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Sample records for intermolecular electron transfer

  1. Mechanism of Intermolecular Electron Transfer in Bionanostructures

    Science.gov (United States)

    Gruodis, A.; Galikova, N.; Šarka, K.; Saul?, R.; Batiuškait?, D.; Saulis, G.

    Hepatocellular carcinoma (HCC) is one of the most common malignant tumors worldwide. Most patients are inoperable and hepatoma cells are resistant to conventional chemotherapies. Thus, the development of novel therapies for HCC treatment is of paramount importance. Amongst different alimentary factors, vitamin C and vitamin K3 In the present work, it has been shown that the treatment of mouse hepatoma MH-22A cells by vitamin C and vitamin K3 at the ratio of 100:1 greatly enhanced their cytotoxicity. When cells were subjected to vitamin C at 200 ?M or to vitamin K3 at 2 ?M separately, their viability reduced by only about 10%. However, when vitamins C and K3 were combined at the same concentrations, they killed more than 90% of cells. To elucidate the mechanism of the synergistic cytotoxicity of the C&K3 mixture, theoretical quantum-chemical analysis of the dynamics of intermolecular electron transfer (IET) processes within the complexes containing C (five forms) and K3 (one form) has been carried out. Optimization of the ground state complex geometry has been provided by means of GAUSSIAN03 package. Simulation of the IET has been carried out using NUVOLA package, in the framework of molecular orbitals (MO). The rate of IET has been calculated using Fermi Golden rule. The results of simulations allow us to create the preliminary model of the reaction pathway.

  2. Electrochemical study of the intermolecular electron transfer to Pseudomonas aeruginosa cytochrome cd1 nitrite reductase

    International Nuclear Information System (INIS)

    The kinetics of electron transfer reaction between cytochrome cd1 nitrite reductase (NiR) from Pseudomonas aeruginosa and various physiological/non physiological redox partners was investigated using cyclic voltammetry at the pyrolytic graphite electrode. While NiR did not exchange electron with the electrode, cytochrome c551 and azurin, both from Ps. aeruginosa, behaved as fast electrochemical systems. The intermolecular electron transfers between NiR and cytochrome c551 or azurin as electron shuttles, in the presence of nitrite, were studied. Second order rate constants of 2x106 and 1.4x105 M-1 s-1 are calculated for cytochrome c551 and azurin, respectively. The dependence of the second-order rate constant on ionic strength and pH is discussed. Finally, the effect of the global charge of the electron shuttles was explored using differently charged species (proteins or small ions). The experimental results suggest involvement of polar interactions as well as of hydrophobic contacts in the protein recognition prior to the intermolecular electron transfer. As the cross-reaction between Ps. nautica cytochrome c552 and Ps. aeruginosa NiR was shown to be as efficient as the catalytic reaction involving the physiological partners, it is concluded to a 'pseudo-specificity' in the recognition between NiR and the electron donor

  3. Solvent and nuclear dynamics in ultrafast intermolecular electron transfer in a diffusionless, weakly polar system

    Science.gov (United States)

    Yartsev, Arkadiy; Nagasawa, Yutaka; Douhal, Abderrazzak; Yoshihara, Keitaro

    1993-05-01

    Femtosecond intermolecular electron (ET) transfer dynamics were studied by time-resolved fluorescence up-conversion technique in contact systems of oxazine dyes in electron-donating solvents. Clearly non-exponential ET time dependence was observed in aniline and explained by the effects of both solvent reorientation and nuclear motion of the reactants. Single exponential processes were measured for nile blue (?160 fs) and oxazine 1 (?280 fs) in N,N-dimethylaniline. The rate of ET is explained to be limited only by ultrafast nuclear relaxation.

  4. Photoinduced intermolecular electron transfer from aromatic amines to coumarin dyes in sodium dodecyl sulphate micellar solutions

    Science.gov (United States)

    Kumbhakar, Manoj; Nath, Sukhendu; Pal, Haridas; Sapre, Avinash V.; Mukherjee, Tulsi

    2003-07-01

    Photoinduced intermolecular electron transfer interaction between coumarin dyes and aromatic amines has been investigated in sodium dodecyl sulphate micellar solutions using steady-state and time-resolved fluorescence quenching measurements. Steady-state fluorescence quenching of the coumarin dyes by the amine quenchers always shows a positive deviation from linear Stern-Volmer relationship, which arises due to the localized high quencher concentrations at the micellar Stern layer. In time-resolved fluorescence measurements, the analysis of the fluorescence decays following a micellar quenching kinetics model assuming a unified quenching constant (kq') per quencher occupancy does not give satisfactory results, especially for the higher quencher concentrations used. The observed fluorescence decays are, however, seen to fit reasonably well following a bi-exponential analysis for all the quencher concentrations used. The average fluorescence lifetimes of the coumarin dyes in the micellar solution as estimated from the bi-exponential decay analysis are seen to undergo a systematic reduction with the effective mean quencher concentrations. The bimolecular quenching constants (kq) thus estimated are seen to be much smaller than those reported in the homogeneous solutions (e.g., in acetonitrile), indicating that the electron transfer in the micellar media is inherently inefficient. Correlation of the observed kq values in the micellar solutions with the free-energy changes (?G0) for electron transfer reactions show an inversion in the observed rates as predicted by Marcus' outer sphere electron transfer theory at exergonicities more that ˜0.65 eV. To the best of our knowledge this is the first report on the Marcus inverted region observed for the electron transfer reactions in micellar solution.

  5. Effect of donor orientation on ultrafast intermolecular electron transfer in coumarin-amine systems

    Science.gov (United States)

    Singh, P. K.; Nath, S.; Bhasikuttan, A. C.; Kumbhakar, M.; Mohanty, J.; Sarkar, S. K.; Mukherjee, T.; Pal, H.

    2008-09-01

    Effect of donor amine orientation on nondiffusive ultrafast intermolecular electron transfer (ET) reactions in coumarin-amine systems has been investigated using femtosecond fluorescence upconversion measurements. Intermolecular ET from different aromatic and aliphatic amines used as donor solvents to the excited coumarin-151 (C151) acceptor occurs with ultrafast rates such that the shortest fluorescence lifetime component (?1) is the measure of the fastest ET rate (?1=?ETfast=(kETfast)-1), assigned to the C151-amine contact pairs in which amine donors are properly oriented with respect to C151 to maximize the acceptor-donor electronic coupling (Vel). It is interestingly observed that as the amine solvents are diluted by suitable diluents (either keeping solvent dielectric constant similar or with increasing dielectric constant), the ?1 remains almost in the similar range as long as the amine dilution does not cross a certain critical limit, which in terms of the amine mole fraction (xA) is found to be ˜0.4 for aromatic amines and ˜0.8 for aliphatic amines. Beyond these dilutions in the two respective cases of the amine systems, the ?1 values are seen to increase very sharply. The large difference in the critical xA values involving aromatic and aliphatic amine donors has been rationalized in terms of the largely different orientational restrictions for the ET reactions as imposed by the aliphatic (n-type) and aromatic (?-type) nature of the amine donors [A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008)]. Since the highest occupied molecular orbital (HOMO) of the n-type aliphatic amines is mostly centralized at the amino nitrogen, only some specific orientations of these amines with respect to the close-contact acceptor dye [also of ?-character; A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008) and E. W. Castner et al., J. Phys. Chem. A 104, 2869 (2000)] can give suitable Vel and thus ultrafast ET reaction. In contrary, the HOMO of the ?-type aromatic amines is largely distributed throughout the whole molecule and thus most of the orientations of these amines can give significant Vel for ultrafast ET reactions with close-contact C151 dyes.

  6. Effect of donor orientation on ultrafast intermolecular electron transfer in coumarin-amine systems

    International Nuclear Information System (INIS)

    Effect of donor amine orientation on nondiffusive ultrafast intermolecular electron transfer (ET) reactions in coumarin-amine systems has been investigated using femtosecond fluorescence upconversion measurements. Intermolecular ET from different aromatic and aliphatic amines used as donor solvents to the excited coumarin-151 (C151) acceptor occurs with ultrafast rates such that the shortest fluorescence lifetime component (?1) is the measure of the fastest ET rate (?1=?ETfast=(kETfast)-1), assigned to the C151-amine contact pairs in which amine donors are properly oriented with respect to C151 to maximize the acceptor-donor electronic coupling (Vel). It is interestingly observed that as the amine solvents are diluted by suitable diluents (either keeping solvent dielectric constant similar or with increasing dielectric constant), the ?1 remains almost in the similar range as long as the amine dilution does not cross a certain critical limit, which in terms of the amine mole fraction (xA) is found to be ?0.4 for aromatic amines and ?0.8 for aliphatic amines. Beyond these dilutions in the two respective cases of the amine systems, the ?1 values are seen to increase very sharply. The large difference in the critical xA values involving aromatic and aliphatic amine donors has been rationalized in terms of the largely different orients of the largely different orientational restrictions for the ET reactions as imposed by the aliphatic (n-type) and aromatic (?-type) nature of the amine donors [A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008)]. Since the highest occupied molecular orbital (HOMO) of the n-type aliphatic amines is mostly centralized at the amino nitrogen, only some specific orientations of these amines with respect to the close-contact acceptor dye [also of ?-character; A. K. Satpati et al., J. Mol. Struct. 878, 84 (2008) and E. W. Castner et al., J. Phys. Chem. A 104, 2869 (2000)] can give suitable Vel and thus ultrafast ET reaction. In contrary, the HOMO of the ?-type aromatic amines is largely distributed throughout the whole molecule and thus most of the orientations of these amines can give significant Vel for ultrafast ET reactions with close-contact C151 dyes.

  7. Coupling of electrons to intermolecular phonons in molecular charge transfer dimers: A resonance Raman study

    Science.gov (United States)

    Pedron, D.; Speghini, A.; Mulloni, V.; Bozio, R.

    1995-08-01

    We report resonance Raman scattering (RRS) spectra and Raman excitation profiles (REP) of a system containing ? dimers of identical molecular radical ions measured with laser excitation in resonance with the charge transfer (CT) transition. A Peierls-Hubbard (PH) Hamiltonian has been used to model the investigated system and to calculate its optical and RRS properties. Results are reported for two polyoxometallate salts of tetrathiafulvalene (TTF), namely (TTF)2(W6O19) and (TTF)2(Mo6O19) whose structures contain almost isolated (TTF+)2 dimers. The RRS spectra of (TTF)2(W6O19), measured in resonance with the CT absorption band centered at 832 nm, show three phonon modes located at 55, 90, and 116 cm-1 which are strongly resonance enhanced. These modes have been associated to the out-of-phase combinations of the translational motions of the two molecules composing the dimer. Such modes are effective in modulating the intradimer transfer integral, thus providing an efficient mechanism for coupling with the electronic system and for enhancement of the scattering intensity at resonance with the CT transition. The REP for the three strongly coupled modes of (TTF)2(W6O19) have been measured with laser excitation wavelengths ranging from 740 to 930 nm. Quantitative analysis of the REP data has been performed based on a perturbative solution of the PH model to second order in the electron-molecular-vibration (EMV) and electron-intermolecular-phonon (EIP) interactions. The CT absorption profile and the REP's have been calculated using a time correlator technique and the model parameters have been optimized in order to fit the experimental REP data. Infrared vibronic absorptions of (TTF)2(W6O19), originated by the EMV coupling, have been measured and independent information on the electronic parameters of the PH model have been derived. This has made the choice of the fitting parameters used for the REP calculations rather unambiguous and has allowed us to obtain, for the first time, reliable experimental estimates of the EIP coupling constants.

  8. Electrochemical study of the intermolecular electron transfer to Pseudomonas aeruginosa cytochrome cd{sub 1} nitrite reductase

    Energy Technology Data Exchange (ETDEWEB)

    Lojou, E.; Cutruzzola, F.; Tegoni, M.; Bianco, P

    2003-04-05

    The kinetics of electron transfer reaction between cytochrome cd{sub 1} nitrite reductase (NiR) from Pseudomonas aeruginosa and various physiological/non physiological redox partners was investigated using cyclic voltammetry at the pyrolytic graphite electrode. While NiR did not exchange electron with the electrode, cytochrome c{sub 551} and azurin, both from Ps. aeruginosa, behaved as fast electrochemical systems. The intermolecular electron transfers between NiR and cytochrome c{sub 551} or azurin as electron shuttles, in the presence of nitrite, were studied. Second order rate constants of 2x10{sup 6} and 1.4x10{sup 5} M{sup -1} s{sup -1} are calculated for cytochrome c{sub 551} and azurin, respectively. The dependence of the second-order rate constant on ionic strength and pH is discussed. Finally, the effect of the global charge of the electron shuttles was explored using differently charged species (proteins or small ions). The experimental results suggest involvement of polar interactions as well as of hydrophobic contacts in the protein recognition prior to the intermolecular electron transfer. As the cross-reaction between Ps. nautica cytochrome c{sub 552} and Ps. aeruginosa NiR was shown to be as efficient as the catalytic reaction involving the physiological partners, it is concluded to a 'pseudo-specificity' in the recognition between NiR and the electron donor.

  9. Photoinduced intermolecular electron transfer and off-resonance Raman characteristics of Rhodamine 101/N,N-diethylaniline

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Li-lin [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); School of Mechanical and Electronic Engineering, Hezhou University, Hezhou 542800 (China); Liu, Wei-long; Song, Yun-fei; He, Xing; Wang, Yang; Wang, Chang; Wu, Hong-lin [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); Yang, Fang [National Key Laboratory of Science and Technology on Tunable Laser, Department of Optoelectronics Information Science Technology, Harbin Institute of Technology, Harbin 150001 (China); Yang, Yan-qiang, E-mail: yqyang@hit.edu.cn [Department of Physics, Harbin Institute of Technology, Harbin 150001 (China); National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, China Academy of Engineering Physics, Mianyang 621900, Sichuan (China)

    2014-01-31

    Highlights: • Mechanism of PIET reaction process for the Rh101{sup +}/DEA system is investigated. • The significant geometrical changes of the charge–transfer complex are explained. • Forward Electron transfer from DEA to Rh101{sup +?} occurs with lifetime of 425–560 fs. • Backward electron transfer occurs with a time constant of 46.16–51.40 ps. • Intramolecular vibrational relaxation occurs with lifetime of 2.77–5.39 ps. - Abstract: The ultrafast photoinduced intermolecular electron transfer (PIET) reaction of Rhodamine 101 (Rh101{sup +}) in N,N-diethylaniline (DEA) was investigated using off-resonance Raman, femtosecond time-resolved multiplex transient grating (TG) and transient absorption (TA) spectroscopies. The Raman spectra indicate that the C=C stretching vibration of the chromophore aromatic ring is more sensitive to ET compared with the C-C stretching mode. The ultrafast photoinduced intermolecular forward ET (FET) from DEA to Rh101{sup +?} occurs on a time scale of ?{sub FET} = 425–560 fs. The backward ET (BET) occurs in the inverted region with a time constant of ?{sub BET} = 46.16–51.40 ps. The intramolecular vibrational relaxation (IVR) process occurs on the excited state potential energy surface with the time constant of ?{sub IVR} = 2.77–5.39 ps.

  10. Inner reorganization limiting electron transfer controlled hydrogen bonding: intra- vs. intermolecular effects.

    Science.gov (United States)

    Martínez-González, Eduardo; Frontana, Carlos

    2014-05-01

    In this work, experimental evidence of the influence of the electron transfer kinetics during electron transfer controlled hydrogen bonding between anion radicals of metronidazole and ornidazole, derivatives of 5-nitro-imidazole, and 1,3-diethylurea as the hydrogen bond donor, is presented. Analysis of the variations of voltammetric EpIcvs. log?KB[DH], where KB is the binding constant, allowed us to determine the values of the binding constant and also the electron transfer rate k, confirmed by experiments obtained at different scan rates. Electronic structure calculations at the BHandHLYP/6-311++G(2d,2p) level for metronidazole, including the solvent effect by the Cramer/Truhlar model, suggested that the minimum energy conformer is stabilized by intramolecular hydrogen bonding. In this structure, the inner reorganization energy, ?i,j, contributes significantly (0.5 eV) to the total reorganization energy of electron transfer, thus leading to a diminishment of the experimental k. PMID:24653999

  11. Intermolecular charge transfer involving tryptophan, tyrosine and three electron-bonded intermediates derived from methionine

    Energy Technology Data Exchange (ETDEWEB)

    Bobrowski, K.; Lubis, R.

    1986-12-01

    Oxidation processes of radiation-generated three-electron-bonded intermediates derived from methionine Met/sub 2/:S therefore + S: and Met:S therefore plus: (X=Cl, Br) were through reaction with tryptophan and tyrosine, using the optical pulse radiolysis method. Bimolecular rate constants have been measured for the reactions Met/sub 2/:S therefore S: with TrpH(k=3.8 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s /sup 1/ and k=4.9 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/ at pH 1 and 4.3, respectively) and Met/sub 2/(S therefore + S) with tyrosine, k=3.8 x 10/sup 7/ dm/sup 3/ mol/sup -1/ s/sup -1/. Rate constants for intermolecular transformation of Met(S Br) and Met(S Cl) into TrpH/sup +/ or Trp were also estimated. They varied from 4.7 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/ (bromide species) to 1.0 x 10/sup 9/ dm/sup 3/ mol/sup -1/ s/sup -1/ (chloride species). It has also been established that azide radicals N 6- anion radicals, N/sub 3/ in contrast to dihalide radicals (X 2- anion radicals) do not form transients of Met(S therefore plus) (X=N/sub 3/)-type. However, oxidation of N/sub 3//sup -/ by Met/sub 2/(S therefore + S) occurs with a bimolecular rate constant of 2.8 x 10/sup 8/ dm/sup 3/ mol/sup -1/ s/sup -1/. These results are discussed in the light of some equilibria which have been proposed earlier for methionine-halide systems.

  12. Photo-induced intermolecular electron transfer from electron donating solvents to Coumarin dyes in bile salt aggregates: Role of diffusion in electron transfer reaction

    Science.gov (United States)

    Chakraborty, Anjan; Chakrabarty, Debdeep; Seth, Debabrata; Hazra, Partha; Sarkar, Nilmoni

    2006-03-01

    The photo-induced electron transfer between Coumarin dyes and aromatic amines has been investigated using steady state and time-resolved fluorescence quenching studies. We have observed a Marcus type inversion in the electron transfer rate in correlation of quenching constant to the free energy change occurred during reaction. To justify the "inverted region" obtained in the correlation of quenching constant versus free energy curve, we have performed anisotropy measurement and estimated the several diffusional parameters. The translational diffusion coefficients exhibit a similar picture like electron transfer rate constant when it is plotted against free energy. Thus we argued that the diffusion has played an important role in the electron transfer kinetics.

  13. Control of emission by intermolecular fluorescence resonance energy transfer and intermolecular charge transfer.

    Science.gov (United States)

    Sun, Mengtao; Pullerits, Tõnu; Kjellberg, Pär; Beenken, Wichard J D; Han, Keli

    2006-05-18

    Control of emission by intermolecular fluorescence resonant energy transfer (IFRET) and intermolecular charge transfer (ICT) is investigated with the quantum-chemistry method using two-dimensional (2D) and three-dimensional (3D) real space analysis methods. The work is based on the experiment of tunable emission from doped 1,3,5-triphenyl-2-pyrazoline (TPP) organic nanoparticles (Peng, A. D.; et al. Adv. Mater. 2005, 17, 2070). First, the excited-state properties of the molecules, which are studied (TPP and DCM) in that experiment, are investigated theoretically. The results of the 2D site representation reveal the electron-hole coherence and delocalization size on the excitation. The results of 3D cube representation analysis reveal the orientation and strength of the transition dipole moments and intramolecular or intermolecular charge transfer. Second, the photochemical quenching mechanism via IFRET is studied (here "resonance" means that the absorption spectrum of TPP overlaps with the fluorescence emission spectrum of DCM in the doping system) by comparing the orbital energies of the HOMO (highest occupied molecular orbital) and the LUMO (lowest unoccupied molecular orbital) of DCM and TPP in absorption and fluorescence. Third, for the DCM-TPP complex, the nonphotochemical quenching mechanism via ICT is investigated. The theoretical results show that the energetically lowest ICT state corresponds to a pure HOMO-LUMO transition, where the densities of the HOMO and LUMO are strictly located on the DCM and TPP moieties, respectively. Thus, the lowest ICT state corresponds to an excitation of an electron from the HOMO of DCM to the LUMO of TPP. PMID:16686468

  14. The study of intermolecular energy transfers in electronic energy quenching for molecular collisions N2-N2, N2-O2, O2-O2

    Directory of Open Access Journals (Sweden)

    A. S. Kirillov

    2008-05-01

    Full Text Available Contributions of intermolecular electron energy transfers in the electronic quenching are calculated for molecular collisions N2(A3?u+, W3?u+N2(X1?g+, v=0, N2(A3?u++N2(X1?g+, v?0, N2(A3?u++O2(X3?g?, v=0–2, O2(a1?g, b1?g++O2(X3?g?, v=0–2. The calculation has allowed one to estimate the product branching ratios. It is shown that there is a dependence of the calculated rate coefficients on the vibrational excitation of N2(X1?g+ and O2(X3?g? molecules. In many cases, the calculated rate coefficients have a good agreement with available experimental data.

  15. Determination of intermolecular transfer integrals from DFT calculations

    Energy Technology Data Exchange (ETDEWEB)

    Baumeier, Bjoern; Andrienko, Denis [Max-Planck Institute for Polymer Research, Mainz (Germany)

    2010-07-01

    Theoretical studies of charge transport in organic conducting systems pose a unique challenge since they require multiscale schemes that combine quantum-chemical, molecular dynamics and kinetic Monte-Carlo calculations. The description of the mobility of electrons and holes in the hopping regime relies on the determination of intermolecular hopping rates in large scale morphologies. Using Marcus theory these rates can be calculated from intermolecular transfer integrals and on-site energies. Here we present a detailed computational study on the accuracy and efficiency of density-functional theory based approaches to the determination of intermolecular transfer integrals. First, it is demonstrated how these can be obtained from quantum-chemistry calculations by forming the expectation value of a dimer Fock operator with frontier orbitals of two neighboring monomers based on a projective approach. We then consider the prototypical example of one pair out of a larger morphology of Tris(8-hydroxyquinolinato)aluminium (Alq3) and study the influence of computational parameters, e.g. the choice of basis sets, exchange-correlation functional, and convergence criteria, on the calculated transfer integrals. The respective accuracies and efficiencies are compared in order to derive an optimal strategy for future simulations based on the full morphology.

