weight lignin functions as a reservoir of electrons facilitating LPMO activity. The electrons are donated to the enzyme by long-range electron transfer involving soluble low molecular weight lignins present in plant cell walls. Electron transfer was confirmed by electron paramagnetic resonance spectroscopy showing that LPMO activity on cellulose changes the level of unpaired electrons in the lignin. The discovery of a long-range electron transfer mechanism links the biodegradation of cellulose and lignin and sheds new light on how oxidative enzymes present in plant degraders may act in concert.

  15. An excited state intramolecular proton transfer dye based fluorescence turn-on probe for fast detection of thiols and its applications in bioimaging

    Science.gov (United States)

    Zhao, Yun; Xue, Yuanyuan; Li, Haoyang; Zhu, Ruitao; Ren, Yuehong; Shi, Qinghua; Wang, Song; Guo, Wei

    2017-03-01

    In this study, a new fluorescent probe 2-(2‧-hydroxy-5‧-N-maleimide phenyl)-benzothiazole (probe 1), was designed and synthesized by linking the excited state intramolecular proton transfer (ESIPT) fluorophore to the maleimide group for selective detection of thiols in aqueous solution. The fluorescence of probe 1 is strongly quenched by maleimide group through the photo-induced electron transfer (PET) mechanism, but after reaction with thiol, the fluorescence of ESIPT fluorophore is restored, affording a large Stokes shifts. Upon addition of cysteine (Cys), probe 1 exhibited a fast response time (complete within 30 s) and a high signal-to-noise ratio (up to 23-fold). It showed a high selectivity and excellent sensitivity to thiols over other relevant biological species, with a detection limit of 3.78 × 10- 8 M (S/N = 3). Moreover, the probe was successfully applied to the imaging of thiols in living cells.

  16. Wave packet evolution approach to ionization of hydrogen molecular ion by fast electrons

    CERN Document Server

    Serov, V V; Joulakian, B B; Vinitsky, S I; Serov, Vladislav V.; Derbov, Vladimir L.; Joulakian, Boghos B.; Vinitsky, Sergue I.

    2000-01-01

    The multiply differential cross section of the ionization of hydrogen molecular ion by fast electron impact is calculated by a direct approach, which involves the reduction of the initial 6D Schr\\"{o}dinger equation to a 3D evolution problem followed by the modeling of the wave packet dynamics. This approach avoids the use of stationary Coulomb two-centre functions of the continuous spectrum of the ejected electron which demands cumbersome calculations. The results obtained, after verification of the procedure in the case atomic hydrogen, reveal interesting mechanisms in the case of small scattering angles.

  17. Fast Ion Induced Shearing of 2D Alfven Eigenmodes Measured by Electron Cyclotron Emission Imaging

    Energy Technology Data Exchange (ETDEWEB)

    Tobias, Ben [University of California, Davis; Classen, I.G.J. [FOM Institute for Plasma Physics Rijnhuizen, Nieuwegein, The Netherlands; Domier, C. W. [University of California, Davis; Heidbrink, W. [University of California, Irvine; Luhmann, N.C. [University of California, Davis; Nazikian, Raffi [Princeton Plasma Physics Laboratory (PPPL); Park, H.K. [Pohang University of Science and Technology (POSTECH), Pohang, Republic of Korea; Spong, Donald A [ORNL; Van Zeeland, Michael [General Atomics

    2011-01-01

    Two-dimensional images of electron temperature perturbations are obtained with electron cyclotron emission imaging (ECEI) on the DIII-D tokamak and compared to Alfven eigenmode structures obtained by numerical modeling using both ideal MHD and hybrid MHD-gyrofluid codes. While many features of the observations are found to be in excellent agreement with simulations using an ideal MHD code (NOVA), other characteristics distinctly reveal the influence of fast ions on the mode structures. These features are found to be well described by the nonperturbative hybrid MHD-gyrofluid model TAEFL.

  18. Experimental Verification of the Role of Electron Pressure in Fast Magnetic Reconnection with a Guide Field.

    Science.gov (United States)

    Fox, W; Sciortino, F; V Stechow, A; Jara-Almonte, J; Yoo, J; Ji, H; Yamada, M

    2017-03-24

    We report detailed laboratory observations of the structure of a reconnection current sheet in a two-fluid plasma regime with a guide magnetic field. We observe and quantitatively analyze the quadrupolar electron pressure variation in the ion-diffusion region, as originally predicted by extended magnetohydrodynamics simulations. The projection of the electron pressure gradient parallel to the magnetic field contributes significantly to balancing the parallel electric field, and the resulting cross-field electron jets in the reconnection layer are diamagnetic in origin. These results demonstrate how parallel and perpendicular force balance are coupled in guide field reconnection and confirm basic theoretical models of the importance of electron pressure gradients for obtaining fast magnetic reconnection.

  19. 27 CFR 41.115a - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... electronic fund transfer. 41.115a Section 41.115a Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Puerto Rican Tobacco Products and Cigarette Papers and....115a Payment of tax by electronic fund transfer. (a) General. (1) Each taxpayer who was liable, during...

  20. 27 CFR 40.357 - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... electronic fund transfer. 40.357 Section 40.357 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Manufacture of Cigarette Papers and Tubes Taxes § 40.357 Payment of tax by electronic fund transfer. (a) General. (1) Each taxpayer who was liable, during a...

  1. 27 CFR 41.63 - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... electronic fund transfer. 41.63 Section 41.63 Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO TAX..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Taxes Customs' Collection of Taxes § 41.63 Payment of tax by electronic fund transfer. (a) Each importer who was liable, during a calendar year, for a gross...

  2. 27 CFR 40.165a - Payment of tax by electronic fund transfer.

    Science.gov (United States)

    2010-04-01

    ... making payment by electronic fund transfer (EFT) of taxes on tobacco products, cigarette papers, and... electronic fund transfer. 40.165a Section 40.165a Alcohol, Tobacco Products and Firearms ALCOHOL AND TOBACCO..., CIGARETTE PAPERS AND TUBES, AND PROCESSED TOBACCO Operations by Manufacturers of Tobacco Products...

  3. 76 FR 67153 - Federal Acquisition Regulation; Submission for OMB Review; Payment by Electronic Fund Transfer

    Science.gov (United States)

    2011-10-31

    ... would enable the Government to make payments under the contract by electronic fund transfer (EFT). The... From the Federal Register Online via the Government Publishing Office ] DEPARTMENT OF DEFENSE... Regulation; Submission for OMB Review; Payment by Electronic Fund Transfer AGENCY: Department of Defense (DOD...

  4. 41 CFR 102-118.70 - Must my agency make all payments via electronic funds transfer?

    Science.gov (United States)

    2010-07-01

    ... payments via electronic funds transfer? 102-118.70 Section 102-118.70 Public Contracts and Property... Services § 102-118.70 Must my agency make all payments via electronic funds transfer? Yes, under 31 U.S.C. 3332, et seq., your agency must make all payments for goods and services via EFT (this includes...

  5. Fast response of electron-scale turbulence to auxiliary heating cessation in National Spherical Torus Experiment

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Y.; Wang, W. X.; LeBlanc, B. P.; Guttenfelder, W.; Kaye, S. M.; Ethier, S.; Mazzucato, E.; Bell, R. [Princeton Plasma Physics Laboratory, Princeton, New Jersey 08543 (United States); Lee, K. C. [National Fusion Research Institute, Daejeon 305-806 (Korea, Republic of); Domier, C. W. [University of California at Davis, Davis, California 95616 (United States); Smith, D. R. [University of Wisconsin-Madison, Madison, Wisconsin 53706 (United States); Yuh, H. [Nova Photonics, Inc., Princeton, New Jersey 08540 (United States)

    2015-11-15

    In this letter, we report the first observation of the fast response of electron-scale turbulence to auxiliary heating cessation in National Spherical Torus eXperiment [Ono et al., Nucl. Fusion 40, 557 (2000)]. The observation was made in a set of RF-heated L-mode plasmas with toroidal magnetic field of 0.55 T and plasma current of 300 kA. It is observed that electron-scale turbulence spectral power (measured with a high-k collective microwave scattering system) decreases significantly following fast cessation of RF heating that occurs in less than 200 μs. The large drop in the turbulence spectral power has a short time delay of about 1–2 ms relative to the RF cessation and happens on a time scale of 0.5–1 ms, much smaller than the energy confinement time of about 10 ms. Power balance analysis shows a factor of about 2 decrease in electron thermal diffusivity after the sudden drop of turbulence spectral power. Measured small changes in equilibrium profiles across the RF cessation are unlikely able to explain this sudden reduction in the measured turbulence and decrease in electron thermal transport, supported by local linear stability analysis and both local and global nonlinear gyrokinetic simulations. The observations imply that nonlocal flux-driven mechanism may be important for the observed turbulence and electron thermal transport.

  6. Superexchange coupling and electron transfer in globular proteins via polaron excitations.

    Science.gov (United States)

    Chuev, G N; Lakhno, V D; Ustitnin, M N

    2000-06-01

    The polaron approach is used to treat long-range electron transfersbetween globular proteins. A rate expression for the polaron transfer model is given along with a description of appropriate conditions forits use. Assuming that electrons transfer via a superexchange couplingdue to a polaron excitation, we have estimated the distance dependenceof the rate constant for the self-exchange reactions between globularproteins in solutions. The distance dependence of the polaron coupling andsolvent reorganization energy are provided as a basis forunderstanding and interpreting a long-range electron transfer experiment.The difficulties and problems of the polaron treatment of long-rangeelectron transfers are discussed, and suggestions for new experimentsare made.

  7. Photoinduced energy and electron transfer in rubrene-benzoquinone and rubrene-porphyrin systems

    KAUST Repository

    Khan, Jafar Iqbal

    2014-11-01

    Excited-state electron and energy transfer from singlet excited rubrene (Ru) to benzoquinone (BQ) and tetra-(4-aminophenyl) porphyrin (TAPP) were investigated by steady-state absorption and emission, time-resolved transient absorption, and femtosecond (fs)-nanosecond (ns) fluorescence spectroscopy. The low reduction potential of BQ provides the high probability of electron transfer from the excited Ru to BQ. Steady-state and time-resolved results confirm such an excited electron transfer scenario. On the other hand, strong spectral overlap between the emission of Ru and absorption of TAPP suggests that energy transfer is a possible deactivation pathway of the Ru excited state.

  8. Fast Transverse Beam Instability Caused by Electron Cloud Trapped in Combined Function Magnets

    Energy Technology Data Exchange (ETDEWEB)

    Antipov, Sergey [Univ. of Chicago, IL (United States)

    2017-03-01

    Electron cloud instabilities affect the performance of many circular high-intensity particle accelerators. They usually have a fast growth rate and might lead to an increase of the transverse emittance and beam loss. A peculiar example of such an instability is observed in the Fermilab Recycler proton storage ring. Although this instability might pose a challenge for future intensity upgrades, its nature had not been completely understood. The phenomena has been studied experimentally by comparing the dynamics of stable and unstable beam, numerically by simulating the build-up of the electron cloud and its interaction with the beam, and analytically by constructing a model of an electron cloud driven instability with the electrons trapped in combined function dipoles. Stabilization of the beam by a clearing bunch reveals that the instability is caused by the electron cloud, trapped in beam optics magnets. Measurements of microwave propagation confirm the presence of the cloud in the combined function dipoles. Numerical simulations show that up to 10$^{-2}$ of the particles can be trapped by their magnetic field. Since the process of electron cloud build-up is exponential, once trapped this amount of electrons significantly increases the density of the cloud on the next revolution. In a combined function dipole this multi-turn accumulation allows the electron cloud reaching final intensities orders of magnitude greater than in a pure dipole. The estimated fast instability growth rate of about 30 revolutions and low mode frequency of 0.4 MHz are consistent with experimental observations and agree with the simulations. The created instability model allows investigating the beam stability for the future intensity upgrades.

  9. Light harvesting, electron transfer and electron cycling of a native photosynthetic membrane adsorbed onto a gold surface

    NARCIS (Netherlands)

    Magis, G.J; Hollander, den M. -J.; Onderwaater, W. G.; Olsen, J.D.; Hunter, C.N.; Aartsma, T.J.; Frese, R.N.

    2010-01-01

    Photosynthetic membranes comprise a network of light harvesting and reaction center pigment–protein complexes responsible for the primary photoconversion reactions: light absorption, energy transfer and electron cycling. The structural organization of membranes of the purple bacterial species Rb. sp

  10. Electron correlations in single-electron capture from helium by fast protons and α particles

    Science.gov (United States)

    Mančev, Ivan; Milojević, Nenad

    2010-02-01

    Single-electron capture from heliumlike atomic systems by bare projectiles is investigated by means of the four-body boundary-corrected first Born approximation (CB1-4B). The effect of the dynamic electron correlation is explicitly taken into account through the complete perturbation potential. The quantum-mechanical post and prior transition amplitudes for single charge exchange encompassing symmetric and/or asymmetric collisions are derived in terms of two-dimensional real integrals in the case of the prior form and five-dimensional quadratures for the post form. An illustrative computation is performed for single-electron capture from helium by protons and α particles at intermediate and high impact energies. The role of dynamic correlations is examined as a function of increased projectile energy. The validity and utility of the proposed CB1-4B method is critically assessed in comparison with the existing experimental data for total cross sections, and excellent agreement is obtained.

  11. Exploration of ultra-fast electron dynamics using time-dependent R-matrix theory

    Science.gov (United States)

    van der Hart, Hugo; Rey, Hector; Hassouneh, Ola; Brown, Andrew

    2014-05-01

    When an atom is subjected to an intense laser field, the full atomic response can involve a collective response involving several electrons. This collective response will be affected by electron-electron repulsion, coupling the overall electron dynamics. In order to investigate this dynamics for a multi-electron system from first principles, we have developed time-dependent R-matrix theory. The theory applies the basic principles of R-matrix theory, in which all interactions between all electrons are taken into account close to the nucleus, but exchange interactions are neglected when one electron has become distanced from the parent atom. In this contribution, we will explain the basic principles of this theory and demonstrate its application to ultra-fast dynamics in C+, and harmonic generation in singly ionised noble-gas atoms. Both studies demonstrate that it is important to go beyond the single-active-electron approximation. This research has been supported by EPSRC UK, and by the EU Initial Training Network CORINF.

  12. Fast Pulse Measurements and Temperature Variation of Enhanced Magnetic Damping of Spin-Transfer Excitation

    Science.gov (United States)

    Ryan, E. M.; Garcia, A. G. F.; Braganca, P. M.; Fuchs, G. D.; Emley, N. C.; Read, J. C.; Tan, E.; Ralph, D. C.; Buhrman, R. A.; Katine, J. A.

    2007-03-01

    Recently, light terbium (Tb) doping in thin films of permalloy (Py) has been shown to increase the damping parameter α by several orders of magnitude [1]. To directly study the effect of increased α on spin-transfer systems, we have fabricated 0.004 um^2 Py/Cu/Py nanopillar spin valves with 0 and 2% Tb in the free layer, and measured critical currents across a range of temperatures from 4.2 K to 295 K. We find that the critical currents for reversibly switching the free layer, generally expected to be proportional to α, are several times larger on average in the 2% Tb samples than in pure Py samples, and increase linearly with decreasing temperature. We will also discuss FMR data, and data for switching with fast pulses from 1 to 100 nsec at both 150 K and room temperature, along with matching simulations that allows us to extract α and other spin-torque parameters [2]. These results suggest one approach for controllably reducing the negative impact of spin-torque effects on nanoscale spin valve and read head sensors, and achieving a deeper understanding of these spin-torque devices. [1] W. Bailey, P. Kabos, F. Mancoff, and S. E. Russek, IEEE Trans. Magn. 37, 1749 (2001). [2] P. M. Braganca, et al. Appl. Phys. Lett. 87, 112507 (2005).

  13. Unified treatment of quantum coherent and incoherent hopping dynamics in electronic energy transfer: reduced hierarchy equation approach.

    Science.gov (United States)

    Ishizaki, Akihito; Fleming, Graham R

    2009-06-21

    A new quantum dynamic equation for excitation energy transfer is developed which can describe quantum coherent wavelike motion and incoherent hopping in a unified manner. The developed equation reduces to the conventional Redfield theory and Forster theory in their respective limits of validity. In the regime of coherent wavelike motion, the equation predicts several times longer lifetime of electronic coherence between chromophores than does the conventional Redfield equation. Furthermore, we show quantum coherent motion can be observed even when reorganization energy is large in comparison to intersite electronic coupling (the Forster incoherent regime). In the region of small reorganization energy, slow fluctuation sustains longer-lived coherent oscillation, whereas the Markov approximation in the Redfield framework causes infinitely fast fluctuation and then collapses the quantum coherence. In the region of large reorganization energy, sluggish dissipation of reorganization energy increases the time electronic excitation stays above an energy barrier separating chromophores and thus prolongs delocalization over the chromophores.

  14. Rates and Equilibrium of CuA to heme a electron transfer in Paracoccus denitrificans cytochrome c oxidase

    DEFF Research Database (Denmark)

    Farver, Ole; Grell, Ernst; Ludwig, Bernd

    2006-01-01

    A reoxidation were identical within experimental error and independent of the enzyme concentration and its degree of reduction, demonstrating that a fast intramolecular electron equilibration is taking place between CuA and heme a. The rate constants for CuA --> heme a ET and the reverse heme a --> CuA process......Intramolecular electron transfer between CuA and heme a in solubilized bacterial (Paracoccus denitrificans) cytochrome c oxidase was investigated by pulse radiolysis. CuA, the initial electron acceptor, was reduced by 1-methylnicotinamide radicals in a diffusion-controlled reaction, as monitored...... by absorption changes at 825 nm, followed by partial restoration of the absorption and paralleled by an increase in the heme a absorption at 605 nm. The latter observations indicate partial reoxidation of the CuA center and the concomitant reduction of heme a. The rate constants for heme a reduction and Cu...

  15. Bio-batteries and bio-fuel cells: leveraging on electronic charge transfer proteins.

    Science.gov (United States)

    Kannan, A M; Renugopalakrishnan, V; Filipek, S; Li, P; Audette, G F; Munukutla, L

    2009-03-01

    Bio-fuel cells are alternative energy devises based on bio-electrocatalysis of natural substrates by enzymes or microorganisms. Here we review bio-fuel cells and bio-batteries based on the recent literature. In general, the bio-fuel cells are classified based on the type of electron transfer; mediated electron transfer and direct electron transfer or electronic charge transfer (ECT). The ECT of the bio-fuel cells is critically reviewed and a variety of possible applications are considered. The technical challenges of the bio-fuel cells, like bioelectrocatalysis, immobilization of bioelectrocatalysts, protein denaturation etc. are highlighted and future research directions are discussed leveraging on the use of electron charge transfer proteins. In addition, the packaging aspects of the bio-fuel cells are also analyzed and the found that relatively little work has been done in the engineering development of bio-fuel cells.