  16. Photoinduced intermolecular electron transfer between Coumarin dyes and electron donating solvents in cetyltrimethylammonium bromide (CTAB) micelles: evidence for Marcus inverted region

    Science.gov (United States)

    Chakraborty, Anjan; Chakrabarty, Debdeep; Hazra, Partha; Seth, Debabrata; Sarkar, Nilmoni

    2003-12-01

    The photoinduced electron transfer between different Coumarin dyes and aromatic amines in cetyltrimethylammonium bromide (CTAB) micellar solution has been reported using both steady state and time resolved fluorescence quenching measurement. The location of the dye molecules in micelles has been confirmed by the time resolved fluorescence anisotropy measurement. The plot of the observed Kq values in the CTAB micellar solution with the free energy change (? G?) for electron transfer reaction show an inversion in the observed rate as predicted by Marcus theory. The two-dimensional electron transfer model has been employed to interpret the Marcus inverted region.

  17. Theoretical study of intermolecular energy transfer involving electronically excited molecules: He(1S) + H2(B 1?/sub u/+)

    International Nuclear Information System (INIS)

    To further understanding of gas phase collision dynamics involving electronically-excited molecules, a fully quantum mechanical study of He + H2(B 1?/sub u/+) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H2(B 1?/sub u/+). The potential energy surface (PES) is highly anisotropic and has a van der Waals well of about 0.03 eV for C/sub 2v/ approach. Avoided PES crossings occur with He + H2(E,F 1?/sub g/+) and with He + H2(X 1?/sub g/+) and cause a local maximum and a deep minimum in the He + H2(B 1?/sub u/+) PES, respectively. The crossing with He + H2(X 1?/sub g/+) provides a mechanism for fluorescence quenching. The computed CI energies were combined with previous multi-reference double excitation CI calculations and fit with analytic functions for convenience in scattering calculations. Accurate dipole polarizabilities and quadrupole moment of H2(B 1?/sub u/+) were computed for use in the multipole expansion, which is the analytic form of the long-range PES. 129 refs., 28 figs., 35 tabs

  18. Effects of competition for charge capture from the matrix on intermolecular electron-tunneling reactions

    International Nuclear Information System (INIS)

    A general method is presented for correcting for the direct capture of matrix charges by the acceptor in an intermolecular electron-transfer reaction in a rigid medium. The method is based on a two-step electron-tunneling model that takes into account the correlation between matrix charge capture and intermolecular electron transfer. As an experimental test of the method, electron transfer from the anion of cinnamaldehyde to neutral pryomellitic dianhydride was studied in 2-methyltetrahydrofuran glass at 770K. Good agreement between the model and the experimental kinetic results was obtained

  19. Intermolecular Hydrogen Transfer in Isobutane Hydrate

    Directory of Open Access Journals (Sweden)

    Takeshi Sugahara

    2012-05-01

    Full Text Available Electron spin resonance (ESR spectra of butyl radicals induced with ?-ray irradiation in the simple isobutane (2-methylpropane hydrate (prepared with deuterated water were investigated. Isothermal annealing results of the ?-ray-irradiated isobutane hydrate reveal that the isobutyl radical in a large cage withdraws a hydrogen atom from the isobutane molecule through shared hexagonal-faces of adjacent large cages. During this “hydrogen picking” process, the isobutyl radical is apparently transformed into a tert-butyl radical, while the sum of isobutyl and tert-butyl radicals remains constant. The apparent transformation from isobutyl to tert-butyl radicals is an irreversible first-order reaction and the activation energy was estimated to be 35 ± 3 kJ/mol, which was in agreement with the activation energy (39 ± 5 kJ/mol of hydrogen picking in the ?-ray-irradiated propane hydrate with deuterated water.

  20. Intermolecular electronic and vibrational energy transfer from the single vibronic levels of p-difluorobenzene (1B2/sub u/) to cyclobutanone

    International Nuclear Information System (INIS)

    An attempt has been made to measure the singlet--singlet electronic energy transfer rates from 17 single vibronic levels (SVL) of p-C6H4F2(1B2/sub u/) to cyclobutanone. No variation in the energy transfer cross sections have been found for the 17 SVL transitions, and an average value of 103 A2 (?sigma/sub c/2) is obtained. This value is nearly identical to the value obtained for the vibrationally relaxed, thermal levels. The reason for the lack of variation is suggested to be the consequence of rapid, intramolecular vibrational energy redistribution induced by collisional perturbation

  1. Intermolecular electronic and vibrational energy transfer from the single vibronic levels of p-difluorobenzene (/sup 1/B/sub 2//sub u/) to cyclobutanone

    Energy Technology Data Exchange (ETDEWEB)

    Volk, L.J.; Lee, E.K.C.

    1977-07-01

    An attempt has been made to measure the singlet--singlet electronic energy transfer rates from 17 single vibronic levels (SVL) of p-C/sub 6/H/sub 4/F/sub 2/(/sup 1/B/sub 2//sub u/) to cyclobutanone. No variation in the energy transfer cross sections have been found for the 17 SVL transitions, and an average value of 103 A/sup 2/ (..pi..sigma/sub c//sup 2/) is obtained. This value is nearly identical to the value obtained for the vibrationally relaxed, thermal levels. The reason for the lack of variation is suggested to be the consequence of rapid, intramolecular vibrational energy redistribution induced by collisional perturbation.

  2. Fluorine-Substituted Phenols as Probes to Study Intermolecular Proton Transfer Induced by Excess Electron Attachment to Uracil-Phenol Complexes

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    Maciej Haranczyk

    2004-07-01

    Full Text Available The experiments suggest that low-energy electrons, possibly localized on nucleic acid bases, induce DNA damage. The results of our recent studies strongly suggest that the excess electron attachment to the complex of a nucleic acid base with an amino acid can induce a barrier-free proton transfer (BFPT from the amino acid to the O8 of uracil. The driving force for the proton transfer is to stabilize the excess electron localized on a ?* orbital. Our further studies also demonstrated that BFPT occurs in anionic complexes of uracil with alanine, formic acid, as well as H2Se and H2S. We briefly determined factors governing the occurrence of proton transfer in complexes between anionic nucleic acid bases (NABs and proton donors. We found that the occurrence of BFPT in the uracil complexes is an outcome of the interplay between the deprotonation energy of a proton donor and the protonation energy of the anion of uracil. The density functional theory (DFT was applied as our research method. The B3LYP and MPW1K exchange-correlation functionals with 6-31++G** (5d basis set were used. The substitution of five hydrogen atoms with fluorine atoms in phenol molecule decreases the energy of deprotonation from 15.3 eV to 14.4 eV. There are 5 groups of F-substituted phenol isomers and 19 structures in total. These 19 molecules provide fine grid on the scale of deprotonation energy and can be used as a probe to study the BFPT phenomenon. In the case of uracil-2,3,4,5,6-pentafluorophenol and uracil-2,4,6-trifluorophenol complexes, the excess electron attachment can induce BFPT from the hydroxyl group to the O8 atom of U, with the products being a hydrogenated uracil and a deprotonated fluorophenol. No BFPT is predicted for the anions of other uracil-phenol complexes. The estimated critical value of deprotonation energy of a F-substituted phenol for which BFPT takes place is 14.86-15.38 eV. Further studies can be preformed to obtain a higher accuracy of this estimation.

  3. Mechanistic studies of photoinduced intramolecular and intermolecular electron transfer processes in RuPt-centred photo-hydrogen-evolving molecular devices.

    Science.gov (United States)

    Suneesh, Chettiyam Veettil; Balan, Bijitha; Ozawa, Hironobu; Nakamura, Yuki; Katayama, Tetsuro; Muramatsu, Masayasu; Nagasawa, Yutaka; Miyasaka, Hiroshi; Sakai, Ken

    2014-01-28

    The photoinduced electron transfer properties of two photo-hydrogen-evolving molecular devices (PHEMDs) [(bpy)2Ru(II)(phen-NHCO-bpy-R)Pt(II)Cl2](2+) (i.e., condensation products of [Ru(bpy)2(5-amino-phen)](2+) and (4-carboxy-4?-R-bpy)PtCl2; bpy = 2,2?-bipyridine, phen = 1,10-phenanthroline; RuPt-COOH for R = COOH and RuPt-CN for R = CN) were investigated. RuPt-CN demonstrates higher photocatalytic performance relative to RuPt-COOH arising from a larger driving force for the intramolecular photoinduced electron transfer (PET) associated with a stronger electron-withdrawing effect of R (?GPET = ?0.43 eV for RuPt-CN and ?0.16 eV for RuPt-COOH). This is the first study on PET events using ultrafast spectroscopy. Dramatic enhancement is achieved in the rate of PET in RuPt-CN (1.78 × 1010 s(?1)) relative to RuPt-COOH (3.1 × 109 s(?1)). For each system, the presence of three different conformers giving rise to three different PET rates is evidenced, which are also discussed with the DFT results. Formation of a charge-separated (CS) state [(bpy)2Ru(III)(phen-NHCO-bpy(??)-R)Pt(II)Cl2](2+) in the sub-picosecond time regime and recombination in the picosecond time regime are characterized spectrophotometrically. The CS-state formation was found to compete with reductive quenching of the triplet excited state by EDTA whose dianionic form ion-pairs with dicationic RuPt-COOH. Thus, a key intermediate [(bpy)2Ru(II)(phen-NHCO-bpy(??)-R)Pt(II)Cl2](+) (i.e., the one-electron-reduced species) prior to the H2 formation was found to be formed either via reduction of the CS state by EDTA or via formation of [(bpy)2Ru(II)(phen(??)-NHCO-bpy-R)Pt(II)Cl2](+) by reductive quenching of the triplet excited state. More importantly, it is also shown that some of the conformers in solution possess a CS lifetime sufficiently long to drive hydrogen evolution from water. PMID:24316670

  4. Intermolecular electron transfer between coumarin dyes and aromatic amines in Triton-X-100 micellar solutions: Evidence for Marcus inverted region

    Science.gov (United States)

    Kumbhakar, Manoj; Nath, Sukhendu; Mukherjee, Tulsi; Pal, Haridas

    2004-02-01

    Photoinduced electron transfer (ET) between coumarin dyes and aromatic amines has been investigated in Triton-X-100 micellar solutions and the results have been compared with those observed earlier in homogeneous medium. Significant static quenching of the coumarin fluorescence due to the presence of high concentration of amines around the coumarin fluorophore in the micelles has been observed in steady-state fluorescence studies. Time-resolved studies with nanosecond resolutions mostly show the dynamic part of the quenching for the excited coumarin dyes by the amine quenchers. A correlation of the quenching rate constants, estimated from the time-resolved measurements, with the free energy changes (?G0) of the ET reactions shows the typical bell shaped curve as predicted by Marcus outer-sphere ET theory. The inversion in the ET rates for the present systems occurs at an exergonicity (-?G0) of ~0.7-0.8 eV, which is unusually low considering the polarity of the Palisade layer of the micelles where the reactants reside. Present results have been rationalized on the basis of the two dimensional ET model assuming that the solvent relaxation in micellar media is much slower than the rate of the ET process. Detailed analysis of the experimental data shows that the diffusional model of the bimolecular quenching kinetics is not applicable for the ET reactions in the micellar solutions. In the present systems, the reactions can be better visualized as equivalent to intramolecular electron transfer processes, with statistical distribution of the donors and acceptors in the micelles. A low electron coupling (Vel) parameter is estimated from the correlation of the experimentally observed and the theoretically calculated ET rates, which indicates that the average donor-acceptor separation in the micellar ET reactions is substantially larger than for the donor-acceptor contact distance. Comparison of the Vel values in the micellar solution and in the donor-acceptor close contact suggests that there is an intervention of a surfactant chain between the interacting donor and acceptor in the micellar ET reaction.

  5. Intermolecular electron transfer between coumarin dyes and aromatic amines in Triton-X-100 micellar solutions: Evidence for Marcus inverted region

    International Nuclear Information System (INIS)

    Photoinduced electron transfer (ET) between coumarin dyes and aromatic amines has been investigated in Triton-X-100 micellar solutions and the results have been compared with those observed earlier in homogeneous medium. Significant static quenching of the coumarin fluorescence due to the presence of high concentration of amines around the coumarin fluorophore in the micelles has been observed in steady-state fluorescence studies. Time-resolved studies with nanosecond resolutions mostly show the dynamic part of the quenching for the excited coumarin dyes by the amine quenchers. A correlation of the quenching rate constants, estimated from the time-resolved measurements, with the free energy changes (?G0) of the ET reactions shows the typical bell shaped curve as predicted by Marcus outer-sphere ET theory. The inversion in the ET rates for the present systems occurs at an exergonicity (-?G0) of ?0.7-0.8 eV, which is unusually low considering the polarity of the Palisade layer of the micelles where the reactants reside. Present results have been rationalized on the basis of the two dimensional ET model assuming that the solvent relaxation in micellar media is much slower than the rate of the ET process. Detailed analysis of the experimental data shows that the diffusional model of the bimolecular quenching kinetics is not applicable for the ET reactions in the micellar solutions. In the present systems, the reactions can be better visualized as reactions can be better visualized as equivalent to intramolecular electron transfer processes, with statistical distribution of the donors and acceptors in the micelles. A low electron coupling (Vel) parameter is estimated from the correlation of the experimentally observed and the theoretically calculated ET rates, which indicates that the average donor-acceptor separation in the micellar ET reactions is substantially larger than for the donor-acceptor contact distance. Comparison of the Vel values in the micellar solution and in the donor-acceptor close contact suggests that there is an intervention of a surfactant chain between the interacting donor and acceptor in the micellar ET reaction

  6. The study of intermolecular energy transfers in electronic energy quenching for molecular collisions N{sub 2}-N{sub 2}, N{sub 2}-O{sub 2}, O{sub 2}-O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Kirillov, A.S. [Kola Science Centre RAS, Apatity (Russian Federation). Polar Geophysical Inst.

    2008-07-01

    Contributions of intermolecular electron energy transfers in the electronic quenching are calculated for molecular collisions N{sub 2}(A{sup 3}{sigma}{sub u}{sup +}, W{sup 3}{delta}{sub u})+N{sub 2}(X{sup 1}{sigma}{sub g}{sup +}, v=0), N{sub 2}(A{sup 3}{sigma}{sub u}{sup +})+N{sub 2}(X{sup 1}{sigma}{sub g}{sup +}, v{>=}0), N{sub 2}(A{sup 3}{sigma}{sub u}{sup +})+O{sub 2}(X{sup 3}{sigma}{sub g}{sup -}, v=0-2), O{sub 2}(a{sup 1}{delta}{sub g}, b{sup 1}{sigma}{sub g}{sup +})+O{sub 2}(X{sup 3}{sigma}{sub g}{sup -}, v=0-2). The calculation has allowed one to estimate the product branching ratios. It is shown that there is a dependence of the calculated rate coefficients on the vibrational excitation of N{sub 2}(X{sup 1}{sigma}{sub g}{sup +}) and O{sub 2}(X{sup 3}{sigma}{sub g}{sup -}) molecules. In many cases, the calculated rate coefficients have a good agreement with available experimental data. (orig.)

  7. Intra- and intermolecular charge transfer in aggregates of tetrathiafulvalene-triphenylmethyl radical derivatives in solution.

    Science.gov (United States)

    Guasch, Judith; Grisanti, Luca; Souto, Manuel; Lloveras, Vega; Vidal-Gancedo, José; Ratera, Imma; Painelli, Anna; Rovira, Concepció; Veciana, Jaume

    2013-05-01

    An extensive investigation of aggregation phenomena occurring in solution for a family of electron donor-acceptor derivatives, based on polychlorotriphenylmethyl radicals (PTM) linked via a vinylene-bridge to tetrathiafulvalene (TTF) units, is presented. A large set of temperature and/or concentration dependent optical absorption and electron spin resonance (ESR) spectra in a solution of dyads bearing different number of electrons and/or with a hydrogenated PTM residue offer reliable information on the formation of homo dimers and mixed valence dimers. The results shed light on the reciprocal influence of intramolecular electron transfer (IET) within a dyad and the intermolecular charge transfer (CT) occurring in a dimer between the TTF residues and are rationalized based on a theoretical model that describes both interactions. PMID:23517105

  8. Polar solvation and electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    1993-04-13

    The report is divided into the following sections: completion of previous studies on solvation dynamics, dipole lattice studies, inertial components of solvation response, simple models of solvation dynamics, rotational dynamics and dielectric friction, intramolecular electron transfer reactions, and intermolecular donor-acceptor complexes.

  9. Dynamics of the Intermolecular Transfer Integral in Crystalline Organic Semiconductors

    CERN Document Server

    Troisi, A; Troisi, Alessandro; Orlandi, Giorgio

    2005-01-01

    In organic crystalline semiconductor molecular components are held together by very weak interactions and the transfer integrals between neighboring molecular orbitals are extremely sensitive to small nuclear displacements. We used a mixed quantum chemical and molecular dynamic methodology to assess the effect of nuclear dynamics on the modulation of the transfer integrals between close molecules. We have found that the fluctuations of the transfer integrals are of the same order of magnitude of their average value for pentacene and anthracene. Under these conditions the usual perturbative treatment of the electron phonon coupling is invalid, the band description of the crystal breaks down and the charge carriers become localized. Organic crystals of pentacene and anthracene, even in the absence of defects, can be regarded as disordered media with respect to their charge transport properties. These results suggest that the dynamic electronic disorder can be the factor limiting the charge mobility in crystalli...

  10. Intermolecular nonradiative energy transfer in clusters with plasmonic nanoparticles

    Science.gov (United States)

    Kucherenko, M. G.; Stepanov, V. N.; Kruchinin, N. Yu.

    2015-01-01

    The influence of carbon (fullerenes, nanotubes) and metal (Ni, Co, Cu, Ag) nanoparticles on the nonradiative electronic excitation energy transfer between the molecules of organic dyes (acrylic orange as a donor and Nile blue as an acceptor) in alcohol solutions of polyvinylbutyral is studied. It is found that, at particular concentrations of the mixture components, plasmonic nanoparticles affect the nonradiative electronic excitation energy transfer, which is manifested in an increase in the intensity of sensitized fluorescence of acceptors with simultaneous quenching of the fluorescence of donors. A very simple model is proposed to illustrate the observed redistribution of luminescence intensity between the spectral bands of the general spectrum. Molecular-dynamic calculations of the structure of nanocomposites performed for the same purpose confirmed the formation of associated molecular plasmonic complexes fixed by macrochain links.

  11. Molecular Basis for Directional Electron Transfer*

    OpenAIRE

    Paquete, Catarina M.; Saraiva, Ivo H.; Calc?ada, Eduardo; Louro, Ricardo O.

    2010-01-01

    Biological macromolecules involved in electron transfer reactions display chains of closely packed redox cofactors when long distances must be bridged. This is a consequence of the need to maintain a rate of transfer compatible with metabolic activity in the framework of the exponential decay of electron tunneling with distance. In this work intermolecular electron transfer was studied in kinetic experiments performed with the small tetraheme cytochrome from Shewanella oneidensis MR-1 and fro...

  12. Intermolecular thermoelectric-like effects in molecular nano electronic systems

    International Nuclear Information System (INIS)

    Intramolecular thermoelectric-like coefficients are introduced and computed of a single molecule nano electronic system. Values of the electronic Intramolecular thermoelectric-like coefficients are calculated based on the density and energy transfers between different parts of the molecule using quantum theory of atoms in molecule. Since, Joule and Peltier heating are even (symmetrical) and odd (antisymmetric) functions of the external bias, it is possible to divide Intramolecular thermoelectric-like coefficients into two components, symmetrical and antisymmetrical Intramolecular thermoelectric-like coefficients, which describe the intramolecular Joule-like and Peltier-like effects, respectively. In addition, a semiclassical temperature model is presented to describe intramolecular temperature mapping (intramolecular energy distributions) in molecular nano electronic systems.

  13. Intermolecular electronic interactions in the primary charge separation in bacterial photosynthesis

    Energy Technology Data Exchange (ETDEWEB)

    Plato, M.; Moebius, K.; Michel-Beyerle, M.E.; Bixon, M.; Jortner, J. (Freie Universitaet Berlin (West Germany))

    1988-10-26

    In this paper the intermolecular overlap approximation is used to calculate the relative magnitudes of the electronic transfer integrals between the excited singlet state ({sup 1}P*) of the bacteriochlorophyll dimer (P) and the accessory bacteriochlorophyll (B) and between B{sup {minus}} and bacteriopheopytin (H), along the L and M subunits of the reaction center (RC) of Rps. viridis. The ratio of the electron-transfer integrals for B{sub L}{sup {minus}}H{sub L}{sup {minus}}B{sub L}H{sub L}{minus} and for B{sub M}{sup {minus}}H{sub M}{minus}B{sub M}H{sub M}{sup {minus}} was calculated to be 2.1 {plus minus} 0.5, which together with the value of 2.8 {plus minus} 0.7 for the ratio of the transfer integrals for {sup 1}P*B{sub L}-P{sup +}B{sub L}- and for {sup 1}P*B{sub M}-P{sup +}B{sub M}- results in the electronic contribution of 33 {plus minus} 16 to the ratio k{sub L}/k{sub m} of the rate constants k{sub L} and k{sub M} for the primary charge separation across the L and M branches of the RC, respectively. The asymmetry of the electronic coupling terms, which originates from the combination of the asymmetry in the charge distribution of {sup 1}P* and of structural asymmetry of the P-M and B-H arrangements across the L and M subunits, provides a major contribution to the unidirectionality of the charge separation in bacterial photosynthesis. A significant contribution to the transfer integrals between adjacent pigments originates from nearby methyl groups through hyperconjugation. The ratio 6 {plus minus} 2 of the transfer integrals for {sup 1}P*B{sub L}-P{sup +}B{sub L}- and for B{sub L}-H{sub L}-B{sub L}H{sub L}- was utilized to estimate the energetic parameters required to ensure the dominance of the superexchange mediated unistep electron transfer {sup 1}P*BH {yields} P{sup +}BH{sup {minus}} over the thermally activated {sup 1}P*B {yields} P{sup +}B{sup {minus}} process. 31 refs., 6 figs., 2 tabs.

  14. Photochemistry on surfaces. Intermolecular energy electron transfer processes between excited Ru(bpy){sub 3}{sup 2+} and H-aggregates of cresyl violet on SiO{sub 2} and SnO{sub 2} colloids

    Energy Technology Data Exchange (ETDEWEB)

    Liu, D.; Hug, G.L.; Kamat, P.V. [Univ. of Notre Dame, IN (United States)

    1995-11-09

    Cresyl violet, a cationic dye (CV{sup +}), forms H-aggregates on the negatively charged SiO{sub 2} and SnO{sub 2} colloids. These aggregates exhibit broad absorbance around 520 nm. By coadsorbing a sensitizer, Ru(bpy){sub 3}{sup 2+}, we are able to characterize the triplet excited state and reduced form of dye-aggregates on the colloidal SiO{sub 2} and SnO{sub 2} suspensions. On SiO{sub 2} surfaces, the excited state quenching of Ru(bpy){sub 3}{sup 2+} by dye-aggregates proceeds via an energy transfer mechanism. Picosecond laser flash photolysis experiments indicate that such a surface-promoted energy transfer is completed within 20 ps. On the other hand dye-aggregates adsorbed onto SnO{sub 2} colloids undergo photosensitized reduction since the excited sensitizer, Ru(bpy){sub 3} {sup 2+}, is efficiently quenched by the semiconductor support. The role of support material in promoting energy and electron transfer processes is described. 87 refs., 11 figs.