  16. Ultrafast electron and energy transfer in dye-sensitized iron oxide and oxyhydroxide nanoparticles

    DEFF Research Database (Denmark)

    Gilbert, Benjamin; Katz, Jordan E.; Huse, Nils

    2013-01-01

    –310 fs were found for all samples. Comparison between TA dynamics on uncoated and dye-sensitized hematite nanoparticles revealed the dye de-excitation pathway to consist of a competition between electron and energy transfer to the nanoparticles. We analyzed the TA data for hematite nanoparticles using...... a four-state model of the dye-sensitized system, finding electron and energy transfer to occur on the same ultrafast timescale. The interfacial electron transfer rates for iron oxides are very close to those previously reported for DCF-sensitized titanium dioxide (for which dye–oxide energy transfer...... photo-initiated interfacial electron transfer. This approach enables time-resolved study of the fate and mobility of electrons within the solid phase. However, complete analysis of the ultrafast processes following dye photoexcitation of the sensitized iron(iii) oxide nanoparticles has not been reported...

  17. Protein electron transfer: is biology (thermo)dynamic?

    Science.gov (United States)

    Matyushov, Dmitry V.

    2015-12-01

    Simple physical mechanisms are behind the flow of energy in all forms of life. Energy comes to living systems through electrons occupying high-energy states, either from food (respiratory chains) or from light (photosynthesis). This energy is transformed into the cross-membrane proton-motive force that eventually drives all biochemistry of the cell. Life’s ability to transfer electrons over large distances with nearly zero loss of free energy is puzzling and has not been accomplished in synthetic systems. The focus of this review is on how this energetic efficiency is realized. General physical mechanisms and interactions that allow proteins to fold into compact water-soluble structures are also responsible for a rugged landscape of energy states and a broad distribution of relaxation times. Specific to a protein as a fluctuating thermal bath is the protein-water interface, which is heterogeneous both dynamically and structurally. The spectrum of interfacial fluctuations is a consequence of protein’s elastic flexibility combined with a high density of surface charges polarizing water dipoles into surface nanodomains. Electrostatics is critical to the protein function and the relevant questions are: (i) What is the spectrum of interfacial electrostatic fluctuations? (ii) Does the interfacial biological water produce electrostatic signatures specific to proteins? (iii) How is protein-mediated chemistry affected by electrostatics? These questions connect the fluctuation spectrum to the dynamical control of chemical reactivity, i.e. the dependence of the activation free energy of the reaction on the dynamics of the bath. Ergodicity is often broken in protein-driven reactions and thermodynamic free energies become irrelevant. Continuous ergodicity breaking in a dense spectrum of relaxation times requires using dynamically restricted ensembles to calculate statistical averages. When applied to the calculation of the rates, this formalism leads to the nonergodic

  18. Electron transfer catalysis with monolayer protected Au25 clusters

    Science.gov (United States)

    Antonello, Sabrina; Hesari, Mahdi; Polo, Federico; Maran, Flavio

    2012-08-01

    Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and the Au25L18+/Au25L18 redox couples as redox mediators. Simulation of the CV curves led to determination of the ET rate constant (kET) values for concerted dissociative ET to the peroxides. The ET free energy ΔG° could be estimated for all donor-acceptor combinations, leading to observation of a nice activation-driving force (log kETvs. ΔG°) relationship. Comparison with the kET obtained using a ferrocene-type donor with a formal potential similar to that of Au25L18/Au25L18- showed that the presence of the capping monolayer affects the ET rate rather significantly, which is attributed to the intrinsic nonadiabaticity of peroxide acceptors.Au25L18 (L = S(CH2)2Ph) clusters were prepared and characterized. The resulting monodisperse clusters were reacted with bis(pentafluorobenzoyl) peroxide in dichloromethane to form Au25L18+ quantitatively. The kinetics and thermodynamics of the corresponding electron transfer (ET) reactions were characterized via electrochemistry and thermochemical calculations. Au25L18+ was used in homogeneous redox catalysis experiments with a series of sym-substituted benzoyl peroxides, including the above peroxide, bis(para-cyanobenzoyl) peroxide, dibenzoyl peroxide, and bis(para-methoxybenzoyl) peroxide. Peroxide dissociative ET was catalyzed using both the Au25L18/Au25L18- and

  19. Fresh look at electron-transfer mechanisms via the donor/acceptor bindings in the critical encounter complex.

    Science.gov (United States)

    Rosokha, Sergiy V; Kochi, Jay K

    2008-05-01

    . First, Q or = 1, the overwhelming dominance of the resonance stabilization (H(DA)) predicts the odd-electron mobility between the donor and acceptor to occur without an activation barrier such that bimolecular electron transfer is coincident with their diffusional encounter. In between lies a potentially infinite set of states, 0 now classical Marcus outer-sphere mechanism. Next, the "inner-sphere" mechanism derives from moderate (localized) donor/acceptor bindings and includes the mechanistic concept of the bridged-activated complex introduced by Taube for a wide variety of ligand-based redox dyads. Finally, the "interior" mechanism is also another subclass of the Taube (inner-sphere) classification, and it lies at the other extreme of very fast electron-transfer rate processes (heretofore unrecognized), arising from the spontaneous annihilation of the donor/acceptor dyad to the delocalized (electron-transfer) complex as it descends barrierlessly into the chemical "black hole" that is rate-limited solely by diffusion.

  20. Measurements of fast electron beams and soft X-ray emission from plasma-focus experiments

    Directory of Open Access Journals (Sweden)

    Surała Władysław

    2016-06-01

    Full Text Available The paper reports results of the recent experimental studies of pulsed electron beams and soft X-rays in plasma-focus (PF experiments carried out within a modified PF-360U facility at the NCBJ, Poland. Particular attention was focused on time-resolved measurements of the fast electron beams by means of two different magnetic analyzers, which could record electrons of energy ranging from about 41 keV to about 715 keV in several (6 or 8 measuring channels. For discharges performed with the pure deuterium filling, many strong electron signals were recorded in all the measuring channels. Those signals were well correlated with the first hard X-ray pulse detected by an external scintillation neutron-counter. In some of the analyzer channels, electron spikes (lasting about dozens of nanoseconds and appearing in different instants after the current peculiarity (so-called current dip were also recorded. For several discharges, fast ion beams, which were emitted along the z-axis and recorded with nuclear track detectors, were also investigated. Those measurements confirmed a multibeam character of the ion emission. The time-integrated soft X-ray images, which were taken side-on by means of a pinhole camera and sensitive X-ray films, showed the appearance of some filamentary structures and so-called hot spots. The application of small amounts of admixtures of different heavy noble gases, i.e. of argon (4.8% volumetric, krypton (1.6% volumetric, or xenon (0.8% volumetric, decreased intensity of the recorded electron beams, but increased intensity of the soft X-ray emission and showed more distinct and numerous hot spots. The recorded electron spikes have been explained as signals produced by quasi-mono-energetic microbeams emitted from tiny sources (probably plasma diodes, which can be formed near the observed hot spots.

  1. Long-range electron transfer in zinc-phthalocyanine-oligo(phenylene-ethynylene)-based donor-bridge-acceptor dyads.

    Science.gov (United States)

    Göransson, Erik; Boixel, Julien; Fortage, Jérôme; Jacquemin, Denis; Becker, Hans-Christian; Blart, Errol; Hammarström, Leif; Odobel, Fabrice

    2012-11-05

    In the context of long-range electron transfer for solar energy conversion, we present the synthesis, photophysical, and computational characterization of two new zinc(II) phthalocyanine oligophenylene-ethynylene based donor-bride-acceptor dyads: ZnPc-OPE-AuP(+) and ZnPc-OPE-C(60). A gold(III) porphyrin and a fullerene has been used as electron accepting moieties, and the results have been compared to a previously reported dyad with a tin(IV) dichloride porphyrin as the electron acceptor (Fortage et al. Chem. Commun. 2007, 4629). The results for ZnPc-OPE-AuP(+) indicate a remarkably strong electronic coupling over a distance of more than 3 nm. The electronic coupling is manifested in both the absorption spectrum and an ultrafast rate for photoinduced electron transfer (k(PET) = 1.0 × 10(12) s(-1)). The charge-shifted state in ZnPc-OPE-AuP(+) recombines with a relatively low rate (k(BET) = 1.0 × 10(9) s(-1)). In contrast, the rate for charge transfer in the other dyad, ZnPc-OPE-C(60), is relatively slow (k(PET) = 1.1 × 10(9) s(-1)), while the recombination is very fast (k(BET) ≈ 5 × 10(10) s(-1)). TD-DFT calculations support the hypothesis that the long-lived charge-shifted state of ZnPc-OPE-AuP(+) is due to relaxation of the reduced gold porphyrin from a porphyrin ring based reduction to a gold centered reduction. This is in contrast to the faster recombination in the tin(IV) porphyrin based system (k(BET) = 1.2 × 10(10) s(-1)), where the excess electron is instead delocalized over the porphyrin ring.

  2. Communication: Charge transfer dominates over proton transfer in the reaction of nitric acid with gas-phase hydrated electrons

    Science.gov (United States)

    Lengyel, Jozef; Med, Jakub; Slavíček, Petr; Beyer, Martin K.

    2017-09-01

    The reaction of HNO3 with hydrated electrons (H2O)n- (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH-(H2O)m is formed primarily via a reaction of the hydrated electron with HNO3 inside the cluster, while proton transfer is not observed and NO3-(H2O)m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol-1. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

  3. Evolution of the angular distribution of laser-generated fast electrons due to resistive self-collimation

    Science.gov (United States)

    Robinson, A. P. L.; Schmitz, H.

    2015-10-01

    The evolution of the angular distribution of laser-generated fast electrons propagating in dense plasmas is studied by 3D numerical simulations. As resistively generated magnetic fields can strongly influence and even pinch the fast electron beam, the question of the effect on the angular distribution is of considerable interest. It was conjectured that in the limit of strong collimation, there will only be minimal changes to the angular distribution, whereas the largest reduction in the angular distribution will occur where there is only modest pinching of the fast electron beam and the beam is able to expand considerably. The results of the numerical simulations indicate this conjecture.

  4. Measuring fast electron spectra and laser absorption in relativistic laser-solid interactions using differential bremsstrahlung photon detectors

    CERN Document Server

    Scott, R H H; Perez, F; Streeter, M J V; Davies, J R; Schlenvoigt, H -P; Santos, J J; Hulin, S; Lancaster, K L; Baton, S D; Rose, S J; Norreys, P A

    2013-01-01

    A photon detector suitable for the measurement of bremsstrahlung spectra generated in relativistically-intense laser-solid interactions is described. The Monte Carlo techniques used to back-out the fast electron spectrum and laser energy absorbed into fast electrons are detailed. A relativistically-intense laser-solid experiment using frequency doubled laser light is used to demonstrate the effective operation of the detector. The experimental data was interpreted using the 3-spatial-dimension Monte Carlo code MCNPX (Pelowitz 2008), and the fast electron temperature found to be 125 keV.

  5. Measuring fast electron spectra and laser absorption in relativistic laser-solid interactions using differential bremsstrahlung photon detectors.

    Science.gov (United States)

    Scott, R H H; Clark, E L; Pérez, F; Streeter, M J V; Davies, J R; Schlenvoigt, H-P; Santos, J J; Hulin, S; Lancaster, K L; Baton, S D; Rose, S J; Norreys, P A

    2013-08-01

    A photon detector suitable for the measurement of bremsstrahlung spectra generated in relativistically intense laser-solid interactions is described. The Monte Carlo techniques used to extract the fast electron spectrum and laser energy absorbed into forward-going fast electrons are detailed. A relativistically intense laser-solid experiment using frequency doubled laser light is used to demonstrate the effective operation of the detector. The experimental data were interpreted using the 3-spatial-dimension Monte Carlo code MCNPX [D. Pelowitz, MCNPX User's Manual Version 2.6.0, Los Alamos National Laboratory, 2008], and the fast electron temperature found to be 125 keV.

  6. Cherenkov-type diagnostics of fast electrons beams escaping from MCF facilities

    Energy Technology Data Exchange (ETDEWEB)

    Jakubowski, L.; Malinowski, K.; Mirowski, R.; Rabinski, M.; Sadowski, M.J.; Zebrowski, J. [Institute for Nuclear Studies - IPJ, 05-400 Otwock-Swierk (Poland)

    2011-07-01

    The paper presents the feasibility study, the measuring system and the first experimental results of a new method developed for direct detection of high-energy (super-thermal, ripple-born and runaway) electrons generated in magnetic confinement fusion (MCF) facilities. The technique in question is based on registration of the Cherenkov radiation, emitted by energetic electrons, moving through a transparent medium (radiator) with a velocity higher than the velocity of light in this material. The main aim of our studies was to develop a diagnostic technique applicable for measurements of fast electron beams within MCF devices. The IPJ team proposed Cherenkov-type probes because of their high spatial- and temporal-resolutions. The most important results of applications of the presented Cherenkov-type diagnostics have proved that the one- and four-channel versions of the detecting head are useful for studies of the fast (ripple-born and runaway) electrons in different MCF experiments. Experience collected during the described studies allows to introduce some changes in the radiator configuration and to modify the Cherenkov probe design. This document is composed of a paper followed by a poster

  7. A Comparison of Electron-Transfer Dynamics inIonic Liquids and Neutral Solvents

    Energy Technology Data Exchange (ETDEWEB)

    Wishart J. F.; Lee, H.Y.; Issa, J.B.; Isied, S.S.; Castner, Jr., E.W.; Pan, Y.; Hussey, C.L.; Lee, K.S.

    2012-03-01

    The effect of ionic liquids on photoinduced electron-transfer reactions in a donor-bridge-acceptor system is examined for two ionic liquid solvents, 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide and tributylmethylammonium bis(trifluoromethylsulfonyl)amide. The results are compared with those for the same system in methanol and acetonitrile solution. Electron-transfer rates were measured using time-resolved fluorescence quenching for the donor-bridge-acceptor system comprising a 1-N,1-N-dimethylbenzene-1,4-diamine donor, a proline bridge, and a coumarin 343 acceptor. The photoinduced electron-transfer processes are in the inverted regime (-{Delta}G > {lambda}) in all four solvents, with driving forces of -1.6 to -1.9 eV and estimated reorganization energies of about 1.0 eV. The observed electron-transfer kinetics have broadly distributed rates that are generally slower in the ionic liquids compared to the neutral solvents, which also have narrower rate distributions. To describe the broad distributions of electron-transfer kinetics, we use two different models: a distribution of exponential lifetimes and a discrete sum of exponential lifetimes. Analysis of the donor-acceptor electronic coupling shows that for ionic liquids this intramolecular electron-transfer reaction should be treated using a solvent-controlled electron-transfer model.

  8. Redox potential of the terminal quinone electron acceptor QB in photosystem II reveals the mechanism of electron transfer regulation.

    Science.gov (United States)

    Kato, Yuki; Nagao, Ryo; Noguchi, Takumi

    2016-01-19

    Photosystem II (PSII) extracts electrons from water at a Mn4CaO5 cluster using light energy and then transfers them to two plastoquinones, the primary quinone electron acceptor QA and the secondary quinone electron acceptor QB. This forward electron transfer is an essential process in light energy conversion. Meanwhile, backward electron transfer is also significant in photoprotection of PSII proteins. Modulation of the redox potential (Em) gap of QA and QB mainly regulates the forward and backward electron transfers in PSII. However, the full scheme of electron transfer regulation remains unresolved due to the unknown Em value of QB. Here, for the first time (to our knowledge), the Em value of QB reduction was measured directly using spectroelectrochemistry in combination with light-induced Fourier transform infrared difference spectroscopy. The Em(QB (-)/QB) was determined to be approximately +90 mV and was virtually unaffected by depletion of the Mn4CaO5 cluster. This insensitivity of Em(QB (-)/QB), in combination with the known large upshift of Em(QA (-)/QA), explains the mechanism of PSII photoprotection with an impaired Mn4CaO5 cluster, in which a large decrease in the Em gap between QA and QB promotes rapid charge recombination via QA (-).

  9. Redox potential of the terminal quinone electron acceptor QB in photosystem II reveals the mechanism of electron transfer regulation

    Science.gov (United States)

    Kato, Yuki; Nagao, Ryo; Noguchi, Takumi

    2016-01-01

    Photosystem II (PSII) extracts electrons from water at a Mn4CaO5 cluster using light energy and then transfers them to two plastoquinones, the primary quinone electron acceptor QA and the secondary quinone electron acceptor QB. This forward electron transfer is an essential process in light energy conversion. Meanwhile, backward electron transfer is also significant in photoprotection of PSII proteins. Modulation of the redox potential (Em) gap of QA and QB mainly regulates the forward and backward electron transfers in PSII. However, the full scheme of electron transfer regulation remains unresolved due to the unknown Em value of QB. Here, for the first time (to our knowledge), the Em value of QB reduction was measured directly using spectroelectrochemistry in combination with light-induced Fourier transform infrared difference spectroscopy. The Em(QB−/QB) was determined to be approximately +90 mV and was virtually unaffected by depletion of the Mn4CaO5 cluster. This insensitivity of Em(QB−/QB), in combination with the known large upshift of Em(QA−/QA), explains the mechanism of PSII photoprotection with an impaired Mn4CaO5 cluster, in which a large decrease in the Em gap between QA and QB promotes rapid charge recombination via QA−. PMID:26715751

  10. Hybrid Simulation of Laser-Plasma Interactions and Fast Electron Transport in Inhomogeneous Plasma

    Energy Technology Data Exchange (ETDEWEB)

    Cohen, B I; Kemp, A; Divol, L

    2009-05-27

    A new framework is introduced for kinetic simulation of laser-plasma interactions in an inhomogenous plasma motivated by the goal of performing integrated kinetic simulations of fast-ignition laser fusion. The algorithm addresses the propagation and absorption of an intense electromagnetic wave in an ionized plasma leading to the generation and transport of an energetic electron component. The energetic electrons propagate farther into the plasma to much higher densities where Coulomb collisions become important. The high-density plasma supports an energetic electron current, return currents, self-consistent electric fields associated with maintaining quasi-neutrality, and self-consistent magnetic fields due to the currents. Collisions of the electrons and ions are calculated accurately to track the energetic electrons and model their interactions with the background plasma. Up to a density well above critical density, where the laser electromagnetic field is evanescent, Maxwell's equations are solved with a conventional particle-based, finite-difference scheme. In the higher-density plasma, Maxwell's equations are solved using an Ohm's law neglecting the inertia of the background electrons with the option of omitting the displacement current in Ampere's law. Particle equations of motion with binary collisions are solved for all electrons and ions throughout the system using weighted particles to resolve the density gradient efficiently. The algorithm is analyzed and demonstrated in simulation examples. The simulation scheme introduced here achieves significantly improved efficiencies.