  15. TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4?-dimethylaminoflavonol in ethanol solvent

    Science.gov (United States)

    Wang, Ye; Shi, Ying; Cong, Lin; Li, Hui

    2015-02-01

    Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4?-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule.

  16. TDDFT study of twisted intramolecular charge transfer and intermolecular double proton transfer in the excited state of 4'-dimethylaminoflavonol in ethanol solvent.

    Science.gov (United States)

    Wang, Ye; Shi, Ying; Cong, Lin; Li, Hui

    2015-02-25

    Time-dependent density functional theory method at the def-TZVP/B3LYP level was employed to investigate the intramolecular and intermolecular hydrogen bonding dynamics in the first excited (S1) state of 4'-dimethylaminoflavonol (DMAF) monomer and in ethanol solution. In the DMAF monomer, we demonstrated that the intramolecular charge transfer (ICT) takes place in the S1 state. This excited state ICT process was followed by intramolecular proton transfer. Our calculated results are in good agreement with the mechanism proposed in experimental work. For the hydrogen-bonded DMAF-EtOH complex, it was demonstrated that the intermolecular hydrogen bonds can induce the formation of the twisted intramolecular charge transfer (TICT) state and the conformational twisting is along the C3-C4 bond. Moreover, the intermolecular hydrogen bonds can also facilitate the intermolecular double proton transfer in the TICT state. A stepwise intermolecular double proton transfer process was revealed. Therefore, the intermolecular hydrogen bonds can alter the mechanism of intramolecular charge transfer and proton transfer in the excited state for the DMAF molecule. PMID:25282020

  17. On the reaction mechanism of the complete intermolecular O2 transfer between mononuclear nickel and manganese complexes with macrocyclic ligands.

    Science.gov (United States)

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J; Liakos, Dimitrios G; Neese, Frank

    2014-10-01

    The recently described intermolecular O2 transfer between the side-on Ni-O2 complex [(12-TMC)Ni-O2](+) and the manganese complex [(14-TMC)Mn](2+), where 12-TMC and 14-TMC are 12- and 14-membered macrocyclic ligands, 12-TMC=1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane and 14-TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane, is studied by means of DFT methods. B3LYP calculations including long-range corrections and solvent effects are performed to elucidate the mechanism. The potential energy surfaces (PESs) compatible with different electronic states of the reactants have been analyzed. The calculations confirm a two-step reaction, with a first rate-determining bimolecular step and predict the exothermic character of the global process. The relative stability of the products and the reverse barrier are in line with the fact that no reverse reaction is experimentally observed. An intermediate with a ?-?(1):?(1)-O2 coordination and two transition states are identified on the triplet PES, slightly below the corresponding stationary points of the quintet PES, suggesting an intersystem crossing before the first transition state. The calculated activation parameters and the relative energies of the two transition sates and the products are in very good agreement with the experimental data. The calculations suggest that a superoxide anion is transferred during the reaction. PMID:25179780

  18. Theoretical study of intermolecular energy transfer involving electronically excited molecules: He(/sup 1/S) + H/sub 2/(B /sup 1/. sigma. /sub u//sup +/). [Solution for coupled channel equations

    Energy Technology Data Exchange (ETDEWEB)

    Grimes, R.M.

    1986-11-01

    To further understanding of gas phase collision dynamics involving electronically-excited molecules, a fully quantum mechanical study of He + H/sub 2/(B /sup 1/..sigma../sub u//sup +/) was undertaken. Iterative natural orbital configuration interaction (CI) calculations were performed to obtain the interaction potential between He and H/sub 2/(B /sup 1/..sigma../sub u//sup +/). The potential energy surface (PES) is highly anisotropic and has a van der Waals well of about 0.03 eV for C/sub 2v/ approach. Avoided PES crossings occur with He + H/sub 2/(E,F /sup 1/..sigma../sub g//sup +/) and with He + H/sub 2/(X /sup 1/..sigma../sub g//sup +/) and cause a local maximum and a deep minimum in the He + H/sub 2/(B /sup 1/..sigma../sub u//sup +/) PES, respectively. The crossing with He + H/sub 2/(X /sup 1/..sigma../sub g//sup +/) provides a mechanism for fluorescence quenching. The computed CI energies were combined with previous multi-reference double excitation CI calculations and fit with analytic functions for convenience in scattering calculations. Accurate dipole polarizabilities and quadrupole moment of H/sub 2/(B /sup 1/..sigma../sub u//sup +/) were computed for use in the multipole expansion, which is the analytic form of the long-range PES. 129 refs., 28 figs., 35 tabs.

  19. Sensitivity analysis of rotational energy transfer processes to the intermolecular potential

    International Nuclear Information System (INIS)

    This paper considers the sensitivity of rotational energy transfer processes to the variation of parameters within an assumed model intermolecular potential. The following cross sections are considered here: integral state to state, pressure broadening, effective diffusion and viscosity, and final state summed integral cross sections. In order to simplify the calculation of cross sections, attention is restricted to the scattering of an atom and linear rigid rotor. Furthermore, the collision dynamics are approximated by using the infinite order sudden (IOS) method. It is shown that use of the IOS method allows for the very simple generation of first order sensitivity coefficients (i.e., the partial derivative of cross sections with respect to potential parameters). Particular attention is focused upon the sensitivities of different cross sections and combinations of cross sections to the various parameters. The first order sensitivities are also used to derive new coefficients which describe how the potential parameters correlate given a limited set of cross section measurements. These coefficients are shown to be particularly important in determining the degree to which a set of measurements is able to define various parameters of the assumed potential

  20. Chemical exchange saturation transfer MRI using intermolecular double-quantum coherences with multiple refocusing pulses.

    Science.gov (United States)

    Lu, Jianhua; Cai, Congbo; Cai, Shuhui; Chen, Zhong; Zhou, Jinyuan

    2014-07-01

    Chemical exchange saturation transfer (CEST) provides a new type of image contrast in MRI. Due to the intrinsically low CEST effect, new and improved experimental techniques are required to achieve reliable and quantitative CEST images. In the present work, we proposed a novel and more sensitive CEST acquisition approach, based on the intermolecular double-quantum coherence with a module of multiple refocusing pulses (iDQC-MRP). Experiments were performed on creatine and egg white phantoms using a Varian 7T animal MRI scanner. The iDQC-MRP CEST technique showed a substantial enhancement in CEST and nuclear Overhauser enhancement (NOE) signal intensities, compared to the standard single-quantum coherence approach. In addition, the iDQC-MRP approach increased the signal-to-noise ratio of acquired saturation images, compared to the conventional iDQC approach. The new iDQC-MRP CEST sequence provides a promising way for exploiting in vivo CEST and NOE imaging applications. PMID:24685983

  1. Intermolecular hydrogen transfer catalyzed by a flavodehydrogenase, bakers' yeast flavocytochrome b2

    International Nuclear Information System (INIS)

    Bakers yeast flavocytochrome b2 is a flavin-dependent L-2-hydroxy acid dehydrogenase which also exhibits transhydrogenase activity. When a reaction takes place between [2-3H]lactate and a halogenopyruvate, tritium is found in water and at the halogenolactate C2 position. When the halogenopyruvate undergoes halide ion elimination, tritium is also found at the C3 position of the resulting pyruvate. The amount tau of this intermolecular tritium transfer depends on the initial keto acid-acceptor concentration. At infinite acceptor concentration, extrapolation yields a maximal transfer of 97 +/- 11%. This indicates that the hydroxy acid-derived hydrogen resides transiently on enzyme monoprotic heteroatoms and that exchange with bulk solvent occurs only at the level of free reduced enzyme. Using a minimal kinetic scheme, the rate constant for hydrogen exchange between Ered and solvent is calculated to be on the order of 10(2) M-1 S-1, which leads to an estimated pK approximately equal to 15 for the ionization of the substrate-derived proton while on the enzyme. It is suggested that this hydrogen could be shared between the active site base and Flred N5 anion. It is furthermore shown that some tritium is incorporated into the products when the transhydrogenation is carried out in tritiated water. Finally, with [2-2H]lactate-reduced enzyme, a deuterium isotope effect is observed on the rate of bromopyruvate disappearance. Extrapolation to infinite bromopyruvate conxtrapolation to infinite bromopyruvate concentration yields DV = 4.4. An apparent inverse isotope effect is determined for bromide ion elimination. These results strengthen the idea that oxidoreduction and elimination pathways involve a common carbanionic intermediate

  2. Electron transfer in biology

    Science.gov (United States)

    Williams, R. J. P.

    Electron transfer is one of the key reactions of biology not just in catalysis of oxidation/reduction reactions but in the conversion of sources of energy such as light to usable form for chemical transformations. There are then two intriguing problems. What is the nature of the matrix in which electrons flow in a biological cell after the initial charge separation due for example to the absorption of light. Here we are examining biological structures similar to man's electronic wires and the construction must be of low resistance in what are apparently insulators - organic polymers. It has been found that the electronic conduction system is largely made from metallo-proteins associated with lipid membranes. We understand much about these biological wires today. The second problem concerns the conversion of the energy captured from the light into usable chemical form. The major synthetic step in the production of biological polymers, including proteins, DNA, RNA, polysaccharides and fats, is condensation, i.e. the removal of water in the formation of amides, esters and so on. Now these condensation reactions are driven in biology by using a drying agent in water, namely the anhydride, pyrophosphate, in a special compound ATP, adenosine triphosphate. The central problem is to discover exactly how the flow of electrons can be related to the synthesis of (bound) pyrophosphate. (In a thermodynamic sense pyrophosphate is a water soluble kinetically stable drying agent comparable with solid P2O5.) In the biological systems the connection between these different classes of reaction, electron transfer and condensation, is known to be via the production of an energized gradient of protons across the biological membrane which arises from the flow of electrons across the same membrane in the electron transport wires of biology. However we do not understand thoroughly the steps which lead from electron flow in a membrane to proton gradients in that membrane, i.e. electron/proton coupling. Again we do not understand thoroughly how subsequently the proton gradient across a membrane makes ATP, pyrophosphate. Today there is good experimental evidence as to the likely answers in principle. These analyse the coupling devices in mechanical terms. In this article I describe at first the 'wires' of biology, uncoupled simple electron flow, and then go on to the ways in which electron flow could be transduced by mechanical devices, also proteins, into proton gradients and then ATP. This will be termed coupled electron flow. The objective of the article is to stimulate participation by physical chemists in the further description of biological energy capture from light or the oxidation of hydrocarbons to a form suitable for driving chemical syntheses in a controlled manner.

  3. Electron-phonon interactions and intra- and intermolecular charge mobility in the monocations of annulenes.

    Science.gov (United States)

    Kato, Takashi; Yamabe, Tokio

    2006-09-21

    Possible electron pairing in pi-conjugated positively charged annulenes such as (CH)(18) (18an) and (CH)(30) (30an) is studied and compared with that in the positively charged acenes. The total electron-phonon coupling constants in the monocations (l(HOMO)) for 18an and 30an are estimated. The E(2g) modes of 1611 and 1201 cm(-1) most strongly couple to the highest occupied molecular orbitals (HOMO) in 18an and 30an, respectively. The l(HOMO) values for annulenes are larger than those for acenes. The phase pattern difference between the HOMO of acenes localized on the edge part of carbon atoms and the delocalized HOMO of annulenes is the main reason for the calculated results. In view of the calculated results of the l(HOMO) values, intramolecular electron mobility (sigma(intra,HOMO)), and the reorganization energies (RE(HOMO)) in the positively charged molecules, the monocations of annulenes cannot easily become good conductors compared with the monocations of acenes, but the condition of the attractive electron-electron interactions is realized more easily in the monocations of annulenes than in the monocations of acenes. The hypothetical intramolecular supercurrent originating from both intramolecular and intermolecular vibrations in the monocations of annulenes and acenes in a case where the distance between two adjacent molecules is too large for the molecular crystal to become normal metallic state, is also discussed. PMID:16970433

  4. Reversible electron-induced cis-trans isomerization mediated by intermolecular interactions

    International Nuclear Information System (INIS)

    Reversible isomerization processes are rarely found when organic molecular switches are adsorbed on metal surfaces. One obstacle is the large energy difference of the isomeric forms, since usually the most planar conformer has the largest adsorption energy. In the example of an imine derivative, we show a strategy for also stabilizing the non-planar isomer by intermolecular bonding to its neighbors. Tunneling electrons from the tip of a scanning tunneling microscope can then be used to induce reversible switching between the trans and cis-like state. Supported by model force-field calculations, we illustrate that the most probable cause of the enhanced stability of the three-dimensional cis state at specific adsorption sites is the electrostatic interaction with N sites of the neighboring molecule.

  5. 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

  6. Identification of molecular crystals capable of undergoing an acyl-transfer reaction based on intermolecular interactions in the crystal lattice.

    Science.gov (United States)

    Tamboli, Majid I; Krishnaswamy, Shobhana; Gonnade, Rajesh G; Shashidhar, Mysore S

    2013-09-16

    Investigation of the intermolecular acyl-transfer reactivity in molecular crystals of myo-inositol orthoester derivatives and its correlation with crystal structures enabled us to identify the essential parameters to support efficient acyl-transfer reactions in crystals: 1)?the favorable geometry of the nucleophile (-OH) and the electrophile (C-O) and 2)?the molecular assembly, reinforced by C-H???? interactions, which supports a domino-type reaction in crystals. These parameters were used to identify another reactive crystal through a data-mining study of the Cambridge Structural Database. A 2:1 co-crystal of 2,3-naphthalene diol and its di-p-methylbenzoate was selected as a potentially reactive crystal and its reactivity was tested by heating the co-crystals in the presence of solid sodium carbonate. A facile intermolecular p-toluoyl group transfer was observed as predicted. The successful identification of reactive crystals opens up a new method for the detection of molecular crystals capable of exhibiting acyl-transfer reactivity. PMID:23934729

  7. Relação entre transferência de carga e as interações intermoleculares em complexos de hidrogênio heterocíclicos / Relationship between charge transfer and intermolecular interactions in heterocyclic hydrogen-bonded complexes

    Scientific Electronic Library Online (English)

    Boaz G., Oliveira; Regiane C. M. U. de, Araújo.

    2007-08-01

    Full Text Available SciELO Brazil | Language: Portuguese Abstract in portuguese [...] Abstract in english Hydrogen-bonded complexes formed by the interaction of the heterocyclic molecules C2H4O and C2H5N with HF, HCN, HNC and C2H2 have been studied using density functional theory. The hydrogen bond strength has been analyzed through electron density charge transfer from the proton acceptor to the proton [...] donor. The density charge transfer has been estimated using different methods such as Mulliken population analysis, CHELPG, GAPT and AIM. It has been shown that AIM-estimated charge transfer correlates very well with the hydrogen bond energy and the infrared bathochromic effect of the proton donor stretching frequencies.

  8. Intermolecular interactions and charge transfer transitions in aromatic hydrocarbon-tetracyanoethylene complexes.

    Science.gov (United States)

    Aquino, Adélia A J; Borges, Itamar; Nieman, Reed; Köhn, Andreas; Lischka, Hans

    2014-10-14

    A comprehensive theoretical study of the electronically excited states in complexes between tetracyanoethylene (TCNE) and three aromatic electron donors, benzene, naphthalene and anthracene, was performed with a focus on charge transfer (CT) transitions. The results show that the algebraic diagrammatic construction method to second order (ADC(2)) provides excellent possibilities for reliable calculations of CT states. Significant improvements in the accuracy of the computed transition energies are obtained by using the scaled opposite-spin (SOS) variant of ADC(2). Solvent effects were examined on the basis of the conductor-like screening model (COSMO) which has been implemented recently in the ADC(2) method. The dielectric constant and the refractive index of dichloromethane have been chosen in the COSMO calculations to compare with experimental solvatochromic effects. The computation of optimized ground state geometries and enthalpies of formation has been performed at the second-order Møller-Plesset perturbation theory (MP2) level. By comparison with experimental data and with high-level coupled-cluster methods including explicitly correlated (F12) wave functions, the importance of the SOS approach is demonstrated for the ground state as well. In the benzene-TCNE complex, the two lowest electronic excitations are of CT character whereas in the naphthalene and anthracene TCNE complexes three low-lying CT states are observed. As expected, they are strongly stabilized by the solvent. Geometry optimization in the lowest excited state allowed the calculation of fluorescence transitions. Solvent effects lead to a zero gap between S1 and S0 for the anthracene-TCNE complex. Therefore, in the series of benzene-TCNE to anthracene a change from a radiative to a nonradiative decay mechanism to the ground state is to be expected. PMID:25156236

  9. Cyclopentanone as a cation-stabilizing electron-pair donor in the calcium-catalyzed intermolecular carbohydroxylation of alkynes.

    Science.gov (United States)

    Stopka, Tobias; Niggemann, Meike

    2015-03-20

    Although they have been used as reactivity-controlling additives in cationic polymerizations for decades, Lewis basic "electron pair donor" (ED) compounds were never used for the stabilization of cationic intermediates in transformations of small molecules. As such an ED, cyclopentanone proved highly efficient for the stabilization of allyl and vinyl cations in combination with our calcium-based catalyst system. Therefore, the first general transition-metal-free intermolecular carbohydroxylation of alkynes with allyl and propargyl alcohols was realized. PMID:25741753

  10. Intermolecular Attractions

    Science.gov (United States)

    The Concord Consortium

    2011-12-11

    Intermolecular attractions are responsible for everything from the temperatures at which substances boil to the power of your immune system in recognizing pathogens and the climbing ability of geckos! Feel the strength of London dispersion and dipole-dipole attractions, explore how intermolecular attractions affect boiling point and solubility, and investigate the special role of hydrogen bonds in DNA. Finally, design your own antibody based on intermolecular attractions.

  11. Intermolecular hydrogen bond complexes by in situ charge transfer complexation of o-tolidine with picric and chloranilic acids

    Science.gov (United States)

    Refat, Moamen S.; Saad, Hosam A.; Adam, Abdel Majid A.

    2011-08-01

    A two new charge transfer complexes formed from the interactions between o-tolidine (o-TOL) and picric (PA) or chloranilic (CA) acids, with the compositions, [(o-TOL)(PA) 2] and [(o-TOL)(CA) 2] have been prepared. The 13C NMR, 1H NMR, 1H-Cosy, and IR show that the charge-transfer chelation occurs via the formation of chain structures O-H⋯N intermolecular hydrogen bond between 2NH 2 groups of o-TOL molecule and OH group in each PA or CA units. Photometric titration measurements concerning the two reactions in methanol were performed and the measurements show that the donor-acceptor molar ratio was found to be 1:2 using the modified Benesi-Hildebrand equation. The spectroscopic data were discussed in terms of formation constant, molar extinction coefficient, oscillator strength, dipole moment, standard free energy, and ionization potential. Thermal behavior of both charge transfer complexes showed that the complexes were more stable than their parents. The thermodynamic parameters were estimated from the differential thermogravimetric curves. The results indicated that the formation of molecular charge transfer complexes is spontaneous and endothermic.

  12. Evidence for alkali metal induced intermolecular acetylenic hydrogen atom transfer between hydrogen-bonded alkyne complexes in solid argon

    International Nuclear Information System (INIS)

    Condensation of acetylene, propyne, and 2-butyne/acetylene mixtures with heavy alkali metal atoms (Na, K, Cs) in an argon matrix at 15 K has led to the appearance of infrared absorptions due to ethylene, propylene, and trans-2-butene, respectively. These results stand in sharp contrast with the products obtained with lithium. Isotopic studies have shown that ethylene formation involved three different acetylene molecules and evidenced a difference in the product yield with hydrogen vs. deuterium as well as a preference for trans- vs. cis-C2H2D2 formation, which is discussed and rationalized by differences in the zero point energies for the different mixed deuterium isotopes of the intermediate vinyl radical. This trend is amplified by methyl substitution. Spectroscopic evidence was found in these experiments for cesium acetylide (Cs+C2H-) and a cesium-acetylene ? complex, which are involved in the intermolecular acetylenic hydrogen atom transfer process. 26 references, 3 figures, 2 tables

  13. Driving unidirectional molecular rotary motors with visible light by intra- and intermolecular energy transfer from palladium porphyrin.

    Science.gov (United States)

    Cnossen, Arjen; Hou, Lili; Pollard, Michael M; Wesenhagen, Philana V; Browne, Wesley R; Feringa, Ben L

    2012-10-24

    Driving molecular rotary motors using visible light (530-550 nm) instead of UV light was achieved using palladium tetraphenylporphyrin as a triplet sensitizer. Visible light driven rotation was confirmed by UV/vis absorption, circular dichroism and (1)H NMR spectroscopy and the rotation was confirmed to be unidirectional and with similar photostationary states, despite proceeding via a triplet instead of a singlet excited state of the molecular motor. Energy transfer proceeds in both inter- and intramolecular fashion from the triplet state of the porphyrin to the motor. Stern Volmer plots show that the rate of intermolecular quenching of the porphyrin excited state by the molecular motor is diffusion-controlled. PMID:23036108

  14. Intramolecular photo-switching and intermolecular energy transfer as primary photoevents in photoreceptive processes: The case of Euglena gracilis

    International Nuclear Information System (INIS)

    In this paper we report the results of measurements performed by FLIM on the photoreceptor of Euglenagracilis. This organelle consists of optically bistable proteins, characterized by two thermally stable isomeric forms: A498, non fluorescent and B462, fluorescent. Our data indicate that the primary photoevent of Euglena photoreception upon photon absorption consists of two contemporaneous different phenomena: an intramolecular photo-switch (i.e., A498 becomes B462), and a intermolecular and unidirectional Forster-type energy transfer. During the FRET process, the fluorescent B462 form acts as donor for the non-fluorescent A498 form of the protein nearby, which acts as acceptor. We hypothesize that in nature these phenomena follow each other with a domino progression along the orderly organized and closely packed proteins in the photoreceptor layer(s), modulating the isomeric composition of the photoreceptive protein pool. This mechanism guarantees that few photons are sufficient to produce a signal detectable by the cell.