  11. Eddy covariance flux measurements of ammonia by electron transfer reaction-mass spectrometry

    Directory of Open Access Journals (Sweden)

    J. Sintermann

    2010-11-01

    Full Text Available A system for fast ammonia (NH3 measurements based on a commercial Proton Transfer Reaction-Mass Spectrometer is presented. It uses electron transfer reaction (eTR as ionisation pathway and features a drift tube of polyetheretherketone (PEEK and silica-coated steel. Heating the instrumental inlet and the drift tube to 180° C enabled an effective time resolution of ~1 s and made it possible to apply the eTR-MS for eddy covariance (EC measurements. EC fluxes of NH3 were measured over two agricultural fields in Oensingen, Switzerland, following fertilisations with cattle slurry. Air was aspirated close to a sonic anemometer at a flow of 100 STP L min−1 and was directed through a 23 m long 1/2" PFA tube heated to 150°C to an air-conditioned trailer where the eTR-MS sub-sampled from the large bypass stream. This setup minimised damping of fast NH3 concentration changes between the sampling point and the actual measurement. High-frequency attenuation loss of the NH3 fluxes of 20 to 40% was quantified and corrected for using an empirical ogive method. The instrumental NH3 background signal showed a minor interference with H2O which was characterised in the laboratory. The resulting correction of the NH3 flux after slurry spreading was less than 1‰. The flux detection limit of the EC system was about 5 ng m−2 s−1 while the accuracy of individual flux measurements was estimated 16% for the high-flux regime during these experiments. The NH3 emissions after broad spreading of the slurry showed an initial maximum of 150 μg m2 s−1 with a fast decline in the following hours.

  12. Optically Forbidden Excitations of 3s Electron of Argon by Fast Electron Impact

    Institute of Scientific and Technical Information of China (English)

    朱林繁; 成华东; 刘小井; 田鹏; 苑震生; 李文斌; 徐克尊

    2003-01-01

    The electron energy loss spectrum of argon in the energy region of 24.5-30.5eV was measured at 2.5 keV impact energy. The line profile parameters of the optically forbidden excitations of 3s-1ns (n = 4-6) and 3s-1nd (n = 3-7) of argon, I.e.,Eγ,Г,q and p,were determined.

  13. 77 FR 50243 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-08-20

    ... From the Federal Register Online via the Government Publishing Office ] Vol. 77 Monday, No. 161... that many senders scheduling preauthorized remittance transfers are more concerned with the convenience... than with comparison shopping with pre-payment disclosures for each transfer. Thus, these commenters...

  14. Excess-Electron Transfer in DNA by a Fluctuation-Assisted Hopping Mechanism.

    Science.gov (United States)

    Lin, Shih-Hsun; Fujitsuka, Mamoru; Majima, Tetsuro

    2016-02-04

    The dynamics of excess-electron transfer in DNA has attracted the attention of scientists from all kinds of research fields because of its importance in biological processes. To date, several studies on excess-electron transfer in consecutive adenine (A):thymine (T) sequences in donor-DNA-acceptor systems have been published. However, the reported excess-electron transfer rate constants for consecutive T's are in the range of 10(10)-10(11) s(-1) depending on the photosensitizing electron donor, which provides various driving forces for excess-electron injection into DNA. In this study, we employed a strongly electron-donating photosensitizer, a dimer of 3,4-ethylenedioxythiophene (2E), and an electron acceptor, diphenylacetylene (DPA), to synthesize a series of modified DNA oligomers (2-Tn, n = 3-6) in order to investigate the excess-electron transfer dynamics in these donor-DNA-acceptor systems using femtosecond laser flash photolysis. The relation between the free energy change for charge injection and the excess-electron transfer rate among consecutive T's provided an intrinsic excess-electron hopping rate constant of (3.8 ± 1.5) × 10(10) s(-1) in the DNA, which is consistent with the fluctuation frequency of the DNA sugar backbone and bases (3.3 × 10(10) s(-1)). Thus, we discuss the effect of structural fluctuations on the excess-electron hopping in DNA.

  15. Where Does the Electron Go? Stable and Metastable Peptide Cation Radicals Formed by Electron Transfer

    Science.gov (United States)

    Pepin, Robert; Layton, Erik D.; Liu, Yang; Afonso, Carlos; Tureček, František

    2017-01-01

    Electron transfer to doubly and triply charged heptapeptide ions containing polar residues Arg, Lys, and Asp in combination with nonpolar Gly, Ala, and Pro or Leu generates stable and metastable charge-reduced ions, (M + 2H)+●, in addition to standard electron-transfer dissociation (ETD) fragment ions. The metastable (M + 2H)+● ions spontaneously dissociate upon resonant ejection from the linear ion trap, giving irregularly shaped peaks with offset m/ z values. The fractions of stable and metastable (M + 2H)+● ions and their mass shifts depend on the presence of Pro-4 and Leu-4 residues in the peptides, with the Pro-4 sequences giving larger fractions of the stable ions while showing smaller mass shifts for the metastables. Conversion of the Asp and C-terminal carboxyl groups to methyl esters further lowers the charge-reduced ion stability. Collisional activation and photodissociation at 355 nm of mass-selected (M + 2H)+● results in different dissociations that give sequence specific MS3 spectra. With a single exception of charge-reduced (LKGLADR + 2H)+●, the MS3 spectra do not produce ETD sequence fragments of the c and z type. Hence, these (M + 2H)+● ions are covalent radicals, not ion-molecule complexes, undergoing dramatically different dissociations in the ground and excited electronic states. The increased stability of the Pro-4 containing (M + 2H)+● ions is attributed to radicals formed by opening of the Pro ring and undergoing further stabilization by hydrogen atom migrations. UV-VIS photodissociation action spectroscopy and time-dependent density functional theory calculations are used in a case in point study of the stable (LKGPADR + 2H)+● ion produced by ETD. In contrast to singly-reduced peptide ions, doubly reduced (M + 3H)+ ions are stable only when formed from the Pro-4 precursors and show all characteristics of even electron ions regarding no photon absorption at 355 nm or ion-molecule reactions, and exhibiting proton driven

  16. Semiclassical study of quantum coherence and isotope effects in ultrafast electron transfer reactions coupled to a proton and a phonon bath.

    Science.gov (United States)

    Venkataraman, Charulatha

    2011-11-28

    The linearized semiclassical initial value representation is employed to describe ultrafast electron transfer processes coupled to a phonon bath and weakly coupled to a proton mode. The goal of our theoretical investigation is to understand the influence of the proton on the electronic dynamics in various bath relaxation regimes. More specifically, we study the impact of the proton on coherences and analyze if the coupling to the proton is revealed in the form of an isotope effect. This will be important in distinguishing reactions in which the proton does not undergo significant rearrangement from those in which the electron transfer is accompanied by proton transfer. Unlike other methodologies widely employed to describe nonadiabatic electron transfer, this approach treats the electronic and nuclear degrees of freedom consistently. However, due to the linearized approximation, quantum interference effects are not captured accurately. Our study shows that at small phonon bath reorganization energies, coherent oscillations and isotope effect are observed in both slow and fast bath regimes. The coherences are more substantially damped by deuterium in comparison to the proton. Further, in contrast to the dynamics of the spin-boson model, the coherences are not long-lived. At large bath reorganization energies, the decay is incoherent in the slow and fast bath regimes. In this case, the extent of the isotope effect depends on the relative relaxation timescales of the proton mode and the phonon bath. The isotope effect is magnified for baths that relax on picosecond timescales in contrast to baths that relax in femtoseconds.

  17. Fast earthward flows, electron cyclotron harmonic waves, and diffuse auroras: Conjunctive observations and a synthesized scenario

    Science.gov (United States)

    Liang, Jun; Ni, B.; Spanswick, E.; Kubyshkina, M.; Donovan, E. F.; Uritsky, V. M.; Thorne, R. M.; Angelopoulos, V.

    2011-12-01

    We present in this paper multi-instrumental observations and analyses of fast earthward flows, electrostatic electron cyclotron harmonic (ECH) waves, and diffuse auroras, during 8-9 UT on February 5, 2009. The event began with a series of fast earthward flows detected on mid-tail probe THEMIS-C. Subsequently, magnetic dipolarizations and strong ECH wave intensifications were observed on THEMIS-D/E probes at L ˜ 11 in the equatorial plasma sheet. Concurrently, Ground optical instruments detected diffuse auroral intensifications in the region surrounding the ionospheric footprints of the THEMIS probes. Together with the theoretical simulation performed by Ni et al. (2011e), we establish a causal conjunction between the ECH waves and diffuse auroras for the reported event. We also propose that the ECH wave and diffuse auroral intensification were likely triggered by the fast flow activity from the mid-tail and its resulting magnetic dipolarization. We discuss possible mechanisms linking the fast flow and its associated dipolarization to the intensification of ECH wave and diffuse aurora in the outer magnetosphere.