  15. 75 FR 31665 - Electronic Fund Transfers

    Science.gov (United States)

    2010-06-04

    ...responsibilities of participants in electronic fund transfer systems. An...one consent form (or in the course of obtaining opt-ins through...205 Consumer protection, Electronic fund transfers, Federal Reserve...as follows: PART 205--ELECTRONIC FUND TRANSFERS...

  16. Comparison of intra- and intermolecular proton transfer in human carbonic anhydrase II.

    Science.gov (United States)

    Taoka, S; Tu, C; Kistler, K A; Silverman, D N

    1994-07-01

    The catalysis of the hydration of CO2 by human carbonic anhydrase II (HCA II) includes the transfer of a proton from zinc-bound water to histidine 64 utilizing a network of intervening hydrogen-bonded water molecules, then the proton is transferred to buffer in solution. We used stopped-flow spectrophotometry and 18O exchange between CO2 and water measured by mass spectrometry to compare catalytic constants dependent on proton transfer in HCA II and in the mutant H64A HCA II containing the replacement His64-->Ala. Maximal velocities and oxygen-18 exchange catalyzed by H64A HCA II showed that nearly all of the proton transfer with this mutant proceeded through the imidazole buffer. The following parameters were very similar or identical in catalysis by H64A HCA II compared with catalysis by wild-type HCA II both in the presence of large concentrations of imidazole (100 mM): the maximal rate of initial velocity and of exchange of 18O between CO2 and water, solvent hydrogen isotope effects on the maximal velocity, and the dependence of these isotope effects on the atom fraction of deuterium in solvent water. These results indicate that the proton transfer involving the zinc-bound water in catalysis is not significantly affected by the difference between the mobility of the free imidazole buffer and the side chain of His 64. Moreover, data for both the wild-type and mutant enzymes are consistent with proton transfer through intervening hydrogen-bonded water bridges in the active sites. These features of the proton transfer are discussed in terms of a model in which the first proton transfer from the zinc-bound water to an adjacent water is rate limiting. PMID:8027057

  17. Electronic structure, intermolecular interactions and electron emission dynamics via anion photoelectron imaging

    Science.gov (United States)

    Grumbling, Emily Rose

    This dissertation explores the use of anion photoelectron imaging to interrogate electronic dynamics in small chemical systems with an emphasis on photoelectron angular distributions. Experimental ion generation, mass selection, laser photodetachment and photoelectron imaging were performed in a negative-ion photoelectron imaging spectrometer described in detail. Results for photodetachment from the simplest anion, H-, are used to illustrate fundamental principles of quantum mechanics and provide basic insight into the physics behind photoelectron imaging from a pedagogical perspective. This perspective is expanded by introducing imaging results for additional, representative atomic and small molecular anions (O-, NH2- and N3-) obtained at multiple photon energies to address the energy-dependence of photoelectron angular distributions both conceptually and semi-quantitatively in terms of interfering partial photoelectron waves. The effect of solvation on several of these species (H-, O-, and NH2 -) is addressed in photoelectron imaging of several series of cluster anions. The 532 and 355 nm energy spectra for H-(NH3) n and NH2-(NH3) n (n = 0-5) reveal that these species are accurately described as the core anion solute stabilized electrostatically by n loosely coordinated NH3 molecules. The photoelectron angular distributions for solvated H- deviate strongly from those predicted for unsolvated H- as the electron kinetic energy approaches zero, indicating a shift in the partial-wave balance consistent with both solvation-induced perturbation (and symmetry-breaking) of the H - parent orbital and photoelectron-solvent scattering. The photoelectron energy spectra obtained for the cluster series [O(N2O) n]- and [NO(N2O) n]- indicate the presence of multiple structural isomers of the anion cores, the former displaying sharp core-switching at n = 4, the latter isomer coexistence over the entire range studied. The photoelectron angular distributions for detachment from the O- (N2O)n and NO-(N 2O)n isomers deviate strongly from those expected for bare O- and NO-, respectively, in the region of an anionic shape resonance of N2O, suggesting resonant photoelectron-solvent scattering. Partial-wave models for two-centered photoelectron interference in photodetachment from dissociating I2 - is presented and discussed in the context of previous results. 10 New time-resolved photoelectron imaging results for I2 -, for both parallel and perpendicular pump and probe beam polarizations, are presented and briefly discussed. Finally, new ideas and directions are proposed.

  18. Polar solvation and electron transfer. Annual progress report, July 1, 1992--June 30, 1993

    Energy Technology Data Exchange (ETDEWEB)

    1993-04-13

    The report is divided into the following sections: completion of previous studies on solvation dynamics, dipole lattice studies, inertial components of solvation response, simple models of solvation dynamics, rotational dynamics and dielectric friction, intramolecular electron transfer reactions, and intermolecular donor-acceptor complexes.

  19. Enhancing intermolecular benzoyl-transfer reactivity in crystals by growing a "reactive" metastable polymorph by using a chiral additive.

    Science.gov (United States)

    Murali, Chebrolu; Shashidhar, Mysore S; Gonnade, Rajesh G; Bhadbhade, Mohan M

    2009-01-01

    Racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate, which normally crystallizes in a monoclinic form (form I, space group P2(1)/n) could be persuaded to crystallize out as a metastable polymorph (form II, space group C2/c) by using a small amount of either D- or L- 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoformate as an additive in the crystallization medium. The structurally similar enantiomeric additive was chosen by the scrutiny of previous experimental results on the crystallization of racemic 2,4-di-O-benzoyl-myo-inositol-1,3,5-orthoacetate. Form II crystals can be thermally transformed to form I crystals at about 145 degrees C. The relative organization of the molecules in these dimorphs vary slightly in terms of the helical assembly of molecules, that is, electrophile (El)...nucleophile (Nu) and C-H...pi interactions, but these minor variations have a profound effect on the facility and specificity of benzoyl-group-transfer reactivity in the two crystal forms. While form II crystals undergo a clean intermolecular benzoyl-group-transfer reaction, form I crystals are less reactive and undergo non-specific benzoyl-group transfer leading to a mixture of products. The role played by the additive in fine-tuning small changes that are required in the molecular packing opens up the possibility of creating new polymorphs that show varied physical and chemical properties. Crystals of D-2,6-di-O-benzoyl-myo-inositol-1,3,5-orthoformate (additive) did not show facile benzoyl-group-transfer reactivity (in contrast to the corresponding racemic compound) due to the lack of proper juxtaposition and assembly of molecules. PMID:19035584

  20. Intermolecular interactions as actors in energy-transfer processes in lanthanide complexes with 2,2'-bipyridine.

    Science.gov (United States)

    Puntus, Lada N; Lyssenko, Konstantin A; Pekareva, Irina S; Bünzli, Jean-Claude G

    2009-07-01

    A series of lanthanide complexes [LnCl(x)(bpy)(y)(H(2)O)(z)]Cl(3-x)(H(2)O)(n)(EtOH)(m) (Ln = Eu, Gd, Tb; x = 1, 2; y = 1, 2; z = 2-4) with different numbers of 2,2'-bipyridine (bpy), chloride ions, and water molecules in the inner coordination sphere were synthesized and investigated with the aim of relating their molecular geometry and crystal packing to the efficiency of ligand-to-metal energy transfer. In conjunction to the rotation of the pyridine rings upon coordination to the Ln ion, the high flexibility displayed by bpy ligands leads to rather unexpected bending of these rings with respect to the central bond, owing to intermolecular interactions such as Cl...pi and pi-stacking ones. Deciphering the luminescence properties of the Eu and Tb complexes needs to take into account both the composition of the inner coordination sphere and the peculiarities of the crystal packing. For instance, in addition to the classical ligand --> Eu charge-transfer state (LMCT), another charge-transfer state induced by pi-stacking interactions (SICT) could be identified. These two states, located between the singlet and triplet states of the bpy ligand(s), provide relays facilitating the energy migration from the singlet to the triplet states and eventually to the excited Eu states, improving the overall ligand-to-Eu energy transfer. Another point is the involvement of the inner-sphere water molecules in H-bonding with chloride ions, which considerably lowers their luminescence quenching ability, so that the adducts remain highly luminescent. For instance, the terbium chloride with two bpy ligands is an efficient near-UV to green light converter, with an overall quantum yield equal to 37% despite the coordinated water molecules. The interpretations given are substantiated by DFT and TD-DFT theoretical calculations of the complexes and ligand assemblies. PMID:19522489

  1. Manifestations of sequential electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Thurnauer, M.C.; Tang, J.

    1996-05-01

    An essential feature of efficient photo-initiated charge separation is sequential electron transfer. Charge separation is initiated by photoexcitation of an electron donor followed by rapid electron transfer steps from the excited donor through a series of electron acceptors, so that, after one or two successive steps, charge separation is stabilized by the physical separation between the oxidized donor and reduced acceptor. The prime example of this process is the sequential electron transfer that takes place in the purple photosynthetic bacterial reaction center, resulting in the charge separation between P{sup +} and Q{sub A}{sup -} across a biological membrane. We have developed magnetic resonance tools to monitor sequential electron transfer. We are applying these techniques to study charge separation in natural photo-synthetic systems in order to gain insights into the features of the reaction center proteins that promote efficient charge separation. As we establish what some of these factors are, we are beginning to design artificial photosynthetic systems that undergo photoinduced sequential electron transfer steps.

  2. Electronic spectra of protonated benzaldehyde clusters with Ar and N2: effect of ??* excitation on the intermolecular potential.

    Science.gov (United States)

    Patzer, Alexander; Zimmermann, Max; Alata, Ivan; Jouvet, Christophe; Dopfer, Otto

    2010-12-01

    Electronic spectra of the S(1)?S(0) transition of dimers of protonated benzaldehyde (BZH(+)) with Ar and N(2) are recorded by resonance-enhanced photodissociation in a tandem mass spectrometer. The S(1) origins observed are shifted to higher frequency upon complexation with Ar (?S(1) = 300 cm(-1)) and N(2) (?S(1) = 628 cm(-1)). Ab initio calculations at the CC2/aug-cc-pVDZ level suggest an assignment to H-bonded dimers of L = Ar and N(2) binding to the cis isomer of O-protonated BZH(+), yielding values of ?S(1) = 242 and 588 cm(-1) for cis-BZH(+)-L(H). Electronic ??* excitation results in a substantial increase of the proton affinity of BZH(+), which in turn destabilizes the intermolecular H-bonds to the inert ligands by 35%. The drastic effects of electronic ??* excitation on the geometric and electronic structure as well as the strength and anisotropy of the intermolecular potential (H-bonding and ?-bonding) are investigated. PMID:21069976

  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. [Electrochemical measurement of intraprorein and interprotein electron transfer].

    Science.gov (United States)

    Shumiantseva, V V; Bulko, T V; Lisitsina, V B; Urlakher, V B; Kuzikov, A B; Suprun, E V; Archakov, A I

    2013-01-01

    Intramolecular and intermolecular direct (unmediated) electron transfer was studied by means of electrochemical techniques in flavohemoprotein cytochrome P450 BM3 (CYP102A1 from Bacillius megaterium) and between cytochrome b5 and cytochrome c. Flavohemoprotein cytochrome P450 BM3 was immobilized on a screen printed graphite electrode, modified with a biocompatible nanocomposite material based on the didodecyldimethylammonium bromide DDAB and gold nanoparticles. Analytical characterictics of DDAB/Au/P450 BM3 electrodes were studied with cyclic voltammetry and square wave voltammetry. It was shown that intramolecular electron transfer was realized between diflavin (FAD/FMN) and heme domain of CYP102A1. An electron transport chain of flavohemoprotein P450 BM3 immobilized at nanostructued electrode is realized as: electrode --> FAD --> FMN --> heme. Electron transfer occurs inside the protein, and it is an evidence of functional interaction between diflavin and heme domains. The effect of a substrate (lauric acid) or inhibitors (metyrapone or imidazole) binding on the electrochemical parameters of flavohemoprotein P450 BM3 was also studied. Interprotein electron transfer was analyzed between cytochrome b5 and cytochrome c. Electrochemical analysis revealed that electron transfer takes place in protein-protein complexes with participants possessing different redox potentials. PMID:24159813

  5. Theoretical study of intermolecular proton transfer reaction in isolated 5-hydroxyisoxazole water complexes

    Science.gov (United States)

    Yi, Ping G.; Liang, Yong H.; Tang, Zhen Q.

    2006-03-01

    A systematic investigation in isolated 5-hydroxyisoxazole-water complexes (5-HIO · (H 2O) nn = 1-3) is performed at the DFT level, employing B3LYP/6-31G(d, p) basis set. Single-point energy calculations are also performed at the MP2 level using B3LYP/6-31G(d, p) optimized geometries and the 6-311++G(d, p) basis set. The computational results show that the keto tautomer K 2 is the most stable isomer in the gas phase, and the tautomer K 1 to be the next most stable tautomer. Hydrogen bonding between HIO and the water molecule(s) will dramatically lower the barrier by a concerted multiple proton transfer mechanism. The proton transfer process of 3WE cis ? 3WK 1 and 2WE trans ? 2WK 2 is found to be more efficient in two tautomerization, and the barrier heights are 7.03 and 14.15 kcal/mol at B3LYP/6-31G(d, p) level, respectively. However, the proton transfer reaction between E cis and K 1 cannot happen without solvent-assisted.

  6. Theoretical study of intermolecular proton transfer reaction in isolated 5-hydroxyisoxazole-water complexes

    International Nuclear Information System (INIS)

    A systematic investigation in isolated 5-hydroxyisoxazole-water complexes (5-HIO . (H2O) n n = 1-3) is performed at the DFT level, employing B3LYP/6-31G(d, p) basis set. Single-point energy calculations are also performed at the MP2 level using B3LYP/6-31G(d, p) optimized geometries and the 6-311++G(d, p) basis set. The computational results show that the keto tautomer K2 is the most stable isomer in the gas phase, and the tautomer K1 to be the next most stable tautomer. Hydrogen bonding between HIO and the water molecule(s) will dramatically lower the barrier by a concerted multiple proton transfer mechanism. The proton transfer process of 3WE cis ? 3WK1 and 2WE trans ? 2WK2 is found to be more efficient in two tautomerization, and the barrier heights are 7.03 and 14.15 kcal/mol at B3LYP/6-31G(d, p) level, respectively. However, the proton transfer reaction between E cis and K1 cannot happen without solvent-assisted

  7. Quantum chemical studies on excited state intermolecular proton transfer of oxazine dyes

    Science.gov (United States)

    Grofcsik, A.; Kubinyi, M.; Ruzsinszky, A.; Veszprémi, T.; Jones, W. J.

    2000-11-01

    The excited state lifetimes of oxazine dyes nile blue and oxazine 720 show a significant solvent dependence. As an aid to the interpretation of the decay in acidic environments the ground electronic states and the first singlet excited states of oxazine monocations and dications have been studied by methods of quantum chemistry. Ab initio calculations carried out on the lower members on this series show a significant increase of the electron densities of the ring nitrogen on excitation. The calculated electron energies also suggest that the second proton attaches to the ring nitrogen in the excited states, in contrast to the ground states where (in the case of oxazine 720) the second proton attaches to the terminal nitrogen. A kinetic scheme is proposed for the decay process in which in acidic environments the main deactivation path is the reaction of excited state monocations with protons, followed by internal conversion and subsequent deprotonation of the ground state dications.

  8. Probing intermolecular protein-protein interactions in the calcium-sensing receptor homodimer using bioluminescence resonance energy transfer (BRET)

    DEFF Research Database (Denmark)

    Jensen, Anders A.; Hansen, Jakob L

    2002-01-01

    The calcium-sensing receptor (CaR) belongs to family C of the G-protein coupled receptor superfamily. The receptor is believed to exist as a homodimer due to covalent and non-covalent interactions between the two amino terminal domains (ATDs). It is well established that agonist binding to family C receptors takes place at the ATD and that this causes the ATD dimer to twist. However, very little is known about the translation of the ATD dimer twist into G-protein coupling to the 7 transmembrane moieties (7TMs) of these receptor dimers. In this study we have attempted to delineate the agonist-induced intermolecular movements in the CaR homodimer using the new bioluminescence resonance energy transfer technique, BRET2, which is based on the transference of energy from Renilla luciferase (Rluc) to the green fluorescent protein mutant GFP2. We tagged CaR with Rluc and GFP2 at different intracellular locations. Stable and highly receptor-specific BRET signals were obtained in tsA cells transfected with Rluc- and GFP2-tagged CaRs under basal conditions, indicating that CaR is constitutively dimerized. However, the signals were not enhanced by the presence of agonist. These results could indicate that at least parts of the two 7TMs of the CaR homodimer are in close proximity in the inactivated state of the receptor and do not move much relative to one another upon agonist activation. However, we cannot exclude the possibility that the BRET technology is unable to register putative conformational changes in the CaR homodimer induced by agonist binding because of the bulk sizes of the Rluc and GFP2 molecules.

  9. The "excited state C-C bond cleavage-luminescence" phenomenon of a biphenyl-substituted methylenecyclopropane triggered by intermolecular energy transfer from triplet benzophenone.

    Science.gov (United States)

    Matsui, Yasunori; Kido, Taiki; Ohta, Eisuke; Ikeda, Hiroshi

    2014-11-21

    Existence of the "excited state C-C bond cleavage-luminescence" phenomenon was demonstrated by utilizing intermolecular energy transfer from the excited-triplet benzophenone to 2,2-di(4-biphenylyl)-1-methylenecyclopropane (3). An excellent linear relationship between the intensity of the excitation laser light and that of luminescence clearly shows that formation of the corresponding excited trimethylenemethane biradical (3)4??* proceeds via a one-photon route. PMID:25267075

  10. The kinetic peculiarities of intermolecular proton transfer from NH groups of octa( m-trifluoromethylphenyl)tetraazaporphin in the nitrogen base-benzene system

    Science.gov (United States)

    Petrov, O. A.; Khelevina, O. G.; Kuzmina, E. L.

    2010-09-01

    The acid-base interaction of octa( m-trifluoromethylphenyl)tetraazaporphin with nitrogen bases in benzene was studied. The rates of intermolecular transfer of sterically screened NH group protons from octa( m-trifluoromethylphenyl)tetraazaporphin to n-butylamine and tert-butylamine were found to be low. A scheme of the process was suggested. The influence of the nature of bases on the kinetic parameters of acid-base interactions was studied.

  11. Electron transfer in pendant-group and molecularly doped polymers

    Science.gov (United States)

    Duke, C. B.; Meyer, R. J.

    1981-03-01

    Utilizing the molecular-ion model previously constructed to describe photoemission and ultraviolet absorption in pendant-group polymers, we derive an expression for the probability of electron transfer between a molecular ion and a neutral molecular species embedded in a frequency-dependent dielectric medium described by the (nonlocal) longitudinal dielectric response function ?(q-->,?). The medium is taken to exhibit three branches of its longitudinal polarization excitation spectrum defined by ?(q-->,?(q-->))=0: a low-frequency branch corresponding to intermolecular motions, an infrared branch corresponding to molecular vibrational modes, and a high-frequency branch corresponding to valence-electron excitations. In addition, the linear coupling of the electron to the intramolecular modes of the initial and final molecular ions is incorporated into the model. The electron-transfer probability is evaluated as a function of the spacing, R, between the molecular-ion sites and the energy difference between the intitial and final molecular-ion states. Utilizing parameters in ?(q-->,?) typical of pendant-group polymers (e.g., polystyrene, polyvinylpyridine) or the matrices utilized in molecularly doped polymers films (e.g., polycarbonates), we find that the electron-transfer process is activated and that the low-frequency dielectric relaxations characteristic of these polymers create this activation. Explicit expressions for the activation energies are derived and evaluated numerically for poly(2-vinylypyridine): a material for which a model of ?(q-->,?) is available in the literature. The valence-electron excitations do not influence the electron-transfer activation energies, but both the intramolecular and longitudinal-polarization vibrational modes increase these activation energies above the values predicted using the low-frequency relaxations alone. The energies, ??n, of many of these vibrational modes are, however, larger than thermal energies, kT. Consequently, the predicted electron-transfer activation energies are smaller than those given by traditional semiclassical models of electron transfer. Moreover, these activation energies also depend explicitly on the spacing, R, between the two sites. This R dependence is evaluated for both classical and quantum-mechanical models of the change densities on the molecular ions. Our analysis predicts, therefore, the complete spacing and temperature dependence of the electron-transfer probabilities as functions of the intramolecular molecular-ion vibrational frequencies and electron-vibration coupling constants, and of the frequency and spatial dependence of the dielectric response of the medium in which these ions are embedded. This prediction permits the identification of scaling laws relating both the activation energies and electron-transfer prefactors to molecular and dielectric observables: an identification which provides valuable guidance in the molecular design of efficient electronic transport media.

  12. Dimensionality of intermolecular interactions in layered crystals by electronic-structure theory and geometric analysis.

    Science.gov (United States)

    George, Janine; Deringer, Volker L; Dronskowski, Richard

    2015-02-01

    Two-dimensional (2D) and layered structures gained a lot of attention in the recent years ("post-graphene era"). The chalcogen cyanides S(CN)(2) and Se(CN)(2) offer themselves as interesting model systems to study layered inorganic crystal structures; both are built up from cyanide molecules connected by chalcogen bonds (ChBs). Here, we investigate ChBs and their cooperativity directly within the layers of the S(CN)(2) and Se(CN)(2) crystal structures and, furthermore, in putative O(CN)(2) and Te(CN)(2) crystal structures derived therefrom. Moreover, we determine the energetic contributions of ChBs within the layers to the overall stabilization energy. To compare these structures not only energetically but also geometrically, we derive a direction-dependent root mean square of the Cartesian displacement, a possible tool for further computational investigations of layered compounds. The molecular chains connected by ChBs are highly cooperative but do not influence each other when combined to layers: the ChBs are nearly orthogonal in terms of energy when connected to the same chalcogen acceptor atom. Layers built up from ChBs account for 41% to 79% of the overall interaction energy in the crystal. This provides new, fundamental insight into the meaning of ChBs, and therefore directed intermolecular interactions, for the stability of crystal structures. PMID:25363246

  13. Electron-transfer organic and bioorganic photochemistry

    International Nuclear Information System (INIS)

    A review is given of the literature on electron transfer in organic and bioorganic photochemistry mainly from 1985 to April 1988. Topics covered include the theory and kinetics of electron transfer, the dynamic and chemical behaviour of the geminate ion-radical pair, the effects of salts on photoinduced electron-transfer reactions, the photorepair of UV-damaged DNA and cyclobutane-ring splitting by photoinduced electron transfer, model compounds of NAD(P)+/NAD(P)H, deazoflavin and flavin and two-electron photoredox reactions and the application of photoinduced electron transfer reactions to organic synthesis. (U.K.)

  14. Catalysis and electron transfer in protein crystals: the binary and ternary complexes of methylamine dehydrogenase with electron acceptors.

    Science.gov (United States)

    Ferrari, Davide; Merli, Angelo; Peracchi, Alessio; Di Valentin, Marilena; Carbonera, Donatella; Rossi, Gian Luigi

    2003-04-11

    Polarized absorption microspectrophotometry has been used to detect catalysis and intermolecular electron transfer in single crystals of two multiprotein complexes: (1) the binary complex between Paracoccus denitrificans methylamine dehydrogenase, which contains tryptophan-tryptophylquinone (TTQ) as a cofactor, and its redox partner, the blue copper protein amicyanin; (2) the ternary complex between the same two proteins and cytochrome c-551i. Continuous wave electron paramagnetic resonance has been used to compare the state of copper in polycrystalline powders of the two systems. While catalysis and intermolecular electron transfer from reduced TTQ to copper are too fast to be accessible to our measurements, heme reduction occurs over a period of several minutes. The observed rate constant is about four orders of magnitude lower than in solution. The analysis of the temperature dependence of this apparent constant provides values for the parameters H(AB), related to electronic coupling between the two centers, and lambda, the reorganizational energy, that are compatible with electron transfer being the rate-determining step. From these parameters and the known distance between copper and heme, it is possible to calculate the parameter beta, which depends on the nature of the intervening medium, obtaining a value typical of electron transfer across a protein matrix. These findings suggest that the ternary complex in solution might achieve a higher efficiency than the rigid crystal structure thanks to an as yet unidentified role of protein dynamics. PMID:12686155

  15. Quantum Plasmonics: Electron transfer processes

    Science.gov (United States)

    Nordlander, Peter

    2013-03-01

    Plasmon energies can be tuned across the spectrum by simply changing the geometrical shape of a nanostructure. Plasmons can efficiently capture incident light and focus it to nanometer sized hotspots which can enhance electronic and vibrational excitations in nearby structures.[1] Another important but still relatively unexplored property of plasmons, is that they can be efficient sources of hot energetic electrons which can transfer into nearby structures and induce a variety of processes. This process is a quantum mechanical effect: the decay of plasmon quanta into electron-hole pairs. I will discuss how plasmon induced hot electrons can be used in various applications: such as to induce chemical reactions in molecules physisorbed on a nanoparticle surface;[2] to inject electrons directly into the conduction band of a nearby substrate;[3] and to induce local doping of a nearby graphene sheet.[4] References [1] N.J. Halas et al., Adv. Mat. 24(2012)4842 [2] R. Huschka et al., JACS 133(2011)12247; S. Mukherjee et al. TBP 2012 [3] M. W. Knight et al., Science 332(2011)702, Z.Y. Fang et al., NL 12(2012)3808 [4] Z.Y. Fang et al., ACS Nano 6(2012)10.1021/nn304028b

  16. Quinone methide generation via photoinduced electron transfer.

    Science.gov (United States)

    Percivalle, Claudia; La Rosa, Andrea; Verga, Daniela; Doria, Filippo; Mella, Mariella; Palumbo, Manlio; Di Antonio, Marco; Freccero, Mauro

    2011-05-01

    Photochemical activation of water-soluble 1,8-naphthalimide derivatives (NIs) as alkylating agents has been achieved by irradiation at 310 and 355 nm in aqueous acetonitrile. Reactivity in aqueous and neat acetonitrile has been extensively investigated by laser flash photolysis (LFP) at 355 nm, as well as by steady-state preparative irradiation at 310 nm in the presence of water, amines, thiols, and ethyl vinyl ether. Product distribution analysis revealed fairly efficient benzylation of the amines, hydration reaction, and 2-ethoxychromane generation, in the presence of ethyl vinyl ether, resulting from a [4 + 2] cycloaddition onto a transient quinone methide. Remarkably, we found that the reactivity was dramatically suppressed under the presence of oxygen and radical scavengers, such as thiols, which was usually associated with side product formation. In order to unravel the mechanism responsible for the photoreactivity of these NI-based molecules, a detailed LFP study has been carried out with the aim to characterize the transient species involved. LFP data suggest a photoinduced electron transfer (PET) involving the NI triplet excited state (?(max) 470 nm) of the NI core and the tethered quinone methide precursor (QMP) generating a radical ions pair NI(•-) (?(max) 410 nm) and QMP(•+). The latter underwent fast deprotonation to generate a detectable phenoxyl radical (?(max) 390 and 700 nm), which was efficiently reduced by the radical anion NI(•-), generating detectable QM. The mechanism proposed has been validated through a LFP investigation at 355 nm exploiting an intermolecular reaction between the photo-oxidant N-pentylnaphthalimide (NI-P) and a quaternary ammonium salt of a Mannich base as QMP (2a), in both neat and aqueous acetonitrile. Remarkably, these experiments revealed the generation of the model o-QM (?(max) 400 nm) as a long living transient mediated by the same reactivity pathway. Negligible QM generation has been observed under the very same conditions by irradiation of the QMP in the absence of the NI. Owing to the NIs redox and recognition properties, these results represent the first step toward new molecular devices capable of both biological target recognition and photoreleasing of QMs as alkylating species, under physiological conditions. PMID:21425810

  17. 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

    2015-02-01

    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. PMID:25591991

  18. Electron-phonon interactions, pair-transfer processes, and superconductivity in TTF[Ni(dmit)2]2

    International Nuclear Information System (INIS)

    A model is developed for superconductivity in TTF[Ni(dmit)2]2. We include both electron-intramolecular and -intermolecular vibration couplings. These interactions are the principal sources of superconducting pairing. The electron-intramolecular vibration coupling constants are estimated after performing a complete normal-mode analysis. The electron-intermolecular vibration coupling constants are also estimated. The unique band structure of this material [with both highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) derived bands crossing the Fermi level] leads to a pair-transfer term between the bands. Estimates for Tc are in reasonable agreement with experimental results. We find that major contribution to the electron-phonon interaction, in this material, comes to the LUMO band from acoustic phonons and pair transfer processes reduce the effects of the intraband Coulomb repulsion. copyright 1997 The American Physical Society

  19. Two-Dimensional Free Energy Surfaces for Electron Transfer Reactions in Solution

    Directory of Open Access Journals (Sweden)

    M. Tachiya

    2008-10-01

    Full Text Available Change in intermolecular distance between electron donor (D and acceptor (A can induce intermolecular electron transfer (ET even in nonpolar solvent, where solvent orientational polarization is absent. This was shown by making simple calculations of the energies of the initial and final states of ET. In the case of polar solvent, the free energies are functions of both D-A distance and solvent orientational polarization. On the basis of 2-dimensional free energy surfaces, the relation of Marcus ET and exciplex formation is discussed. The transient effect in fluorescence quenching was measured for several D-A pairs in a nonpolar solvent. The results were analyzed by assuming a distance dependence of the ET rate that is consistent with the above model.

  20. Intramolecular electron transfer in the inverted region

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Pingyun; Duesing, R.; Tapolsky, G.; Meyer, T.J. (Univ. of North Carolina, Chapel Hill (USA))

    1989-10-11

    In 1960 Marcus predicted that rate constants for electron transfer should decrease with -{Delta}G in the inverted region. In the inverted region, -{Delta}G > {lambda}, where {lambda} is the reorganization energy and {Delta}G the free energy loss associated with the electron transfer. Experimental verification of this prediction has been difficult to obtain but has been found by pulse radiolysis in rigid organic glasses, by Closs, Miller, and co-workers in unsymmetrical, linked organics, in accounting for separation yields in photoinduced electron transfer, and by light-induced electron transfer in linked porphyrin-quinone systems. The authors report here the first examples based on transition-metal complexes and, as predicted theoretically, that there is a clear relationship between electron transfer in the inverted region and nonradiative decay in a closely related family of excited states.

  1. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    CERN Document Server

    Haverkate, Lucas; Johnson, Mark; Carter, Elisabeth; Kotlewski, Arek; Picken, Stephen; Mulder, Fokko; Kearley, Gordon

    2013-01-01

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics within the CT complex, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the groundstate of the complex: a charge delocalization of about 10-2 electron from the HAT6 core to TNF is deduced from both Raman and NMR measurements, implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visi...

  2. Influence of intermolecular vibrations on the electronic coupling in organic semiconductors: the case of anthracene and perfluoropentacene.

    Science.gov (United States)

    Martinelli, Nicolas G; Olivier, Yoann; Athanasopoulos, Stavros; Ruiz Delgado, Mari-Carmen; Pigg, Kathryn R; da Silva Filho, Demétrio A; Sánchez-Carrera, Roel S; Venuti, Elisabetta; Della Valle, Raffaele G; Brédas, Jean-Luc; Beljonne, David; Cornil, Jérôme

    2009-09-14

    We have performed classical molecular dynamics simulations and quantum-chemical calculations on molecular crystals of anthracene and perfluoropentacene. Our goal is to characterize the amplitudes of the room-temperature molecular displacements and the corresponding thermal fluctuations in electronic transfer integrals, which constitute a key parameter for charge transport in organic semiconductors. Our calculations show that the thermal fluctuations lead to Gaussian-like distributions of the transfer integrals centered around the values obtained for the equilibrium crystal geometry. The calculated distributions have been plugged into Monte-Carlo simulations of hopping transport, which show that lattice vibrations impact charge transport properties to various degrees depending on the actual crystal structure. PMID:19637205

  3. Electron transfer: classical approaches and new frontiers

    Science.gov (United States)

    Tributsch; Pohlmann

    1998-03-20

    Electron transfer, under conditions of weak interaction and a medium acting as a passive thermal bath, is very well understood. When electron transfer is accompanied by transient chemical bonding, such as in interfacial coordination electrochemical mechanisms, strong interaction and molecular selectivity are involved. These mechanisms, which take advantage of "passive self-organization," cannot yet be properly described theoretically, but they show substantial experimental promise for energy conversion and catalysis. The biggest challenge for the future, however, may be dynamic, self-organized electron transfer. As with other energy fluxes, a suitable positive feedback mechanism, through an active molecular environment, can lead to a (transient) decrease of entropy equivalent to an increase of molecular electronic order for the activated complex. A resulting substantial increase in the rate of electron transfer and the possibility of cooperative transfer of several electrons (without intermediates) can be deduced from phenomenological theory. The need to extend our present knowledge may be derived from the observation that chemical syntheses and fuel utilization in industry typically require high temperatures (where catalysis is less relevant), whereas corresponding processes in biological systems are catalyzed at environmental conditions. This article therefore focuses on interfacial or membrane-bound electron transfer and investigates an aspect that nature has developed to a high degree of perfection: self-organization. PMID:9506932

  4. Nuclear reorganization barriers to electron transfer

    International Nuclear Information System (INIS)

    The nuclear barrier to electron transfer arises from the need for reorganization of intramolecular and solvent internuclear distances prior to electron transfer. For reactions with relatively small driving force (''normal'' free-energy region) the nuclear factors and rates increase as intrinsic inner-shell and outer-shell barriers decrease; this is illustrated by data for transition metal complexes in their ground electronic states. By contrast, in the inverted free-energy region, rates and nuclear factors decrease with decreasing ''intrinsic'' barriers; this is illustrated by data for the decay of charge-transfer excited states. Several approaches to the evaluation of the outer-shell barrier are explored in an investigation of the distance dependence of the nuclear factor in intramolecular electron-transfer processes. 39 refs., 14 figs., 3 tabs

  5. 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.

  6. 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.

  7. Effect of surface-plasmon polaritons on spontaneous emission and intermolecular energy-transfer rates in multilayered geometries

    Energy Technology Data Exchange (ETDEWEB)

    Marocico, C. A.; Knoester, J. [Zernike Institute for Advanced Materials, University of Groningen, Nijenborgh 4, NL-9747 AG Groningen (Netherlands)

    2011-11-15

    We use a Green's tensor method to investigate the spontaneous emission rate of a molecule and the energy-transfer rate between molecules placed in two types of layered geometries: a slab geometry and a planar waveguide. We focus especially on the role played by surface-plasmon polaritons in modifying the spontaneous emission and energy-transfer rates as compared to free space. In the presence of more than one interface, the surface-plasmon polariton modes split into several branches, and each branch can contribute significantly to modifying the electromagnetic properties of atoms and molecules. Enhancements of several orders of magnitude both in the spontaneous emission rate of a molecule and the energy-transfer rate between molecules are obtained and, by tuning the parameters of the geometry, one has the ability to control the range and magnitude of these enhancements. For the energy-transfer rate interference effects between contributions of different plasmon-polariton branches are observed as oscillations in the distance dependence of this rate.

  8. Intermolecular Proton Transfer in Microhydrated Guanine-Cytosine Base Pairs: a New Mechanism for Spontaneous Mutation in DNA

    Science.gov (United States)

    Cerón-Carrasco, J. P.; Requena, A.; Zúñiga, J.; Michaux, C.; Perpête, E. A.; Jacquemin, D.

    2009-09-01

    Accurate calculations of the double proton transfer (DPT) in the adenine-thymine base pair (AT) were presented in a previous work [ J. Phys. Chem. A 2009, 113, 7892. ] where we demonstrated that the mechanism of the reaction in solution is strongly affected by surrounding water. Here we extend our methodology to the guanine-cytosine base pair (GC), for which it turns out that the proton transfer in the gas phase is a synchronous concerted mechanism. The O(G)-H-N(C) hydrogen bond strength emerges as the key parameter in this process, to the extent that complete transfer takes place by means of this hydrogen bond. Since the main effect of the molecular environment is precisely to weaken this bond, the direct proton transfer is not possible in solution, and thus the tautomeric equilibrium must be assisted by surrounding water molecules in an asynchronous concerted mechanism. This result demonstrates that water plays a crucial role in proton reactions. It does not act as a passive element but actually catalyzes the DPT.

  9. Intermolecular Adhesion in Conjugated Polymers

    CERN Document Server

    Schmit, J D; Schmit, Jeremy D.; Levine, Alex J.

    2006-01-01

    Conjugated polymers are observed to aggregate in solution. To account for this observation we propose a inter-chain binding mechanism based on the intermolecular tunneling of the delocalized $\\pi$-electrons occurring at points where the polymers cross. This tunneling mechanism predicts specific bound structures of chain that depend on whether they are semiconducting or metallic. Semiconducting chains should form polyacene-like states exhibiting binding at every other site, while (doped) metallic chains can bind at each site. We also show that solitons co-localize with the intermolecular binding sites thereby strengthening the binding effect and investigate the conformational statistics of the resulting bimolecular aggregates.

  10. Low Temperature Electronic Transport and Electron Transfer through Organic Macromolecules

    OpenAIRE

    Zimbovskaya, Natalya A.

    2002-01-01

    It is shown that at low temperatures and moderate electron dephasing the electron transmission function reveales a structure containing information about donor/acceptor sites effectively participating in the electron transfer (ET) processes and primary pathways of electrons tunneling through molecular bridges in macromolecules. This important information can be obtained as a result of analysis of experimental low temperature current-voltage characteristics for chosen molecules.

  11. H2 and (H2)2 molecules with an ab initio optimization of wave functions in correlated state: electron-proton couplings and intermolecular microscopic parameters

    Science.gov (United States)

    K?dzielawa, Andrzej P.; Bielas, Agata; Acquarone, Marcello; Biborski, Andrzej; Ma?ka, Maciej M.; Spa?ek, Józef

    2014-12-01

    The hydrogen molecules H2 and {{?ft( {{H}2} \\right)}2} are analyzed with electronic correlations taken into account between the 1s electrons in an exact manner. The optimal single-particle Slater orbitals are evaluated in the correlated state of H2 by combining their variational determination with the diagonalization of the full Hamiltonian in the second-quantization language. All electron-ion coupling constants are determined explicitly and their relative importance is discussed. Sizable zero-point motion amplitude and the corresponding energy are then evaluated by taking into account the anharmonic contributions up to the ninth order in the relative displacement of the ions from their static equilibrium value. The applicability of the model to solid molecular hydrogen is briefly analyzed by calculating intermolecular microscopic parameters for the 2× {{H}2} rectangular configuration, as well its ground state energy.

  12. Pseudospin Transfer Torques in Semiconductor Electron Bilayers

    OpenAIRE

    Kim, Youngseok; Macdonald, Allan H.; Gilbert, Matthew J.

    2012-01-01

    We use self-consistent quantum transport theory to investigate the influence of electron-electron interactions on interlayer transport in semiconductor electron bilayers in the absence of an external magnetic field. We conclude that, even though spontaneous pseudospin order does not occur at zero field, interaction-enhanced quasiparticle tunneling amplitudes and pseudospin transfer torques do alter tunneling I-V characteristics, and can lead to time-dependent response to a d...

  13. Single Molecule Spectroscopy of Electron Transfer

    International Nuclear Information System (INIS)

    The objectives of this research are threefold: (1) to develop methods for the study electron transfer processes at the single molecule level, (2) to develop a series of modifiable and structurally well defined molecular and nanoparticle systems suitable for detailed single molecule/particle and bulk spectroscopic investigation, (3) to relate experiment to theory in order to elucidate the dependence of electron transfer processes on molecular and electronic structure, coupling and reorganization energies. We have begun the systematic development of single molecule spectroscopy (SMS) of electron transfer and summaries of recent studies are shown. There is a tremendous need for experiments designed to probe the discrete electronic and molecular dynamic fluctuations of single molecules near electrodes and at nanoparticle surfaces. Single molecule spectroscopy (SMS) has emerged as a powerful method to measure properties of individual molecules which would normally be obscured in ensemble-averaged measurement. Fluctuations in the fluorescence time trajectories contain detailed molecular level statistical and dynamical information of the system. The full distribution of a molecular property is revealed in the stochastic fluctuations, giving information about the range of possible behaviors that lead to the ensemble average. In the case of electron transfer, this level of understanding is particularly important to the field of molecular and nanoscale electronics: from a device-design standpoint, understanding and controlling this picture of the overall range of possible behaviors will likely prove to be as important as designing ia the ideal behavior of any given molecule.

  14. Bioinspired electron-transfer systems and applications

    International Nuclear Information System (INIS)

    Bioinspired electron-transfer systems including artificial photosynthesis and respiration are presented herein together with some of their applications. First, multi-step electron-transfer systems composed of electron donor-acceptor ensembles have been developed, mimicking functions of the photosynthetic reaction center. However, a significant amount of energy is lost during the multi-step electron-transfer processes. Then, as an alternative to conventional charge-separation functional molecular models based on multi-step long-range electron transfer within redox cascades, simple donor-acceptor dyads have been developed to attain along-lived and high energy charge-separated state without significant loss of excitation energy, by fine control of the redox potentials and of the geometry of donor-acceptor dyads that have small reorganization energies of electron transfer. Such simple molecular dyads, capable of fast charge separation but extremely slow charge recombination, have significant advantages with regard to synthetic feasibility, providing a variety of applications including construction of organic solar cells and development of efficient photo-catalytic systems for the solar energy conversion. An efficient four-electron reduction of dioxygen to water by one-electron reductants such as ferrocene derivatives as well as by an NADH analog has also been achieved as a respiration model by using a cofacial dicobalt porphyrin that can form the ?-peroxo Co(III)-O2hat can form the ?-peroxo Co(III)-O2Co(III) complex. The catalytic mechanism of the four-electron reduction of dioxygen has been clarified based on the detailed kinetic study and the detection of the intermediate. (author)

  15. Protein electron transfer: Dynamics and statistics

    Science.gov (United States)

    Matyushov, Dmitry V.

    2013-07-01

    Electron transfer between redox proteins participating in energy chains of biology is required to proceed with high energetic efficiency, minimizing losses of redox energy to heat. Within the standard models of electron transfer, this requirement, combined with the need for unidirectional (preferably activationless) transitions, is translated into the need to minimize the reorganization energy of electron transfer. This design program is, however, unrealistic for proteins whose active sites are typically positioned close to the polar and flexible protein-water interface to allow inter-protein electron tunneling. The high flexibility of the interfacial region makes both the hydration water and the surface protein layer act as highly polar solvents. The reorganization energy, as measured by fluctuations, is not minimized, but rather maximized in this region. Natural systems in fact utilize the broad breadth of interfacial electrostatic fluctuations, but in the ways not anticipated by the standard models based on equilibrium thermodynamics. The combination of the broad spectrum of static fluctuations with their dispersive dynamics offers the mechanism of dynamical freezing (ergodicity breaking) of subsets of nuclear modes on the time of reaction/residence of the electron at a redox cofactor. The separation of time-scales of nuclear modes coupled to electron transfer allows dynamical freezing. In particular, the separation between the relaxation time of electro-elastic fluctuations of the interface and the time of conformational transitions of the protein caused by changing redox state results in dynamical freezing of the latter for sufficiently fast electron transfer. The observable consequence of this dynamical freezing is significantly different reorganization energies describing the curvature at the bottom of electron-transfer free energy surfaces (large) and the distance between their minima (Stokes shift, small). The ratio of the two reorganization energies establishes the parameter by which the energetic efficiency of protein electron transfer is increased relative to the standard expectations, thus minimizing losses of energy to heat. Energetically efficient electron transfer occurs in a chain of conformationally quenched cofactors and is characterized by flattened free energy surfaces, reminiscent of the flat and rugged landscape at the stability basin of a folded protein.

  16. Ultra-fast charge transfer in organic electronic materials and at hybrid interfaces studied using the core-hole clock technique

    International Nuclear Information System (INIS)

    Research highlights: ? The use of resonant photoemission in its 'core-hole clock' expression for the study of the dynamical charge transfer across hybrid organic-inorganic interfaces and for the intermolecular charge transfer in the bulk of organic thin films is reviewed. ? The electronic coupling to the substrate and the efficiency of charge transport across hybrid interfaces is different for individual electronic subsystems of the molecular adsorbate. ? The intermolecular charge transfer in the bulk of discotic liquid crystals occurs on the order of a few femtoseconds and is faster than expected from the macroscopic charge transport characteristics of the material. -- Abstract: The focus of this brief review is the use of resonant photoemission in its 'core-hole clock' expression for the study of two important problems relevant for the field of organic electronics: the dynamical charge transfer across hybrid organic-inorganic interfaces, and the intermolecular charge transfer in the bulk of organic thin films. Following an outline of the technique, a discussion of its applicability and a short overview of experimental results obtained thus far, two examples are used to illustrate particular results relevant for the understanding of the charge transport in organic electronic devices. First, for Fe(II)-tetraphenylporphyrin molecules on semi-metallic molybdenum disulfide substrates, the electronic coupling to the substrate and the efficiency of charge transport athe efficiency of charge transport across the interface different for the individual molecular electronic subsystems is discussed. And second, a discotic liquid crystalline material forming columnar assemblies is used to illustrate ultra-fast intermolecular charge transfer on the order of a few femtoseconds indicating an electronic coupling between the phthalocyanine units stronger than expected from the macroscopic charge transport characteristics of the material.