  18. Studies on electron transfer reactions of Keggin-type mixed addenda heteropolytungstovanadophosphates with NADH

    Indian Academy of Sciences (India)

    Ponnusamy Sami; Kasi Rajasekaran

    2009-03-01

    The coenzyme nicotinamide adenine dinucleotide (NADH) undergoes facile electron transfer reaction with vanadium (V) substituted Keggin-type heteropolyanions (HPA) [PVVW11O40]4- (PV1) and [PV$^{V}_{2}$W10O40]5- (PV2) in aqueous phosphate buffer of pH 6 at ambient temperature. Electrochemical and optical studies show that the stoichiometry of the reaction is 1 : 2 (NADH : HPA). EPR and optical studies show that HPA act as one electron acceptor and the products of electron transfer reactions are one electron reduced heteropoly blues (HPB), viz. [PVIVW11O40]5- and [PVIVVVW10O40]6-. Oxygraph measurements show that there is no uptake of molecular oxygen during the course of reaction. The reaction proceeds through multi-step electron-proton-electron transfer mechanism, with rate limiting initial one electron transfer from NADH to HPA by outer sphere electron transfer process. Bimolecular rate constant for electron transfer reaction between NADH and PV2 in phosphate buffer of pH = 6 has been determined spectrophotometrically.

  19. Electron transfer and catalysis with high-valent metal-oxo complexes.

    Science.gov (United States)

    Fukuzumi, Shunichi

    2015-04-21

    High-valent metal-oxo complexes are produced by reductive activation of dioxygen via reduction of metal complexes with reductants and dioxygen. Photoinduced electron transfer from substrates to metal complexes with dioxygen also leads to the generation of high-valent metal-oxo complexes that can oxygenate substrates. In such a case metal complexes act as a photocatalyst to oxygenate substrates with dioxygen. High-valent metal-oxo complexes are also produced by proton-coupled electron-transfer oxidation of metal complexes by one-electron oxidants with water, oxygenating substrates to regenerate metal complexes. In such a case metal complexes act as a catalyst for electron-transfer oxygenation of substrates by one-electron oxidants with water that acts as an oxygen source. The one-electron oxidants which can oxidize metal complexes can be replaced by much weaker oxidants by a combination of redox photocatalysts and metal complexes. Thus, photocatalytic oxygenation of substrates proceeds via photoinduced electron transfer from a photocatalyst to reductants followed by proton-coupled electron transfer oxidation of metal complexes with the oxidized photocatalyst to produce high-valent metal-oxo complexes that oxygenate substrates. Thermal and photoinduced electron-transfer catalytic reactions of high-valent metal-oxo complexes for oxygenation of substrates using water or dioxygen as an oxygen source are summarized in this perspective.

  20. Vlasov-Fokker-Planck simulations of fast-electron transport with hydrodynamic plasma response

    Energy Technology Data Exchange (ETDEWEB)

    Kingham, R J; Sherlock, M; Ridgers, C P; Evans, R G, E-mail: rj.kingham@imperial.ac.u [Plasma Physics Group, Imperial College London, London SW7 2AZ (United Kingdom)

    2010-08-01

    We report on kinetic simulations of the transport of laser-produced relativistic electron beams (REB) through solid-density plasma, including the hydrodynamic response of the plasma. We consider REBs with parameters relevant to fast-ignition of compressed inertial confinement fusion capsules. We show that over the 10-20ps timescales required for fast-ignition, thermal pressure (from Ohmic heating) can significantly modify the density which in turn strongly affects the propagation of injected fast-electrons; it allows them to re-collimate into a narrow, intense beam under conditions where they initially undergo beam-hollowing. Similar static-density calculations do not show re-collimation. The re-collimation effect is attributed to PdV cooling in the pressure-induced density-channel, which in turn suppresses defocusing magnetic fields generated by resistivity gradients. These simulations have been carried out using the new 2D-3V Vlasov-Fokker-Planck (VFP) code FIDO running in hybrid mode.

  1. Sensitisation of Eu(III)- and Tb(III)-based luminescence by Ir(III) units in Ir/lanthanide dyads: evidence for parallel energy-transfer and electron-transfer based mechanisms.

    Science.gov (United States)

    Sykes, Daniel; Cankut, Ahmet J; Ali, Noorshida Mohd; Stephenson, Andrew; Spall, Steven J P; Parker, Simon C; Weinstein, Julia A; Ward, Michael D

    2014-05-07

    A series of blue-luminescent Ir(III) complexes with a pendant binding site for lanthanide(III) ions has been synthesized and used to prepare Ir(III)/Ln(III) dyads (Ln = Eu, Tb, Gd). Photophysical studies were used to establish mechanisms of Ir→Ln (Ln = Tb, Eu) energy-transfer. In the Ir/Gd dyads, where direct Ir→Gd energy-transfer is not possible, significant quenching of Ir-based luminescence nonetheless occurred; this can be ascribed to photoinduced electron-transfer from the photo-excited Ir unit (*Ir, (3)MLCT/(3)LC excited state) to the pendant pyrazolyl-pyridine site which becomes a good electron-acceptor when coordinated to an electropositive Gd(III) centre. This electron transfer quenches the Ir-based luminescence, leading to formation of a charge-separated {Ir(4+)}˙-(pyrazolyl-pyridine)˙(-) state, which is short-lived possibly due to fast back electron-transfer (transfer pathway is again operative and leads to sensitisation of Eu-based and Tb-based emission using the energy liberated from the back electron-transfer process. In addition direct Dexter-type Ir→Ln (Ln = Tb, Eu) energy-transfer occurs on a similar timescale, meaning that there are two parallel mechanisms by which excitation energy can be transferred from *Ir to the Eu/Tb centre. Time-resolved luminescence measurements on the sensitised Eu-based emission showed both fast and slow rise-time components, associated with the PET-based and Dexter-based energy-transfer mechanisms respectively. In the Ir/Tb dyads, the Ir→Tb energy-transfer is only just thermodynamically favourable, leading to rapid Tb→Ir thermally-activated back energy-transfer and non-radiative deactivation to an extent that depends on the precise energy gap between the *Ir and Tb-based (5)D4 states. Thus, the sensitised Tb(iii)-based emission is weak and unusually short-lived due to back energy transfer, but nonetheless represents rare examples of Tb(III) sensitisation by a energy donor that could be excited using visible

  2. Multislice theory of fast electron scattering incorporating atomic inner-shell ionization.

    Science.gov (United States)

    Dwyer, C

    2005-09-01

    It is demonstrated how atomic inner-shell ionization can be incorporated into a multislice theory of fast electron scattering. The resulting theory therefore accounts for both inelastic scattering due to inner-shell ionization and dynamical elastic scattering. The theory uses a description of the ionization process based on the angular momentum representation for both the initial and final states of the atomic electron. For energy losses near threshold, only a small number of independent states of the ejected atomic electron need to be considered, reducing demands on computing time, and eliminating the need for tabulated inelastic scattering factors. The theory is used to investigate the influence of the collection aperture size on the spatial origin of the silicon K-shell EELS signal generated by a STEM probe. The validity of a so-called local approximation is also considered.

  3. Concerted proton-coupled electron transfer from a metal-hydride complex.

    Science.gov (United States)

    Bourrez, Marc; Steinmetz, Romain; Ott, Sascha; Gloaguen, Frederic; Hammarström, Leif

    2014-02-01

    Metal hydrides are key intermediates in the catalytic reduction of protons and CO2 as well as in the oxidation of H2. In these reactions, electrons and protons are transferred to or from separate acceptors or donors in bidirectional protoncoupled electron transfer (PCET) steps. The mechanistic interpretation of PCET reactions of metal hydrides has focused on the stepwise transfer of electrons and protons. A concerted transfer may, however, occur with a lower reaction barrier and therefore proceed at higher catalytic rates. Here we investigate the feasibility of such a reaction by studying the oxidation–deprotonation reactions of a tungsten hydride complex. The rate dependence on the driving force for both electron transfer and proton transfer—employing different combinations of oxidants and bases—was used to establish experimentally the concerted, bidirectional PCET of a metal-hydride species. Consideration of the findings presented here in future catalyst designs may lead to more-efficient catalysts.