  17. Ultra-fast charge transfer in organic electronic materials and at hybrid interfaces studied using the core-hole clock technique

    Energy Technology Data Exchange (ETDEWEB)

    Friedlein, R. [School of Materials Science and Research Center for Integrated Science, Japan Advanced Institute of Science and Technology, Nomi, Ishikawa 923-1292 (Japan); Braun, S. [Department of Physics, Chemistry and Biology (IFM), Linkoeping University, S-581 83 Linkoeping (Sweden); Jong, M.P. de [University of Twente, 7500 AE, Enschede (Netherlands); Osikowicz, W. [SAPA Industries, 61281 Finspang (Sweden); Fahlman, M. [Department of Physics, Chemistry and Biology (IFM), Linkoeping University, S-581 83 Linkoeping (Sweden); Salaneck, W.R., E-mail: wrs@ifm.liu.s [Department of Physics, Chemistry and Biology (IFM), Linkoeping University, S-581 83 Linkoeping (Sweden)

    2011-01-15

    Research highlights: {yields} The use of resonant photoemission in its 'core-hole clock' expression for the study of the dynamical charge transfer across hybrid organic-inorganic interfaces and for the intermolecular charge transfer in the bulk of organic thin films is reviewed. {yields} The electronic coupling to the substrate and the efficiency of charge transport across hybrid interfaces is different for individual electronic subsystems of the molecular adsorbate. {yields} The intermolecular charge transfer in the bulk of discotic liquid crystals occurs on the order of a few femtoseconds and is faster than expected from the macroscopic charge transport characteristics of the material. -- Abstract: The focus of this brief review is the use of resonant photoemission in its 'core-hole clock' expression for the study of two important problems relevant for the field of organic electronics: the dynamical charge transfer across hybrid organic-inorganic interfaces, and the intermolecular charge transfer in the bulk of organic thin films. Following an outline of the technique, a discussion of its applicability and a short overview of experimental results obtained thus far, two examples are used to illustrate particular results relevant for the understanding of the charge transport in organic electronic devices. First, for Fe(II)-tetraphenylporphyrin molecules on semi-metallic molybdenum disulfide substrates, the electronic coupling to the substrate and the efficiency of charge transport across the interface different for the individual molecular electronic subsystems is discussed. And second, a discotic liquid crystalline material forming columnar assemblies is used to illustrate ultra-fast intermolecular charge transfer on the order of a few femtoseconds indicating an electronic coupling between the phthalocyanine units stronger than expected from the macroscopic charge transport characteristics of the material.

  18. New Type of Dual Solid-State Thermochromism: Modulation of Intramolecular Charge Transfer by Intermolecular ?-? Interactions, Kinetic Trapping of the Aci-Nitro Group, and Reversible Molecular Locking

    Science.gov (United States)

    Naumov, Pan?e; Lee, Sang Cheol; Ishizawa, Nobuo; Jeong, Young Gyu; Chung, Ihn Hee; Fukuzumi, Shunichi

    2009-09-01

    When heated above room temperature, some crystalline polymorphs of the 1,3-bis(hydroxyalkylamino)-4,6-dinitrobenzenes (BDBn, n = 2-5), bis(hydroxyalkyl) analogues of the intramolecular charge-transfer molecule 1,3-diamino-4,6-dinitrobenzene, exhibit "dual" thermochromism: gradual color change from yellow to orange at lower temperatures, and sharp color change from orange to red at higher temperatures. These two thermochromic changes are related to different solid-state processes. When allowed to cool to room temperature, the yellow color of the thermochromic molecules with different alkyl length (n) is recovered with unexpectedly different kinetics, the order of the respective rate constants ranging from 10-7-10-6 s-1 for BDB2 to about 0.1 s-1 in the case of BDB3. The thermochromic mechanism and the reasons behind the different kinetics were clarified on the basis of detailed crystallographic characterization, kinetic thermoanalysis, and spectroscopic study of eight crystalline forms (seven polymorphs and one solvate). It was found that the polymorphism is due to the possibility of "locking" and "unlocking" of the alkyl arms by formation of a strong intramolecular hydrogen bond between the hydroxyl groups at their hydroxyl termini. The locking of BDB2, with shortest alkyl arms, is reversible and it can be controlled thermally; either of the two conformations can be obtained in the solid state by proper thermal treatment. By use of high temperature in situ single crystal X-ray diffraction analysis of BDB3, direct evidence was obtained that the gradual thermochromic change is related to increased distance and weakened ?-? interactions between the stacked benzene rings: the lattice expands preferably in the stacking direction, causing enhanced oscillator strength and red shift of the absorption edge of the intramolecular charge transfer transition. The second, sharp thermochromic change had been assigned previously to solid-solid phase transition triggered by intramolecular proton transfer of one amino proton to the nitro group, whereupon an aci-nitro form is thermally populated. Contrary to the numerous examples of solid thermochromic molecules based on either pericyclic reactions or keto-enol tautomerism, this system appears to be the first organic thermochromic family where the thermochromic change appears as an effect of intermolecular ?-? interactions and thermal intramolecular proton transfer to aromatic nitro group.

  19. Intermolecular hydrogen transfer between guest species in small and large cages of methane + propane mixed gas hydrates.

    Science.gov (United States)

    Sugahara, Takeshi; Kobayashi, Yusuke; Tani, Atsushi; Inoue, Tatsuya; Ohgaki, Kazunari

    2012-03-15

    To investigate the molecular interaction between guest species inside of the small and large cages of methane + propane mixed gas hydrates, thermal stabilities of the methyl radical (possibly induced in small cages) and the normal propyl and isopropyl radicals (induced in large cages) were investigated by means of electron spin resonance measurements. The increase of the total amount of the normal propyl and isopropyl radicals reveals that the methyl radical in the small cage withdraws one hydrogen atom from the propane molecule enclathrated in the adjacent large cage of the structure-II hydrate. A guest species in a hydrate cage has the ability to interact closely with the other one in the adjacent cages. The clathrate hydrate may be utilized as a possible nanoscale reaction field. PMID:22352402

  20. 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

  1. Quantum effects in biological electron transfer.

    Czech Academy of Sciences Publication Activity Database

    de la Lande, A.; Babcock, N. S.; ?ezá?, Jan; Levy, B.; Sanders, B. C.; Salahub, D.

    2012-01-01

    Ro?. 14, ?. 17 (2012), s. 5902-5918. ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40550506 Keywords : electron transfer * tunnelling * decoherence * semi-classical molecular dynamics * density functional theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.829, year: 2012

  2. Femtosecond events in the free electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Brede, Ortwin [Interdisciplinary Group Time-Resolved Spectroscopy, University of Leipzig (Germany)]. E-mail: brede@mpgag.uni-leipzig.de; Naumov, Sergej [Institute of Surface Modification, Leipzig (Germany)

    2007-08-15

    The ion-molecule reaction between solvent parent radical cations and hetero group-substituted aromatics in non-polar media shows a characteristic product distribution, which depends strongly on the mobility of the substituent. This electron transfer phenomenon seems to reflect femtodynamics of the donor molecule, which is appearing in the nanosecond time range.

  3. Monitoring molecule dynamics by free electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Brede, O. E-mail: brede@mpgag.uni-leipzig.de; Naumov, S.; Hermann, R

    2003-06-01

    Molecular oscillations take place in the time range of some 10-100 fs. In asymmetric molecules, accompanied with rotation and necking motions of molecule parts changes of the electron distribution of the molecular orbitals occur. In phenols the rotation motion of the C-OH bond with a frequency around 10{sup 13} Hz causes dramatical electron motions in the molecule. These motions could be monitored with an extremely rapid chemical reaction (free electron transfer) which results in product characteristics for the assumed different borderline structures of the phenol molecule.

  4. Experimental and database-transferred electron-density analysis and evaluation of electrostatic forces in coumarin-102 dye.

    Science.gov (United States)

    Bibila Mayaya Bisseyou, Yvon; Bouhmaida, Nouhza; Guillot, Benoit; Lecomte, Claude; Lugan, Noel; Ghermani, Noureddine; Jelsch, Christian

    2012-12-01

    The electron-density distribution of a new crystal form of coumarin-102, a laser dye, has been investigated using the Hansen-Coppens multipolar atom model. The charge density was refined versus high-resolution X-ray diffraction data collected at 100?K and was also constructed by transferring the charge density from the Experimental Library of Multipolar Atom Model (ELMAM2). The topology of the refined charge density has been analysed within the Bader `Atoms In Molecules' theory framework. Deformation electron-density peak heights and topological features indicate that the chromen-2-one ring system has a delocalized ?-electron cloud in resonance with the N (amino) atom. The molecular electrostatic potential was estimated from both experimental and transferred multipolar models; it reveals an asymmetric character of the charge distribution across the molecule. This polarization effect is due to a substantial charge delocalization within the molecule. The molecular dipole moments derived from the experimental and transferred multipolar models are also compared with the liquid and gas-phase dipole moments. The substantial molecular dipole moment enhancements observed in the crystal environment originate from the crystal field and from intermolecular charge transfer induced and controlled by C-H···O and C-H···N intermolecular hydrogen bonds. The atomic forces were integrated over the atomic basins and compared for the two electron-density models. PMID:23165601

  5. Vibrational spectroscopic studies of the chemical dynamics in charge transfer complexes of the type iodine-pyridine 2. Intermolecular dynamics from far infrared bands

    Science.gov (United States)

    Tassaing, T.; Besnard, M.; Yarwood, J.

    Detailed interpretation of the far infrared spectra of the pyridine-I complex (in ternary mixtures with an inert solvent) has been attempted using models for elucidation of intermolecular dynamics between components of a liquid mixture. For the complex very diluted in an inert solvent, in the framework of the Robertson-Yarwood model, it is found that the bandshape of the upsilon mode originates from the phase relaxation of the I-I oscillator due to its I- I anharmonic 'indirect' coupling with the upsilon mode. The frequency shifts and widths of the two bands observed at higher concentrations of pyridine in the mixture are then explored by applying the vibrational relaxation formalism of Kubo with the analytical expression of Fukuda, T., Ikawa, S., and Kimura, M., (1989, Chem. Phys ., 133,137) to treat the 'direct' coupling of the transition dipole of the complex with the dipole moment of the solvent molecule. Both phase and energy relaxation contributions have been considered. It has been found that band intensities are intimately related to the extent of charge transfer between the complex components, and that the frequency shifts and widths are dependent on these intensities and on the signs of the transition dipole. At low concentrations of donor, the harmonic contribution /q totally dominates the bandwidths, but at higher concentrations 2/2 q is needed. In addition, the upsilonband phase relaxation explains the bandwidth perfectly well, but for the (lower frequency) upsilon band there is a significant contribution from energy relaxation processes. A study of the effects of the diffusion coefficients on the bandwidths has shown that the reorientational motion of pyridine lies at the origin of the observed broadening. 2 D- I I- I D- I

  6. Estimates of electronic coupling for excess electron transfer in DNA

    Science.gov (United States)

    Voityuk, Alexander A.

    2005-07-01

    Electronic coupling Vda is one of the key parameters that determine the rate of charge transfer through DNA. While there have been several computational studies of Vda for hole transfer, estimates of electronic couplings for excess electron transfer (ET) in DNA remain unavailable. In the paper, an efficient strategy is established for calculating the ET matrix elements between base pairs in a ? stack. Two approaches are considered. First, we employ the diabatic-state (DS) method in which donor and acceptor are represented with radical anions of the canonical base pairs adenine-thymine (AT) and guanine-cytosine (GC). In this approach, similar values of Vda are obtained with the standard 6-31G* and extended 6-31++G** basis sets. Second, the electronic couplings are derived from lowest unoccupied molecular orbitals (LUMOs) of neutral systems by using the generalized Mulliken-Hush or fragment charge methods. Because the radical-anion states of AT and GC are well reproduced by LUMOs of the neutral base pairs calculated without diffuse functions, the estimated values of Vda are in good agreement with the couplings obtained for radical-anion states using the DS method. However, when the calculation of a neutral stack is carried out with diffuse functions, LUMOs of the system exhibit the dipole-bound character and cannot be used for estimating electronic couplings. Our calculations suggest that the ET matrix elements Vda for models containing intrastrand thymine and cytosine bases are essentially larger than the couplings in complexes with interstrand pyrimidine bases. The matrix elements for excess electron transfer are found to be considerably smaller than the corresponding values for hole transfer and to be very responsive to structural changes in a DNA stack.

  7. Chemical origin of blue- and redshifted hydrogen bonds: Intramolecular hyperconjugation and its coupling with intermolecular hyperconjugation

    Science.gov (United States)

    Li, An Yong

    2007-04-01

    Upon formation of a H bond Y ⋯H-XZ, intramolecular hyperconjugation n(Z )??*(X-H) of the proton donor plays a key role in red- and blueshift characters of H bonds and must be introduced in the concepts of hyperconjugation and rehybridization. Intermolecular hyperconjugation transfers electron density from Y to ?*(X-H) and causes elongation and stretch frequency redshift of the X-H bond; intramolecular hyperconjugation couples with intermolecular hyperconjugation and can adjust electron density in ?*(X-H); rehybridization causes contraction and stretch frequency blueshift of the X-H bond on complexation. The three factors—intra- and intermolecular hyperconjugations and rehybridization determine commonly red- or blueshift of the formed H bond. A proton donor that has strong intramolecular hyperconjugation often forms blueshifted H bonds.

  8. Electron transfer reactions in microporous solids

    Science.gov (United States)

    Mallouk, T. E.

    1993-01-01

    The research program involves the use of microporous solids (zeolites, clays, layered, and tunnel structure oxide semiconductors) as organizing media for artificial photosynthetic systems. The purpose of the microporous solid is twofold. First, it induces spatial organization of photoactive and electroactive components (sensitizers, semiconductor particles, electron relays, and catalysts) at the solid-solution interface, enhancing the quantum efficiency of charge separation and separating physically the ultimate electron donor and acceptor in the electron transport chain. Second, since the microcrystalline solid admits only molecules of a certain charge and size, it is possible to achieve permanent charge separation by sieving chemical photoproducts (e.g., H2 and I3(-), or H2 and O2) from each other. Spectroscopic and electrochemical methods are used to study the kinetics of electron transfer reactions in these hybrid molecular/solid state assemblies.

  9. Electron transfer in branched expanded pyridinium molecules.

    Czech Academy of Sciences Publication Activity Database

    Hromadová, Magdaléna; Lachmanová, Št?pánka; Pospíšil, Lubomír; Fortage, J.; Dupeyre, G.; Perruchot, Ch.; Lainé, P. P.

    Aveiro : DEMAC - Universidade de Aveiro , 2014. s. 99-99. [Meeting of the Portuguese Electrochemical Society /19./. Iberian Meeting of Electrochemistry /16./. 30.06.2014-02.07.2014, Aveiro ] R&D Projects: GA ?R(CZ) GA14-05180S Grant ostatní: Rada Programu interní porpory projekt? mezinárodní spolupráce AV ?R M200401202 Institutional support: RVO:61388955 Keywords : electron transfer * electrochemistry * pyridinium Subject RIV: CG - Electrochemistry

  10. Promoting Interspecies Electron Transfer with Biochar

    OpenAIRE

    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...

  11. Resonant electron transfer between quantum dots

    OpenAIRE

    Openov, Leonid A.

    1999-01-01

    An interaction of electromagnetic field with a nanostructure composed of two quantum dots is studied theoretically. An effect of a resonant electron transfer between the localized low-lying states of quantum dots is predicted. A necessary condition for such an effect is the existence of an excited bound state whose energy lies close to the top of the barrier separating the quantum dots. This effect may be used to realize the reversible quantum logic gate NOT if the superposi...

  12. Kinetic ion thermometers for electron transfer dissociation.

    Science.gov (United States)

    Pepin, Robert; Ture?ek, František

    2015-02-19

    Peptide fragment ions of the z-type were used as kinetic ion thermometers to gauge the internal energy of peptide cation-radicals produced by electron transfer in the gas-phase. Electron transfer dissociation (ETD)-produced z2 ions containing the leucine residue, z2(Leu-Lys) and z2(Leu-Arg), were found to undergo spontaneous dissociation by loss of C3H7 that was monitored by time-resolved kinetic measurements on the time scale of the linear ion trap mass spectrometer. Kinetic modeling of the dissociations, including collisional cooling and product loss by neutralization, provided unimolecular rate constants for dissociation that were converted to the z ion internal energies using RRKM theory. The internal energy of z2(Leu-Lys) and z2(Leu-Arg) fragment ions was found to decrease with the increasing size of the precursor peptide ion, indicating vibrational energy partitioning between the ion and neutral fragments and ergodic behavior. The experimentally determined excitation in the peptide cation-radicals upon electron transfer (285-327 kJ mol(-1)) was found to be lower than that theoretically calculated from the reaction exothermicity. The reasons for this missing energy are discussed. PMID:25594857

  13. Transfer coating by electron initiated polymerization

    International Nuclear Information System (INIS)

    The high speed and depth of cure possible with electron initiated monomer/oligomer coating systems provide many new opportunities for approaches to product finishing. Moreover, the use of transfer or cast coating using films or metallic surfaces offers the ability to precisely control the surface topology of liquid film surfaces during polymerization. Transfer coating such as with textiles has been a commercial process for many years and the synergistic addition of EB technology permits the manufacture of unusual new products. One of these, the casting paper used in the manufacture of vinyl and urethane fabrics, is the first EB application to use a drum surface for pattern replication in the coating. In this case the coated paper is cured against, and then released from, an engraved drum surface. Recent developments in the use of plastic films for transfer have been applied to the manufacture of transfer metallized and coated paper and paperboard products for packaging. Details of these and related processes will be presented as well as a discussion of the typical product areas using this high speed transfer technology. (author)

  14. Theory of intermolecular forces

    CERN Document Server

    Margenau, H; Ter Haar, D

    1971-01-01

    Theory of Intermolecular Forces deals with the exposition of the principles and techniques of the theory of intermolecular forces. The text focuses on the basic theory and surveys other aspects, with particular attention to relevant experiments. The initial chapters introduce the reader to the history of intermolecular forces. Succeeding chapters present topics on short, intermediate, and long range atomic interactions; properties of Coulomb interactions; shape-dependent forces between molecules; and physical adsorption. The book will be of good use to experts and students of quantum mechanics

  15. Switching of the triplet-triplet-annihilation upconversion with photoresponsive triplet energy acceptor: photocontrollable singlet/triplet energy transfer and electron transfer.

    Science.gov (United States)

    Xu, Kejing; Zhao, Jianzhang; Cui, Xiaoneng; Ma, Jie

    2015-01-22

    A photoswitchable fluorescent triad based on two 9,10-diphenylanthracene (DPA) and one dithienylethene (DTE) moiety is prepared for photoswitching of triplet-triplet annihilation upconversion. The DPA and DTE moieties in the triad were connected via Click reaction. The DPA unit in the triad was used as the triplet energy acceptor and upconverted fluorescence emitter. The fluorescence of the triad is switched ON with the DTE moiety in open form [DTE-(o)] (upconversion quantum yield ?UC = 1.2%). Upon UV irradiation, photocyclization of the DTE-(o) moiety produces the closed form [DTE-(c)], as a result the fluorescence of DPA moiety was switched off (?UC is negligible). Three different mechanisms are responsible for the upconverted fluorescence photoswitching effect (i.e., the photoactivated fluorescence resonance energy transfer, the intramolecular electron transfer, as well as the photoactivated intermolecular triplet energy transfer between the photosensitizer and DTE-(c) moiety). Previously, the photoswitching of TTA upconversion was accomplished with only one mechanism (i.e., the triplet state quenching of the photosensitizer by DTE-(c) via either the intermolecular or intramolecular energy transfer). The photophysical processes involved in the photochromism and photoswitching of TTA upconversion were studied with steady-state UV-vis absorption and fluorescence emission spectroscopies, nanosecond transient absorption spectroscopy, electrochemical characterization, and DFT/TDDFT calculations. PMID:25514195

  16. 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

  17. Promoting interspecies electron transfer with biochar

    DEFF Research Database (Denmark)

    Chen, Shanshan; Rotaru, Amelia-Elena

    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.

  18. 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

  19. Photoinduced electron transfer within a zinc porphyrin-cyclobis(paraquat-p-phenylene) donor-acceptor dyad.

    Science.gov (United States)

    Fathalla, Maher; Barnes, Jonathan C; Young, Ryan M; Hartlieb, Karel J; Dyar, Scott M; Eaton, Samuel W; Sarjeant, Amy A; Co, Dick T; Wasielewski, Michael R; Stoddart, J Fraser

    2014-11-01

    Understanding the mechanism of efficient photoinduced electron-transfer processes is essential for developing molecular systems for artificial photosynthesis. Towards this goal, we describe the synthesis of a donor-acceptor dyad comprising a zinc porphyrin donor and a tetracationic cyclobis(paraquat-p-phenylene) (CBPQT(4+) ) acceptor. The X-ray crystal structure of the dyad reveals the formation of a dimeric motif through the intermolecular coordination between the triazole nitrogen and the central Zn metal of two adjacent units of the dyad. Photoinduced electron transfer within the dyad in MeCN was investigated by femtosecond and nanosecond transient absorption spectroscopy, as well as by transient EPR spectroscopy. Photoexcitation of the dyad produced a weakly coupled ZnP(+.) -CBPQT(3+.) spin-correlated radical-ion pair having a ?=146?ns lifetime and a spin-spin exchange interaction of only 0.23?mT. The long radical-ion-pair lifetime results from weak donor-acceptor electronic coupling as a consequence of having nine bonds between the donor and the acceptor, and the reduction in reorganization energy for electron transfer caused by charge dispersal over both paraquat units within CBPQT(3+.) . PMID:25258209

  20. Intermolecular hydrogen bond energies in crystals evaluated using electron density properties: DFT computations with periodic boundary conditions.

    Science.gov (United States)

    Vener, M V; Egorova, A N; Churakov, A V; Tsirelson, V G

    2012-11-01

    The hydrogen bond (H-bond) energies are evaluated for 18 molecular crystals with 28 moderate and strong O-H···O bonds using the approaches based on the electron density properties, which are derived from the B3LYP/6-311G** calculations with periodic boundary conditions. The approaches considered explore linear relationships between the local electronic kinetic G(b) and potential V(b) densities at the H···O bond critical point and the H-bond energy E(HB). Comparison of the computed E(HB) values with the experimental data and enthalpies evaluated using the empirical correlation of spectral and thermodynamic parameters (Iogansen, Spectrochim. Acta Part A 1999, 55, 1585) enables to estimate the accuracy and applicability limits of the approaches used. The V(b)-E(HB) approach overestimates the energy of moderate H-bonds (E(HB) X-ray diffraction experiments. PMID:22786749

  1. 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.