  4. Mitigation of corrosion and mass transfer in sodium-cooled fast reactors

    Energy Technology Data Exchange (ETDEWEB)

    Latge, C. [CEA Cadarache, Dir. de l' Energie Nucleaire, 13 - Saint-Paul-lez-Durance (France); Feron, D. [CEA Saclay, Dir. de l' Energie Nucleaire, 91 - Gif-sur-Yvette (France)

    2009-07-01

    Full text of publication follows: Several coolants can be used for the development of the Fast Reactors, as sodium, gas, lead or lead-bismuth eutectic, and have been selected in the Generation IV forum. The high density energy requires a coolant with a very good thermal conductivity. Liquid sodium is such a medium which is liquid between 97.8 up to 880 C at dynamic pressure below 4 bars, and with compatible neutron-physical properties. Its viscosity is comparable to that of water and its compatibility with metallic materials is fairly satisfactory. It is however necessary to keep the conditions of operation within a range such that corrosion is limited. Several materials are suitable for use in liquid sodium reactors, among ferritic and austenitic steels and high temperature alloys with up to 32% nickel contents. The designer has however to consider the mass transfer between materials of different compositions. The exchange and transfer of non-metallic elements such as carbon or nitrogen has to be taken into account. The corrosion mechanisms of austenitic steels have been extensively studied and described in the literature: surface cleaning, austenitic dissolution, formation of a ferrite layer, steady state equilibrium and several models have been proposed: main parameters include oxygen content, sodium velocity and steel temperature. Operating experience has shown that, if there are no cladding failures, the main source of radioactivity in the primary circuit is the activated corrosion products, like {sup 54}Mn, {sup 51}Cr,..., induced by the activation of core materials which are dissolved into the sodium and mainly deposited in the coldest parts of the reactor i.e. the Intermediate Heat Exchanger (IHX) and pumps. Radio-cobalt such as {sup 60}Co are also produced and a low fraction is deposited in primary components. The corrosion rates estimated and the contamination induced by activated corrosion products observed in SFR like Phenix, JOYO, BN600, PFR, EBR2 have

  5. High throughput electron transfer from carbon dots to chloroplast: a rationale of enhanced photosynthesis

    Science.gov (United States)

    Chandra, Sourov; Pradhan, Saheli; Mitra, Shouvik; Patra, Prasun; Bhattacharya, Ankita; Pramanik, Panchanan; Goswami, Arunava

    2014-03-01

    A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH).A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH). Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr06079a

  6. Enhanced Performance of Dye-Sensitized Solar Cells with Nanostructure Graphene Electron Transfer Layer

    Directory of Open Access Journals (Sweden)

    Chih-Hung Hsu

    2014-01-01

    Full Text Available The utilization of nanostructure graphene thin films as electron transfer layer in dye-sensitized solar cells (DSSCs was demonstrated. The effect of a nanostructure graphene thin film in DSSC structure was examined. The nanostructure graphene thin films provides a great electron transfer channel for the photogenerated electrons from TiO2 to indium tin oxide (ITO glass. Obvious improvements in short-circuit current density of the DSSCs were observed by using the graphene electron transport layer modified photoelectrode. The graphene electron transport layer reduces effectively the back reaction in the interface between the ITO transparent conductive film and the electrolyte in the DSSC.

  7. Fast variability of tera-electron volt gamma rays from the radio galaxy M87.

    Science.gov (United States)

    Aharonian, F; Akhperjanian, A G; Bazer-Bachi, A R; Beilicke, M; Benbow, W; Berge, D; Bernlöhr, K; Boisson, C; Bolz, O; Borrel, V; Braun, I; Brown, A M; Bühler, R; Büsching, I; Carrigan, S; Chadwick, P M; Chounet, L-M; Coignet, G; Cornils, R; Costamante, L; Degrange, B; Dickinson, H J; Djannati-Ataï, A; Drury, L O'c; Dubus, G; Egberts, K; Emmanoulopoulos, D; Espigat, P; Feinstein, F; Ferrero, E; Fiasson, A; Fontaine, G; Funk, Seb; Funk, S; Füssling, M; Gallant, Y A; Giebels, B; Glicenstein, J F; Goret, P; Hadjichristidis, C; Hauser, D; Hauser, M; Heinzelmann, G; Henri, G; Hermann, G; Hinton, J A; Hoffmann, A; Hofmann, W; Holleran, M; Hoppe, S; Horns, D; Jacholkowska, A; de Jager, O C; Kendziorra, E; Kerschhaggl, M; Khélifi, B; Komin, Nu; Konopelko, A; Kosack, K; Lamanna, G; Latham, I J; Le Gallou, R; Lemière, A; Lemoine-Goumard, M; Lenain, J-P; Lohse, T; Martin, J M; Martineau-Huynh, O; Marcowith, A; Masterson, C; Maurin, G; McComb, T J L; Moulin, E; de Naurois, M; Nedbal, D; Nolan, S J; Noutsos, A; Orford, K J; Osborne, J L; Ouchrif, M; Panter, M; Pelletier, G; Pita, S; Pühlhofer, G; Punch, M; Ranchon, S; Raubenheimer, B C; Raue, M; Rayner, S M; Reimer, A; Ripken, J; Rob, L; Rolland, L; Rosier-Lees, S; Rowell, G; Sahakian, V; Santangelo, A; Saugé, L; Schlenker, S; Schlickeiser, R; Schröder, R; Schwanke, U; Schwarzburg, S; Schwemmer, S; Shalchi, A; Sol, H; Spangler, D; Spanier, F; Steenkamp, R; Stegmann, C; Superina, G; Tam, P H; Tavernet, J-P; Terrier, R; Tluczykont, M; van Eldik, C; Vasileiadis, G; Venter, C; Vialle, J P; Vincent, P; Völk, H J; Wagner, S J; Ward, M

    2006-12-01

    The detection of fast variations of the tera-electron volt (TeV) (10(12) eV) gamma-ray flux, on time scales of days, from the nearby radio galaxy M87 is reported. These variations are about 10 times as fast as those observed in any other wave band and imply a very compact emission region with a dimension similar to the Schwarzschild radius of the central black hole. We thus can exclude several other sites and processes of the gamma-ray production. The observations confirm that TeV gamma rays are emitted by extragalactic sources other than blazars, where jets are not relativistically beamed toward the observer.

  8. Sequential energy and electron transfer in a three-component system aligned on a clay nanosheet.

    Science.gov (United States)

    Fujimura, Takuya; Ramasamy, Elamparuthi; Ishida, Yohei; Shimada, Tetsuya; Takagi, Shinsuke; Ramamurthy, Vaidhyanathan

    2016-02-21

    To achieve the goal of energy transfer and subsequent electron transfer across three molecules, a phenomenon often utilized in artificial light harvesting systems, we have assembled a light absorber (that also serves as an energy donor), an energy acceptor (that also serves as an electron donor) and an electron acceptor on the surface of an anionic clay nanosheet. Since neutral organic molecules have no tendency to adsorb onto the anionic surface of clay, a positively charged water-soluble organic capsule was used to hold neutral light absorbers on the above surface. A three-component assembly was prepared by the co-adsorption of a cationic bipyridinium derivative, cationic zinc porphyrin and cationic octaamine encapsulated 2-acetylanthracene on an exfoliated anionic clay surface in water. Energy and electron transfer phenomena were monitored by steady state fluorescence and picosecond time resolved fluorescence decay. The excitation of 2-acetylanthracene in the three-component system resulted in energy transfer from 2-acetylanthracene to zinc porphyrin with 71% efficiency. Very little loss due to electron transfer from 2-acetylanthracene in the cavitand to the bipyridinium derivative was noticed. Energy transfer was followed by electron transfer from the zinc porphyrin to the cationic bipyridinium derivative with 81% efficiency. Analyses of fluorescence decay profiles confirmed the occurrence of energy transfer and subsequent electron transfer. Merging the concepts of supramolecular chemistry and surface chemistry we realized sequential energy and electron transfer between three hydrophobic molecules in water. Exfoliated transparent saponite clay served as a matrix to align the three photoactive molecules at a close distance in aqueous solutions.

  9. Allosteric control of internal electron transfer in cytochrome cd1 nitrite reductase

    DEFF Research Database (Denmark)

    Farver, Ole; Kroneck, Peter M H; Zumft, Walter G

    2003-01-01

    Cytochrome cd1 nitrite reductase is a bifunctional multiheme enzyme catalyzing the one-electron reduction of nitrite to nitric oxide and the four-electron reduction of dioxygen to water. Kinetics and thermodynamics of the internal electron transfer process in the Pseudomonas stutzeri enzyme have...

  10. Photoinduced electron transfer processes in oligothiophene/C60 composite films

    NARCIS (Netherlands)

    Janssen, R.A.J.; Christiaans, M.P.T.; Pakbaz, K.; Moses, D.; Hummelen, Jan C.; Sariciftci, N.S.

    1995-01-01

    We present near steady-state photoinduced absorption (PIA) spectroscopy and steady-state light-induced electron spin resonance (LESR) studies on photoinduced electron transfer reactions in composite films of well defined α-oligothiophenes (Tn, n=6, 7, 9, and 11) as electron donor with

  11. Photoinduced electron transfer processes in oligothiophene/C60 composite films

    NARCIS (Netherlands)

    Janssen, R.A.J.; Christiaans, M.P.T.; Pakbaz, K.; Moses, D.; Hummelen, Jan C.; Sariciftci, N.S.

    1995-01-01

    We present near steady-state photoinduced absorption (PIA) spectroscopy and steady-state light-induced electron spin resonance (LESR) studies on photoinduced electron transfer reactions in composite films of well defined α-oligothiophenes (Tn, n=6, 7, 9, and 11) as electron donor with buckminsterful

  12. High throughput electron transfer from carbon dots to chloroplast: a rationale of enhanced photosynthesis.

    Science.gov (United States)

    Chandra, Sourov; Pradhan, Saheli; Mitra, Shouvik; Patra, Prasun; Bhattacharya, Ankita; Pramanik, Panchanan; Goswami, Arunava

    2014-04-07

    A biocompatible amine functionalized fluorescent carbon dots were developed and isolated for gram scale applications. Such carbogenic quantum dots can strongly conjugate over the surface of the chloroplast and due to that strong interaction the former can easily transfer electrons towards the latter by assistance of absorbed light or photons. An exceptionally high electron transfer from carbon dots to the chloroplast can directly effect the whole chain electron transfer pathway in a light reaction of photosynthesis, where electron carriers play an important role in modulating the system. As a result, carbon dots can promote photosynthesis by modulating the electron transfer process as they are capable of fastening the conversion of light energy to the electrical energy and finally to the chemical energy as assimilatory power (ATP and NADPH).

  13. From charge transfer to electron transfer in halogen-bonded complexes of electrophilic bromocarbons with halide anions.

    Science.gov (United States)

    Rosokha, Sergiy V; Traversa, Alfredo

    2015-02-21

    Experimental and computational studies of the halogen-bonded complexes, [R-Br, X(-)], of bromosubstituted electrophiles, R-Br, and halide anions, X(-), revealed that decrease of a gap between the frontier orbitals of interacting species led to reduction of the energy of the optical charge-transfer transition and to increase in the ground-state charge transfer (X(-) → R-Br) in their associates. These variations were accompanied by weakening of the intramolecular, C-Br, and strengthening of the intermolecular, BrX(-), bonds. In the limit of the strongest electron donor-acceptor pairs, formation of the halogen-bonded complexes was followed by the oxidation of iodide to triiodide, which took place despite the fact that the I(-) → R-Br electron-transfer step was highly endergonic and the calculated outer-sphere rate constant was negligibly small. However, the calculated barrier for the inner-sphere electron transfer accompanied by the halogen transfer, R-BrI(-) → R˙Br-I(-)˙, was nearly 24 kcal mol(-1) lower as compared to that calculated for the outer-sphere process and the rate constant of such reaction was consistent with the experimental kinetics. A dramatic decrease of the electron-transfer barriers (leading to 18-orders of magnitude increase of the rate constant) was related to the strong electronic coupling of the donor and acceptor within the halogen-bonded precursor complex, as well as to the lower solvent reorganization energy and the successor-complex stabilization.

  14. Identification of fast particle triggered modes by means of correlation electron cyclotron emission on Tore Supra

    Energy Technology Data Exchange (ETDEWEB)

    Goniche, M.; Huysmans, G.T.A.; Turco, F.; Maget, P.; Segui, J.L.; Artaud, J.F.; Giruzzi, G.; Imbeaux, F.; Lotte, P.; Mazon, D.; Molina, D. [CEA Cadarache, Assoc EURATOM DRFC, SCCP, F-13108 St Paul Les Durance (France); Udintsev, V.S. [EPFL /SB/CRPP, Assoc EURATOM Confederat Suisse, CH-1015 Lausanne (Switzerland)

    2008-07-01

    Low-frequency (5- to 20-kHz) and high-frequency (40- to 200-kHz) modes are studied during radio-frequency heating experiments on the Tore Supra tokamak by means of correlation electron cyclotron emission. High-frequency modes are detected when the plasma is heated by ion cyclotron range of frequency waves in the minority D(H) heating scheme in combination with lower hybrid current drive (LHCD) producing a flat or slightly reversed q-profile. They are identified as Alfven cascade modes. When this mode is triggered, fast ion losses ({<=} 20%) are detected from the neutron emission rate, and an additional heat load on plasma-facing components can be measured by an infrared camera when the fast ion energy is sufficiently large. Low-frequency modes are commonly triggered during LHCD experiments performed at low loop voltage. This mode can be observed with moderate lower hybrid power when the q-profile is monotonic or at higher power when the q-profile is flat in the core (r/a {<=} 0.2) or reversed. It is identified, in most cases, as an electron fishbone-like mode. These modes can be stabilized by a slight modification of the q-profile provided by an increase of lower hybrid power or by a small addition of electron cyclotron current device. (authors)

  15. Study of fast electron transport and ionization in isochorically heated solid foil

    Science.gov (United States)

    Sawada, Hiroshi; Sentoku, Yasuhiko; Pandit, Rishi; Yabuuchi, Toshinori; Zastrau, Ulf; Foerster, Eckhart; Beg, Farhat; McLean, Harry; Chen, Hui; Park, J.-B.; Patel, Prav; Link, Anthony; Ping, Yuan

    2016-10-01

    Interaction of a high-power, short-pulse laser with a solid target generates a significant number of relativistic MeV electrons, subsequently heating the target isochorically in the transport process. Fast electron driven ionization of a solid titanium foil was studied by measuring Ti K-alpha x-rays and performing 2-D particle-in-cell simulations. The experiment was performed using the 50 TW Leopard short-pulse laser at UNR's Nevada Terawatt Facility. The 15 J, 0.35 ps laser was tightly focused on to a various sized, 2- μm thick Ti foil within a 8 μm spot to achieve the peak intensity of 2×1019 W/cm2. The transport of the fast electrons produced 4.51 keV Ti K-alpha x-rays. The yields and 2-D monochromatic images were recorded with a Bragg crystal spectrometer and a spherically bent crystal imager. The ionization degree of the heated foil was determined to be 15 from the ionized K-alpha lines and the missing emission in the images. 2-D PIC simulations using a PICLS code with a radiation transport module were performed to calculate the K-alpha profiles and spectra. Details of the experiment and comparison will be presented.

  16. Intramolecular electron transfer in cytochrome cd(1) nitrite reductase from Pseudomonas stutzeri; kinetics and thermodynamics

    DEFF Research Database (Denmark)

    Farver, Ole; Kroneck, Peter M H; Zumft, Walter G

    2002-01-01

    , internal electron transfer between these sites is an inherent element in the catalytic cycle of this enzyme. We have investigated the internal electron transfer reaction employing pulse radiolytically produced N-methyl nicotinamide radicals as reductant which reacts solely with the heme-c in an essentially...... diffusion controlled process. Following this initial step, the reduction equivalent is equilibrating between the c and d(1) heme sites in a unimolecular process (k=23 s(-1), 298 K, pH 7.0) and an equilibrium constant of 1.0. The temperature dependence of this internal electron transfer process has been...

  17. Theoretical Study of Electron Transfer in Bimolecular System of NH3 and H2O

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Mulliken, NPA, MK and CHelpG population analyses have been accomplished at the level of MP2/6-31G(d,p) for the title system. The variations of four kinds of charges on NH3 with intermolecular distance infer that electron transfers from NH3 to H2O. MK and CHelpG population analyses indicate more electron transfer than Mulliken and NPA ones. The atomic charges resulted from MK and CHelpG schemes infer that electron transfers from N in NH3 to H in H2O, which confirms that this bimolecular complex possesses linear structure as H3N…HOH.

  18. High-Mobility Two-Dimensional Electron Gases at ZnO/ZnMgO Interfaces for Ultra-Fast Electronics Applications

    Science.gov (United States)

    2014-11-17

    AFRL-AFOSR-UK-TR-2015-0007 High-mobility two-dimensional electron gases at ZnO /ZnMgO interfaces for ultra-fast electronics...two-dimensional electron gases at ZnO /ZnMgO interfaces for ultra-fast electronics applications 5a. CONTRACT NUMBER 5b. GRANT NUMBER FA8655-12...strain. This will necessitate the growth of a thin film of ZnO between the ZnO single crystal substrate and the ZnMgO thin film. 15

  19. Intermolecular electron transfer from intramolecular excitation and coherent acoustic phonon generation in a hydrogen-bonded charge-transfer solid

    Science.gov (United States)

    Rury, Aaron S.; Sorenson, Shayne; Dawlaty, Jahan M.

    2016-03-01

    Organic materials that produce coherent lattice phonon excitations in response to external stimuli may provide next generation solutions in a wide range of applications. However, for these materials to lead to functional devices in technology, a full understanding of the possible driving forces of coherent lattice phonon generation must be attained. To facilitate the achievement of this goal, we have undertaken an optical spectroscopic study of an organic charge-transfer material formed from the ubiquitous reduction-oxidation pair hydroquinone and p-benzoquinone. Upon pumping this material, known as quinhydrone, on its intermolecular charge transfer resonance as well as an intramolecular resonance of p-benzoquinone, we find sub-cm-1 oscillations whose dispersion with probe energy resembles that of a coherent acoustic phonon that we argue is coherently excited following changes in the electron density of quinhydrone. Using the dynamical information from these ultrafast pump-probe measurements, we find that the fastest process we can resolve does not change whether we pump quinhydrone at either energy. Electron-phonon coupling from both ultrafast coherent vibrational and steady-state resonance Raman spectroscopies allows us to determine that intramolecular electronic excitation of p-benzoquinone also drives the electron transfer process in quinhydrone. These results demonstrate the wide range of electronic excitations of the parent of molecules found in many functional organic materials that can drive coherent lattice phonon excitations useful for applications in electronics, photonics, and information technology.

  20. Time-dependent calculations of transfer ionization by fast proton-helium collision in one-dimensional kinematics

    OpenAIRE

    Serov, Vladislav V.; Kheifets, A. S.

    2014-01-01

    We analyze a transfer ionization (TI) reaction in the fast proton-helium collision $\\rm H^+ + He \\to H^0 + He^{2+} + e^-$ by solving a time-dependent Schr\\"odinger equation (TDSE) under the classical projectile motion approximation in one-dimensional kinematics. In addition, we construct various time independent analogues of our model using lowest order perturbation theory in the form of the Born series. By comparing various aspects of the TDSE and the Born series calculations, we conclude th...