  2. Electron transfer pathways in microbial oxygen biocathodes

    International Nuclear Information System (INIS)

    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 O2 reduction by heme compounds. Here we showed that 1 ?M 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 O2 reduction to H2O2 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.

  3. 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.

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

    CERN Multimedia

    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.

  5. Devices which transfer electrons one-by-one

    International Nuclear Information System (INIS)

    An introduction is given to the field of single-electron devices, which are electronic circuits across which electrons may be transferred one by one. Experiments are described on the single-junction box and the four-junction box, devices in which electrons were transferred to a metallic island and their presence detected using a single-electron electrometer. The single-junction box, the simpler of the two devices, allows one to control the thermally-averaged number of excess electrons on the metallic island, whereas with the four-junction box one can actually control the transfer of individual electrons. (author) 11 refs.; 5 figs

  6. Reaction of electron-transfer flavoprotein with electron-transfer flavoprotein-ubiquinone oxidoreductase

    International Nuclear Information System (INIS)

    The oxidative half-reaction of electron-transfer flavoprotein (ETF), electron transfer from ETF to electron-transfer flavoprotein-ubiquinone oxidoreductase (ETF-QO), is dependent on complementary surface charges on the two proteins. ETF is the positively charged member of the redox pair. The evidence is based on the pH and ionic strength dependencies of the comproportionation of oxidized ETF and ETF hydroquinone catalyzed by ETF-QO and on the effects of chemical modification of ETF on the comproportionation reaction. Acetylation of one and five epsilon-amino groups of lysyl residues results in 3- and 13-fold increases, respectively, in the K/sub m/ of ETF-QO for ETF but no change in V/sub max/. Amidination, which maintains positive charge at modified loci, has no effect on steady-state kinetic constants. These chemical modifications have no effect on the equilibrium constant for equilibration of ETF redox states. The K/sub m/ of ETF-QO for ETF is pH dependent above pH 8.5, suggesting titration of lysyl residues. The ionic strength dependence of TN/KmETF for the reaction follows the limiting Bronsted equation. The ETF-QO-catalyzed comproportionation reaction exhibits a primary deuterium isotope effect in D2O, perhaps indicating the participation of solvent water in the electron-transfer reaction

  7. Path integral approach to non-relativistic electron charge transfer

    Energy Technology Data Exchange (ETDEWEB)

    Laskin, N. [IsoTrace Laboratory, University of Toronto, Toronto, ON (Canada)]. E-mail: nlaskin@rocketmail.com; Tomski, I. [IsoTrace Laboratory, University of Toronto, Toronto, ON (Canada)

    2001-11-28

    A path integral approach has been generalized for the non-relativistic electron charge transfer processes. The charge transfer - the capture of an electron by an ion passing another atom, or more generally the problem of rearrangement collisions - is formulated in terms of influence functionals. It has been shown that the electron charge transfer process can be treated either as an electron transition problem or as ion and atom elastic scattering in the effective potential field. The first-order Born approximation for the electron charge transfer reaction cross section has been reproduced to prove the adequacy of the path integral approach for this problem. (author)

  8. 77 FR 6310 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-02-07

    ...CFPB-2011-0009] RIN 3170-AA15 Electronic Fund Transfers (Regulation...Regulation E, which implements the Electronic Fund Transfer Act, and the...respect to the phrase ``normal course of business'' in the definition...the following methods: Electronic:...

  9. Electron transfer in gas surface collisions

    International Nuclear Information System (INIS)

    In this thesis electron transfer between atoms and metal surfaces in general is discussed and the negative ionization of hydrogen by scattering protons at a cesiated crystalline tungsten (110) surface in particular. Experimental results and a novel theoretical analysis are presented. In Chapter I a theoretical overview of resonant electron transitions between atoms and metals is given. In the first part of chapter II atom-metal electron transitions at a fixed atom-metal distance are described on the basis of a model developed by Gadzuk. In the second part the influence of the motion of the atom on the atomic charge state is incorporated. Measurements presented in chapter III show a strong dependence of the fraction of negatively charged H atoms scattered at cesiated tungsten, on the normal as well as the parallel velocity component. In chapter IV the proposed mechanism for the parallel velocity effect is incorporated in the amplitude method. The scattering process of protons incident under grazing angles on a cesium covered surface is studied in chapter V. (Auth.)

  10. 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.

  11. Intermolecular and surface forces

    CERN Document Server

    Israelachvili, Jacob N

    2011-01-01

    This reference describes the role of various intermolecular and interparticle forces in determining the properties of simple systems such as gases, liquids and solids, with a special focus on more complex colloidal, polymeric and biological systems. The book provides a thorough foundation in theories and concepts of intermolecular forces, allowing researchers and students to recognize which forces are important in any particular system, as well as how to control these forces. This third edition is expanded into three sections and contains five new chapters over the previous edition.· starts fr

  12. Intermolecular and Surface Forces

    CERN Document Server

    Israelachvili, Jacob N

    2010-01-01

    This reference describes the role of various intermolecular and interparticle forces in determining the properties of simple systems such as gases, liquids and solids, with a special focus on more complex colloidal, polymeric and biological systems. The book provides a thorough foundation in theories and concepts of intermolecular forces, allowing researchers and students to recognize which forces are important in any particular system, as well as how to control these forces. This third edition is expanded into three sections and contains five new chapters over the previous edition.· starts fr

  13. Activation entropy of electron transfer reactions

    CERN Document Server

    Milischuk, A A; Newton, M D; Milischuk, Anatoli A.; Matyushov, Dmitry V.; Newton, Marshall D.

    2005-01-01

    We report microscopic calculations of free energies and entropies for intramolecular electron transfer reactions. The calculation algorithm combines the atomistic geometry and charge distribution of a molecular solute obtained from quantum calculations with the microscopic polarization response of a polar solvent expressed in terms of its polarization structure factors. The procedure is tested on a donor-acceptor complex in which ruthenium donor and cobalt acceptor sites are linked by a four-proline polypeptide. The reorganization energies and reaction energy gaps are calculated as a function of temperature by using structure factors obtained from our analytical procedure and from computer simulations. Good agreement between two procedures and with direct computer simulations of the reorganization energy is achieved. The microscopic algorithm is compared to the dielectric continuum calculations. We found that the strong dependence of the reorganization energy on the solvent refractive index predicted by conti...

  14. Direct electron transfer based enzymatic fuel cells

    International Nuclear Information System (INIS)

    In this mini-review we briefly describe some historical developments made in the field of enzymatic fuel cells (FCs), discussing important design considerations taken when constructing mediator-, cofactor-, and membrane-less biological FCs (BFCs). Since the topic is rather extensive, only BFCs utilizing direct electron transfer (DET) reactions on both the anodic and cathodic sides are considered. Moreover, the performance of mostly glucose/oxygen biodevices is analyzed and compared. We also present some unpublished results on mediator-, cofactor-, and membrane-less glucose/oxygen BFCs recently designed in our group and tested in different human physiological fluids, such as blood, plasma, saliva, and tears. Finally, further perspectives for BFC applications are highlighted.

  15. Theory of plasmon enhanced interfacial electron transfer

    Science.gov (United States)

    Wang, Luxia; May, Volkhard

    2015-04-01

    A particular attempt to improve the efficiency of a dye sensitized solar cell is it's decoration with metal nano-particles (MNP). The MNP-plasmon induced enhancement of the local field enlarges the photoexcitation of the dyes and a subsequent improvement of the charge separation efficiency may result. In a recent work (2014 J. Phys. Chem. C 118 2812) we presented a theory of plasmon enhanced interfacial electron transfer for perylene attached to a TiO2 surface and placed in the proximity of a spherical MNP. These earlier studies are generalized here to the coupling of to up to four MNPs and to the use of somewhat altered molecular parameters. If the MNPs are placed close to each other strong hybridization of plasmon excitations appears and a broad resonance to which molecular excitations are coupled is formed. To investigate this situation the whole charge injection dynamics is described in the framework of the density matrix theory. The approach accounts for optical excitation of the dye coupled to the MNPs and considers subsequent electron injection into the rutile TiO2-cluster. Using a tight-binding model for the TiO2-system with about 105 atoms the electron motion in the cluster is described. We again consider short optical excitation which causes an intermediate steady state with a time-independent overall probability to have the electron injected into the cluster. This probability is used to introduce an enhancement factor which rates the influence of the MNP. Values larger than 500 are obtained.

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

    OpenAIRE

    PravinMallaShrestha; Amelia-ElenaRotaru

    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 whi...

  17. Electron transfer reactions of metal complexes in solution

    International Nuclear Information System (INIS)

    A few representative electron-transfer reactions are selected and their kinetic parameters compared with the predictions of activated complex models. Since Taube has presented an elegant treatment of intramolecular electron-transfer reactions, emphasis is on bimolecular reactions. The latter electron-transfer reactions are more complicated to treat theoretically since the geometries of their activated complexes are not as well known as for the intramolecular case. In addition in biomolecular reactions, the work required to bring the two reactants together needs to be calculated. Since both reactants generally carry charges this presents a non-trivial problem at the ionic strengths usually used to study bimolecular electron transfer

  18. Intermolecular spectroscopy of gases

    International Nuclear Information System (INIS)

    Spectroscopic techniques have been very successfully applied to the study of individual molecules. The same techniques can also be used to investigate intermolecular interactions. Collision-induced absorption (CIA) and collision-induced light scattering (CILS) are important examples of intermolecular interactions. These effects can be described by the dynamical information contained in the general intermolecular correlation functions. One of the aims of this review is to stress the central role of these correlation functions in the field of intermolecular spectroscopy. Because they have a well-defined physical meaning, they are very suitable for the purpose of introducing new physical approximations, particularly in the case of liquids. Some aspects of the theory of CIA will be discussed, mainly as applied to gases. References to similar situations in CILS will occasionally be made, but no comprehensive review will be attempted. One of the basic quantities in CIA is the absorption coefficient. The question is investigated wether it can be expanded in powers of the density. Finally, the moments of the spectrum, interference effects and line shapes are discussed. (KBE)

  19. A ferredoxin Arg-Glu pair important for efficient electron transfer between ferredoxin and ferredoxin-NADP(+) reductase.

    Science.gov (United States)

    Teshima, Keizo; Fujita, Shinobu; Hirose, Syuuichi; Nishiyama, Daisuke; Kurisu, Genji; Kusunoki, Masami; Kimata-Ariga, Yoko; Hase, Toshiharu

    2003-07-10

    In order to elucidate the importance of a ferredoxin (Fd) Arg-Glu pair involved in dynamic exchange from intra- to intermolecular salt bridges upon complex formation with ferredoxin-NADP(+) oxidoreductase (FNR), Equisetum arvense FdI and FdII were investigated as normal and the pair-lacking Fd, respectively. The FdI mutant lacking this pair was unstable and rapidly lost the [2Fe-2S] cluster. The catalytic constant (k(cat)) of the electron transfer for FdI is 5.5 times that for FdII and the introduction of this pair into FdII resulted in the increase of k(cat) to a level comparable to that for FdI, demonstrating directly that the Arg-Glu pair is important for efficient electron transfer between Fd and FNR. PMID:12832038

  20. Transcriptomic and Genetic Analysis of Direct Interspecies Electron Transfer

    OpenAIRE

    Shrestha, Pravin Malla; Rotaru, Amelia-elena; Summers, Zarath M.; Shrestha, Minita; Liu, Fanghua; Lovley, Derek R.

    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 electron-accepting partner for either Geobacter metallireducens, which performs DIET, or Pelobacter carbinolicus, which relies on HIT. Transcript abundance for G. sulfurreducens uptake hydrogenase genes wa...

  1. Computer Simulation of Electron Transfer at Hematite Surfaces

    International Nuclear Information System (INIS)

    Molecular dynamics simulations in combination with ab initio calculations were carried out to determine the rate of electron transfer in bulk hematite (?-Fe2O3) and at two low-index surfaces, namely the (012) and (001) surfaces. The electron transfer reactions considered here involve the II/III valence interchange between nearest-neighbor iron atoms. Two electron transfer directions were investigated namely the basal plane and c direction charge transfers. Electron transfer rates obtained in bulk hematite were in good agreement with ab initio electronic structure calculations thus validating the potential model. The surfaces were considered both in vacuum and in contact with an equilibrated aqueous solution. The reorganization energy is found to increase significantly at the first surface layer and this value is little affected by the presence of water. In addition, in the case of the (012) surface, the electronic coupling matrix element for the topmost basal plane transfer was calculated at the Hartree-Fock level and was found to be weak compared to the corresponding charge transfer in the bulk. Therefore, most surfaces show a decrease in the rate of charge transfer at the surface. However, where iron atoms involved in the charge transfer reaction are directly coordinated to water molecules, water lowers the free energy of activation to a great extent and provides a large driving force for electrons to diffuse toward the bulk thus opposing the intrinsic surface effec thus opposing the intrinsic surface effect. The surfaces considered in this work show different charge transfer properties. Hematite has been shown to exhibit anisotropic conductivity and thus different surfaces will show different intra- and inter-layer rates depending on their orientation. Moreover, the calculations of charge transfers at the hydroxyl- and iron-terminated (001) surfaces revealed that surface termination has a significant effect on the charge transfer parameters in the vicinity of the surface. Finally, our findings indicate that undercoordinated terminal iron atoms could act as electron traps at the surface

  2. Kinetics of inter- and intramolecular electron transfer of Pseudomonas nautica cytochrome cd1 nitrite reductase: regulation of the NO-bound end product.

    Science.gov (United States)

    Lopes, H; Besson, S; Moura, I; Moura, J J

    2001-01-01

    The intermolecular electron transfer kinetics between nitrite reductase (NiR, cytochrome cd1) isolated from Pseudomonas nautica and three cytochromes c isolated from the same strain, as well as the intramolecular electron transfer between NiR heme c and NiR heme d1, were investigated by cyclic voltammetry. All cytochromes (cytochrome c552, cytochrome c553 and cytochrome C553(548)) exhibited well-behaved electrochemistry. The individual diffusion coefficients and mid-point redox potentials were determined. Under the experimental conditions, only cytochrome c552 established a rapid electron transfer with NiR. At acidic pH, the intermolecular electron transfer (cytochrome c(552red)-->NiR heme cox) is a second-order reaction with a rate constant (k2) of 4.1+/-0.1x10(5) M(-1) s(-1) (pH=6.3 and 100 mM NaCl). Under these conditions, the intermolecular reaction represents the rate-limiting step. A minimum estimate of 33 s(-1) could be determined for the first-order rate constant (k1) of the intramolecular electron transfer reaction NiR heme c(red)-->NiR heme d1ox. The pH dependence of k2 values was investigated at pH values ranging from 5.8 to 8.0. When the pH is progressively shifted towards basic values, the rate constant of the intramolecular electron transfer reaction NiR heme c(red)-->NiR heme d1ox decreases gradually to a point where it becomes rate limiting. At pH 8.0 we determined a value of 1.4+/-0.7 s(-1), corresponding to a k2 value of 2.2+/-1.1x10(4) M(-1) s(-1) for the intermolecular step. The physiological relevance of these results is discussed with a particular emphasis on the proposed mechanism of "dead-end product" formation. PMID:11191223

  3. Quantum coherent contributions in biological electron transfer

    CERN Document Server

    Dorner, Ross; Heaney, Libby; Farrow, Tristan; Roberts, Philippa G; Hirst, Judy; Vedral, Vlatko

    2011-01-01

    Many biological electron transfer (ET) reactions are mediated by metal centres in proteins. NADH:ubiquinone oxidoreductase (complex I) contains an intramolecular chain of seven iron-sulphur (FeS) clusters, one of the longest chains of metal centres in biology and a test case for physical models of intramolecular ET. In biology, intramolecular ET is commonly described as a diffusive hopping process, according to the semi-classical theories of Marcus and Hopfield. However, recent studies have raised the possibility that non-trivial quantum mechanical effects play a functioning role in certain biomolecular processes. Here, we extend the semi-classical model for biological ET to incorporate both semi-classical and coherent quantum phenomena using a quantum master equation based on the Holstein Hamiltonian. We test our model on the structurally-defined chain of FeS clusters in complex I. By exploring a wide range of realistic parameters we and that, when the energy profile for ET along the chain is relatively at, ...

  4. The distance and temperature dependence of electron-transfer rates

    International Nuclear Information System (INIS)

    Electron transfer occurs over relatively long distances in a variety of systems. In interpreting the measured electron-transfer rates it is usually assumed that the rate constants depend exponentially on the distance separating the two redox sites and that this distance dependence arises from the decrease in the electronic coupling of the redox sites with increasing separation. Although the electronic coupling is an important factor determining the distance dependence of the rate, theoretical considerations suggest that the nuclear factors are also important. The various factors determining long-range electron-transfer rates are discussed and it is shown that very different distance dependences are predicted for reactions in the normal and inverted free-energy regions. The effect of the enthalpy change on the electron-transfer rate is also considered; three enthalpy regions are identified depending on the overall free energy and entropy changes for the reaction

  5. Electron transfer reactivity of the Arabidopsis thaliana sulfhydryl oxidase AtErv1

    DEFF Research Database (Denmark)

    Farver, Ole; Vitu, Elvira

    2009-01-01

    The redox reactivity of the three disulfide bridges and the flavin present in each protomer of the wild-type Arabidopsis thaliana mitochondrial sulfhydryl oxidase (AtErv1) homodimer has been investigated. Pulse radiolytically produced CO2- radical ions were found to reduce the disulfide bridges to yield disulfide radicals, RSS*R-. Rates and absorption changes due to formation or decay of RSS*R- and the flavin quinone, semiquinone, and hydroquinone were measured and analyzed. During the first 100 micros following the pulse, the flavin was reduced to the semiquinone by intramolecular electron transfer from the active site disulfide radical. The semiquinone and the remaining disulfide radicals then reacted by much slower, 40 ms to 40 s, inter-homodimer electron transfer reactions, culminating in reduced flavin and dithiols. The dithiols were then subject to oxidation by enzyme molecules via their intrinsic enzymatic activity, at a rate comparable to the slower intermolecular processes in the 10-s time regime. Mutants of AtErv1 lacking each of the three individual cysteine pairs were studied to determine the involvement of the respective disulfide groups in these reactions. Elimination of the active site disulfide bridge increased the stability of the flavin semiquinone making it a long-lived product. Relevance of these observations to the design and function of the sulfhydryl oxidases is discussed.

  6. Inorganic and biological electron transfer across an electronically conductive composite polymer membrane. Interim report

    Energy Technology Data Exchange (ETDEWEB)

    Lawson, D.R.; Liang, W.; Martin, C.R.

    1993-02-22

    We describe in this paper an experiment involving an electronically conductive polymer that, to our knowledge, has not been described previously. A free-standing conductive polymer (polypyrrole)-based membrane separates a solution of an electron donor from a solution of an electron acceptor. Because the conductive polymer is both electronically and anionically conductive, the membrane can transport electrons from the donor solution to the acceptor solution, and anions in the opposite direction, such that a sustainable electron-transfer reaction is driven across the conductive polymer membrane. We demonstrate such transmembrane electron/ion-transfer processes using both an inorganic and a-biochemical electron donor/acceptor system. The biochemical case is of particular interest because we show that the reduced form of the enzyme glucose oxidase can give its electrons directly to the polypyrrolemembrane surface. Direct electron transfer is usually not possible at inorganic metals.... Biological electron transfer, Conducting polymers.

  7. Computational Approach to Electron Charge Transfer Reactions

    DEFF Research Database (Denmark)

    Jónsson, Elvar Örn

    2013-01-01

    The step from ab initio atomic and molecular properties to thermodynamic - or macroscopic - properties requires the combination of several theoretical tools. This dissertation presents constant temperature molecular dynamics with bond length constraints, a hybrid quantum mechanics-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 and asymmetric charge transfer reactions between several first-row transition metals in water. The results are compared to experiments and rationalised with classical analytic expressions. Shortcomings of the methods are accounted for with clear steps towards improved accuracy. Later the analysis is extended to more complex systems composed of a larger osmium complex in solution and at the solute-substrate interfaces, where in particular the redox state of the complex is controlled through chemical means. The efficiency of the hybrid-classical and quantum mechanics method is used to generate adequate statistics and a simple post-sampling scheme used to generate free energy surfaces - which compare to full ab initio calculations. In the last part both the molecular dynamics and hybrid classical and quantum mechanics method are used to generate a vast data set for the accurate analysis of dynamical structure modes. This is for a large iridium-iridium dimer complex which shows a dramatic structural (and vibrational) change upon electronic excitation.

  8. Shewanella secretes flavins that mediate extracellular electron transfer

    OpenAIRE

    Marsili, Enrico; Baron, Daniel B.; Shikare, Indraneel D.; Coursolle, Dan; Gralnick, Jeffrey A.; Bond, Daniel R.

    2008-01-01

    Bacteria able to transfer electrons to metals are key agents in biogeochemical metal cycling, subsurface bioremediation, and corrosion processes. More recently, these bacteria have gained attention as the transfer of electrons from the cell surface to conductive materials can be used in multiple applications. In this work, we adapted electrochemical techniques to probe intact biofilms of Shewanella oneidensis MR-1 and Shewanella sp. MR-4 grown by using a poised electrode as an electron acc...

  9. Electrostatic influence on energetics of electron transfer reactions.

    OpenAIRE

    Rees, D. C.

    1985-01-01

    Electron transfer chains in biological systems must operate efficiently to satisfy metabolic energetic requirements. The component proteins in these chains are expected to exhibit characteristic structural features that facilitate electron transfer to the appropriate donor and acceptor proteins. A survey of soluble one-electron carrier proteins indicates a significant tendency for lower potential proteins to be more negatively charged than higher potential proteins. Consideration of the elect...

  10. Electron Transfer Dissociation of iTRAQ Labeled Peptide Ions

    OpenAIRE

    Han, Hongling; Pappin, Darryl J.; Ross, Philip L.; Mcluckey, Scott A.

    2008-01-01

    Triply and doubly charged iTRAQ (isobaric tagging for relative and absolute quantitation) labeled peptide cations from a tryptic peptide mixture of bovine carbonic anhydrase II were subjected to electron transfer ion/ion reactions to investigate the effect of charge bearing modifications associated with iTRAQ on the fragmentation pattern. It was noted that electron transfer dissociation (ETD) of triply charged or activated ETD (ETD + supplemental collisional activation of intact electron tran...

  11. Inelastic electron scattering at low momentum transfer

    International Nuclear Information System (INIS)

    Recent advances of high energy resolution (?E approx. 30 keV FWHM) inelastic electron scattering at low momentum transfer (q -1) using selected experimental data from the Darmstadt electron linear accelerator are discussed. Strong emphasis is given to a comparison of the data with theoretical nuclear model predictions. Of the low multipolarity electric transitions investigated, as examples only E1 transitions to unnatural parity states in 11B and E2 transitions of the very fragmented isoscalar quadrupole giant resonance in 208Pb are considered. In 11B the role of the Os hole in the configuration of the 1/2+, 3/2+ and 5/2+ states is quantitatively determined via an interference mechanism in the transition probability. By comparison of the high resolution data with RPA calculations the E2 EWSR in 208Pb is found to be much less exhausted than anticipated from previous medium energy resolution (e,e) and hadron scattering experiments. In the case of M1 transitions it is shown that the simplest idealized independent particle shell-model prediction breaks down badly. In 28Si, ground-state correlations influence largely the detected M1 strength and such ground-state correlations are also responsible for the occurence of a strong M1 transition to a state at Ex = 10.319 MeV in 40Ca. In 90Zr only about 10% of the theoretically expected M1 strength is he theoretically expected M1 strength is seen in (e,e) and in 140Ce and 208Pb none (detection limit 1-2 ?2K). In the case of 208Pb high resolution spectra exist now up to an excitation energy of Ex = approx. 12MeV. The continuous decrease of the M1 strength with mass number is corroborated by the behaviour of strong but very fragmented M2 transitions which are detected in 28Si, 90Zr, 140Ce and 208Pb concentrated at an excitation energy E x approx. 44A-1/3MeV. In 90Zr, the distribution of spacings and widths of the many J? = 2 states are consistent with a Wigner and Porter-Thomas distribution, respectively. (orig.) 891 KBE/orig. 892 ARA

  12. Charge-Transfer State Dynamics Following Hole and Electron Transfer in Organic Photovoltaic Devices

    OpenAIRE

    Bakulin, Artem A.; Dimitrov, Stoichko D.; Rao, Akshay; Chow, Philip C. Y.; Nielsen, Christian B.; Schroeder, Bob C.; Mcculloch, Iain; Bakker, Huib J.; Durrant, James R.; Friend, Richard H.

    2013-01-01

    The formation of bound electron-hole pairs, also called charge-transfer (CT) states, in organic-based photovoltaic devices is one of the dominant loss mechanisms hindering performance. While CT state dynamics following electron transfer from donor to acceptor have been widely studied, there is not much known about the dynamics of bound CT states produced by hole transfer from the acceptor to the donor. In this letter, we compare the dynamics of CT states formed in the differ...

  13. Mechanism for electron transfer in fast ion-atomic collisions.

    Science.gov (United States)

    Najjari, A B Voitkiv B; Ullrich, J

    2008-11-28

    We discuss a mechanism for electron capture in fast ion-atom collisions which has not been considered so far. Similarly as in the radiative capture, where the electron transfer occurs due to photon emission, within the mechanism under consideration the electron capture takes place due to the emission of an additional electron. This first-order capture mechanism leads to the so-called transfer ionization and has a number of interesting features; in particular, in the target frame it results in electron emission mainly into the backward semisphere. PMID:19113481

  14. Proton-transfer mediated enhancement of nonlocal electronic relaxation processes in X-ray irradiated liquid water.

    Science.gov (United States)

    Slaví?ek, Petr; Winter, Bernd; Cederbaum, Lorenz S; Kryzhevoi, Nikolai V

    2014-12-31

    We have simulated the oxygen 1s Auger-electron spectra of normal and heavy liquid water using ab initio and quantum dynamical methods. The computed spectra are analyzed and compared to recently reported experimental data. The electronic relaxation in liquid water exposed to ionizing X-ray radiation is shown to be far more diverse and complex than anticipated and extremely different than for an isolated water molecule. A core-level ionized water molecule in the liquid phase, in addition to a local Auger process, relaxes through nonlocal energy and charge transfer, such as intermolecular Coulombic decay and electron-transfer mediated decay (ETMD). We evaluate the relative efficiencies for these three classes of relaxation processes. The quantitative estimates for the relative efficiencies of different electronic decay modes help determine yields of various reactive species produced by ionizing X-rays. The ETMD processes which are considered here for the first time in the core-level regime are found to have a surprisingly high efficiency. Importantly, we find that all nonlocal electronic relaxation processes are significantly enhanced by ultrafast proton transfer between the core-ionized water and neighboring molecules. PMID:25493917

  15. Stochastic mechanical approach to electron transfer in acene molecules

    Energy Technology Data Exchange (ETDEWEB)

    Sakamoto, Shoichi; Tomiya, Mitsuyoshi

    2004-10-01

    By using stochastic mechanical simulations, we numerically investigate electron transfers in oligoacenes (anthracene, tetracene and pentacene). These {pi}-conjugated oligomers are applied to organic devices and the performance depends on the electronic transfer properties. From quantum mechanical or quantum chemical calculations, estimation of the transport properties have been so far discussed via transfer integrals. Stochastic mechanics provide the quantum motion of electrons from the wave functions. From the analysis of the quantum motion of electrons, we calculate some dynamical properties, such as mean-square displacement relating with the mobility and the electron transfer rate between two anthracenes. Our dynamical approach is efficient and practical and especially important for analysis of molecular or nanoscale devices.

  16. Single-molecule kinetics of interfacial electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Lu, H.P.; Xie, X.S. [Pacific Northwest National Lab., Richland, WA (United States)

    1997-04-10

    Measurements of single-molecule chemical reaction kinetics are demonstrated for interfacial electron transfer from excited cresyl violet molecules to the conduction band of indium tin oxide (ITO) or energetically accessible surface electronic states under ambient conditions by using a far-field fluorescence microscope. In this system, each single molecule exhibits a single-exponential electron transfer kinetics. A wide distribution of site-specific electron transfer rates is observed for many single cresyl violet molecules examined. This work reveals that the physical origin of multiexponential kinetics of electron transfer in this system is the inhomogeneity of molecular interactions on the semiconductor surface of ITO. We illustrate that the single-molecule experiments provide detailed information not obtainable from experiments conducted on large ensembles of molecules. Single-molecule kinetics is particularly useful in understanding multiexponential behavior of chemical reactions in heterogeneous systems. 42 refs., 4 figs.

  17. Final Report: Vibrational Dynamics in Photoinduced Electron Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Kenneth G. Spears

    2006-04-19

    The objective of this grant was to understand how molecular vibrational states (geometry distortions) are involved in photoinduced electron transfer rates of molecules. This subject is an important component of understanding how molecular absorbers of light convert that energy into charge separation. This is important because the absorption usually excites molecular vibrations in a new electronic state prior to electron transfer to other molecules or semiconductor nanoparticles, as in some types of solar cells. The speeds of charge separation and charge recombination are key parameters that require experiments such as those in this work to test the rules governing electron transfer rates. Major progress was made on this goal. Some of the molecular structures selected for developing experimental data were bimolecular charge transfer complexes that contained metals of cobalt or vanadium. The experiments used the absorption of an ultrafast pulse of light to directly separate charges onto the two different molecular parts of the complex. The charge recombination then proceeds naturally, and one goal was to measure the speed of this recombination for different types of molecular vibrations. We used picosecond and femtosecond duration pulses with tunable colors at infrared wavelengths to directly observe vibrational states and their different rates of charge recombination (also called electron transfer). We discovered that different contact geometries in the complexes had very different electron transfer rates, and that one geometry had a significant dependence on the amount of vibration in the complex. This is the first and only measurement of such rates, and it allowed us to confirm our interpretation with a number of molecular models and test the sensitivity of electron transfer to vibrational states. This led us to develop a general theory, where we point out how molecular distortions can change the electron transfer rates to be much faster than prior theories predict. This provides a new method to predict electron transfer rates for particular conditions, and it will be important in designing new types of solar cells. A related set of studies were also done to understand how much the environment around the active charge transfer molecules can control the speed of charge transfer. We studied different complexes with femtosecond transient absorption spectroscopy to show that solvent or components of a matrix environment can directly control ultrafast electron transfer when the environmental relaxation time response is on a similar time-scale as the natural electron transfer. Understanding such processes in both liquids and in a matrix is essential for designing new types of solar cells.

  18. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    International Nuclear Information System (INIS)

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10?2 electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems

  19. Electronic and vibronic properties of a discotic liquid-crystal and its charge transfer complex

    Energy Technology Data Exchange (ETDEWEB)

    Haverkate, Lucas A.; Mulder, Fokko M. [Reactor Institute Delft, Faculty of Applied Sciences, Delft University of Technology, Mekelweg 15, 2629JB Delft (Netherlands); Zbiri, Mohamed, E-mail: zbiri@ill.fr; Johnson, Mark R. [Institut Laue Langevin, 38042 Grenoble Cedex 9 (France); Carter, Elizabeth [Vibrational Spectroscopy Facility, School of Chemistry, The University of Sydney, NSW 2008 (Australia); Kotlewski, Arek; Picken, S. [ChemE-NSM, Faculty of Chemistry, Delft University of Technology, 2628BL/136 Delft (Netherlands); Kearley, Gordon J. [Bragg Institute, Australian Nuclear Science and Technology Organisation, Menai, NSW 2234 (Australia)

    2014-01-07

    Discotic liquid crystalline (DLC) charge transfer (CT) complexes combine visible light absorption and rapid charge transfer characteristics, being favorable properties for photovoltaic (PV) applications. We present a detailed study of the electronic and vibrational properties of the prototypic 1:1 mixture of discotic 2,3,6,7,10,11-hexakishexyloxytriphenylene (HAT6) and 2,4,7-trinitro-9-fluorenone (TNF). It is shown that intermolecular charge transfer occurs in the ground state of the complex: a charge delocalization of about 10{sup ?2} electron from the HAT6 core to TNF is deduced from both Raman and our previous NMR measurements [L. A. Haverkate, M. Zbiri, M. R. Johnson, B. Deme, H. J. M. de Groot, F. Lefeber, A. Kotlewski, S. J. Picken, F. M. Mulder, and G. J. Kearley, J. Phys. Chem. B 116, 13098 (2012)], implying the presence of permanent dipoles at the donor-acceptor interface. A combined analysis of density functional theory calculations, resonant Raman and UV-VIS absorption measurements indicate that fast relaxation occurs in the UV region due to intramolecular vibronic coupling of HAT6 quinoidal modes with lower lying electronic states. Relatively slower relaxation in the visible region the excited CT-band of the complex is also indicated, which likely involves motions of the TNF nitro groups. The fast quinoidal relaxation process in the hot UV band of HAT6 relates to pseudo-Jahn-Teller interactions in a single benzene unit, suggesting that the underlying vibronic coupling mechanism can be generic for polyaromatic hydrocarbons. Both the presence of ground state CT dipoles and relatively slow relaxation processes in the excited CT band can be relevant concerning the design of DLC based organic PV systems.

  20. 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.

  1. Proton-coupled electron transfer with photoexcited metal complexes.

    Science.gov (United States)

    Wenger, Oliver S

    2013-07-16

    Proton-coupled electron transfer (PCET) plays a crucial role in many enzymatic reactions and is relevant for a variety of processes including water oxidation, nitrogen fixation, and carbon dioxide reduction. Much of the research on PCET has focused on transfers between molecules in their electronic ground states, but increasingly researchers are investigating PCET between photoexcited reactants. This Account describes recent studies of excited-state PCET with d(6) metal complexes emphasizing work performed in my laboratory. Upon photoexcitation, some complexes release an electron and a proton to benzoquinone reaction partners. Others act as combined electron-proton acceptors in the presence of phenols. As a result, we can investigate photoinduced PCET involving electron and proton transfer in a given direction, a process that resembles hydrogen-atom transfer (HAT). In other studies, the photoexcited metal complexes merely serve as electron donors or electron acceptors because the proton donating and accepting sites are located on other parts of the molecular PCET ensemble. We and others have used this multisite design to explore so-called bidirectional PCET which occurs in many enzymes. A central question in all of these studies is whether concerted proton-electron transfer (CPET) can compete kinetically with sequential electron and proton transfer steps. Short laser pulses can trigger excited-state PCET, making it possible to investigate rapid reactions. Luminescence spectroscopy is a convenient tool for monitoring PCET, but unambiguous identification of reaction products can require a combination of luminescence spectroscopy and transient absorption spectroscopy. Nevertheless, in some cases, distinguishing between PCET photoproducts and reaction products formed by simple photoinduced electron transfer (ET) (reactions that don't include proton transfer) is tricky. Some of the studies presented here deal directly with this important problem. In one case study we employed a cyclometalated iridium(III) complex. Our other studies with ruthenium(II) complexes and phenols focused on systematic variations of the reaction free energies for the CPET, ET, and proton transfer (PT) steps to explore their influence on the overall PCET reaction. Still other work with rhenium(I) complexes concentrated on the question of how the electronic structure of the metal-to-ligand charge transfer (MLCT) excited states affects PCET. We used covalent rhenium(I)-phenol dyads to explore the influence of the electron donor-electron acceptor distance on bidirectional PCET. In covalent triarylamine-Ru(bpy)?²?/Os(bpy)?²?-anthraquinone triads (bpy = 2,2'-bipyridine), hydrogen-bond donating solvents significantly lengthened the lifetimes of photogenerated electron/hole pairs because of hydrogen-bonding to the quinone radical anion. Until now, comparatively few researchers have investigated this variation of PCET: the strengthening of H-bonds upon photoreduction. PMID:23402212

  2. 77 FR 24667 - TANF Assistance and Electronic Benefit Transfer Transactions; Request for Public Comment

    Science.gov (United States)

    2012-04-25

    ...to prevent electronic benefit transfer transactions...gambling casinos, or other gaming establishments, and...used in any electronic benefit transfer transaction...gambling casino, or gaming establishment; or any...defines an electronic benefit transfer...

  3. Mediated catalysis of Paracoccus pantotrophus cytochrome c peroxidase by P. pantotrophus pseudoazurin: kinetics of intermolecular electron transfer

    OpenAIRE

    Sousa, P. M. Paes; Pauleta, Sofia R.; Gonc?alves, M. L. Simo?es; Pettigrew, Graham W.; Moura, Isabel; Moura, Jose? J. G.; Santos, Margarida M. Correia Dos

    2007-01-01

    This work reports the direct electrochemistry of Paracoccus pantotrophus pseudoazurin and the mediated catalysis of cytochrome c peroxidase from the same organism. The voltammetric behaviour was examined at a gold membrane electrode, and the studies were performed in the presence of calcium to enable the peroxidase activation. A formal reduction potential, E (0)', of 230 +/- 5 mV was determined for pseudoazurin at pH 7.0. Its voltammetric signal presented a pH dependence, defined by pK values...

  4. Theory of electron transfer and ionization

    International Nuclear Information System (INIS)

    The main effort reported is directed toward charge transfer and ionization in high energy atomic collisions. The research may be divided into classical trajectory calculations, quantum - mechanical collision theory, and phenomenological treatments of quantal interference effects in heavy ion collisions

  5. Electron-Transfer Acceleration Investigated by Time Resolved Infrared Spectroscopy.

    Czech Academy of Sciences Publication Activity Database

    Vl?ek Jr., Antonín; Kvapilová, Hana; Towrie, M.; Záliš, Stanislav

    2015-01-01

    Ro?. 48, ?. 3 (2015), s. 868-876. ISSN 0001-4842 Institutional support: RVO:61388955 Keywords : electron transfer * infrared spectroscopy Subject RIV: CG - Electrochemistry Impact factor: 24.348, year: 2013

  6. Length-Dependence of Electron Transfer in Conjugated Molecular Wires

    Science.gov (United States)

    Karna, Shashi; Mallick, Govind; Pandey, Ravindra

    2007-03-01

    The electron transfer (ET) properties of ?-electron conjugated molecular wires consisting of polyene chain, [>C=CVDA decreases exponentially with increase in the length of the molecular wire. However, in contrast with the rigid ?-bonded molecular wires, the decay constant, ?, for the conjugated systems exhibits three different regimes over the calculated length. This is attributed to the delocalized nature of the electrons along molecular length that facilitates retention of the electron coupling even at large separations between the donor and acceptor centers.

  7. Adiabatic transfer of net electron polarization to nuclear polarization

    OpenAIRE

    Lukzen, Nikita N.; Steiner, Ulrich

    1995-01-01

    A new type of spin chemical experiment is suggested which utilizes adiabatic reversion of a low magnetic Bo field for an efficient transfer of net electron spin polarization, as arising from some CIDEP mechanism, to the nuclear polarization of radicals. After trapping the radicals in diamagnetic products and transferring the sample to a NMR probe, the adiabatic polarization transfer effect can be measured as induced CIDNP, as in the recently established SNP method. The optimum conditions conc...

  8. Initial experience with a electronic CT image transfer system.

    OpenAIRE

    Bell, K. E.; Loughrey, C.; Morrison, C. M.

    1994-01-01

    An electronic image transfer system for computed tomographic images links the CT scanner in Altnagelvin Hospital, Londonderry with the regional neuroradiology department in the Royal Victoria Hospital, Belfast. In the first 13 months of operation, scans of 100 patients were transferred; 49 scans were taken in acute neurosurgical emergencies, and 51 were non-acute sent for a specialist neuroradiological opinion. Potentially hazardous inter-hospital transfer was avoided in 21 cases of acute neu...

  9. Interfacial Electron Transfer into Functionalized Crystalline Polyoxotitanate Nanoclusters

    OpenAIRE

    Snoeberger, Robert C.; Young, Karin J.; Tang, Jiji; Allen, Laura J.; Crabtree, Robert H.; Brudvig, Gary W.; Coppens, Philip; Batista, Victor S.; Benedict, Jason B.

    2012-01-01

    Interfacial electron transfer (IET) between a chromophore and a semi-conductor nanoparticle is one of the key processes in a dye sensitized solar cell. Theoretical simulations of the electron transfer in polyoxotitanate nanoclusters Ti17O24(OPri)20 (Ti17) functionalized with four para-nitrophenyl acetylacetone (NPA-H) adsorbates, of which the atomic structure has been fully established by X-ray diffraction measurements, are presented. Complementary experimental information showing IET has bee...

  10. Single-molecule electron transfer reactions in nanomaterials

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Dehong; Lei, Chenghong; Ackerman, Eric J.

    2009-07-26

    Here we report the study of single molecule electron transfer dynamics by coupling fluorescence microscopy at a conventional electrochemical cell. The single-molecule fluorescence spectroelectrochemistry of cresyl violet in aqueous solution and on nanoparticle surface were studied. We observed that the single-molecule fluorescence intensity of cresyl violet is modulated synchronously with the cyclic voltammetric potential scanning. We attribute the fluorescence intensity change of single cresyl violet molecules to the electron transfer reaction driven by the electrochemical potential.

  11. Thermodynamics of electron transfer in Escherichia coli cytochrome bo3

    OpenAIRE

    Schultz, Brian E.; Chan, Sunney I.

    1998-01-01

    The proton translocation mechanism of the Escherichia coli cytochrome bo3 complex is intimately tied to the electron transfers within the enzyme. Herein we evaluate two models of proton translocation in this enzyme, a cytochrome c oxidase-type ion-pump and a Q-cycle mechanism, on the basis of the thermodynamics of electron transfer. We conclude that from a thermodynamic standpoint, a Q-cycle is the more favorable mechanism for proton translocation and is likely occ...

  12. Single Molecule Electron Transfer Dynamics in Complex Environments

    International Nuclear Information System (INIS)

    We propose a new theoretical approach to study the kinetics of the electron transfer (ET) under the dynamical influence of the complex environments with the first passage times (FPT) of the reaction events. By measuring the mean and high order moments of FPT and their ratios, the full kinetics of ET, especially the dynamical transitions across different temperature zones, is revealed. The potential applications of the current results to single molecule electron transfer are discussed

  13. Improved heterogeneous electron transfer kinetics of fluorinated graphene derivatives

    Science.gov (United States)

    Boopathi, Sidhureddy; Narayanan, Tharangattu N.; Senthil Kumar, Shanmugam

    2014-08-01

    Though graphitic carbons are commercially available for various electrochemical processes, their performance is limited in terms of various electrochemical activities. Recent experiments on layered carbon materials, such as graphene, demonstrated an augmented performance of these systems in all electrochemical activities due to their unique electronic properties, enhanced surface area, structure and chemical stabilities. Moreover, flexibility in controlling electronic, as well as electrochemical activities by heteroatom doping brings further leverage in their practical use. Here, we study the electron transfer kinetics of fluorinated graphene derivatives, known as fluorinated graphene oxide (FGO) and its reduced form, RFGO. Enhanced electron transfer kinetics (heterogeneous electron transfer (HET)) is observed from these fluorinated systems in comparison to their undoped systems such as graphene oxide (GO) and reduced GO. A detailed study has been conducted using standard redox probes and biomolecules revealing the enhanced electro-catalytic activities of FGO and RFGO, and electron transfer rates are simulated theoretically. This study reveals that fluorine not only induces defects in graphitic lattice leading to an enhanced HET process but also can modify the electronic structure of graphene surface.Though graphitic carbons are commercially available for various electrochemical processes, their performance is limited in terms of various electrochemical activities. Recent experiments on layered carbon materials, such as graphene, demonstrated an augmented performance of these systems in all electrochemical activities due to their unique electronic properties, enhanced surface area, structure and chemical stabilities. Moreover, flexibility in controlling electronic, as well as electrochemical activities by heteroatom doping brings further leverage in their practical use. Here, we study the electron transfer kinetics of fluorinated graphene derivatives, known as fluorinated graphene oxide (FGO) and its reduced form, RFGO. Enhanced electron transfer kinetics (heterogeneous electron transfer (HET)) is observed from these fluorinated systems in comparison to their undoped systems such as graphene oxide (GO) and reduced GO. A detailed study has been conducted using standard redox probes and biomolecules revealing the enhanced electro-catalytic activities of FGO and RFGO, and electron transfer rates are simulated theoretically. This study reveals that fluorine not only induces defects in graphitic lattice leading to an enhanced HET process but also can modify the electronic structure of graphene surface. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr02563f

  14. Intermolecular Coulomb Decay at Weakly Coupled Heterogeneous Interfaces

    Science.gov (United States)

    Grieves, Gregory A.; Orlando, Thomas M.

    2011-07-01

    Surface ejection of H+(H2O)n=1-8 from low energy electron irradiated water clusters adsorbed on graphite and graphite with overlayers of Ar, Kr or Xe results from intermolecular Coulomb decay (ICD) at the mixed interface. Inner valence holes in water (2a1-1), Ar (3s-1), Kr (4s-1), and Xe (5s-1) correlate with the cluster appearance thresholds and initiate ICD. Proton transfer occurs during or immediately after ICD and the resultant Coulomb explosion leads to H+(H2O)n=1-8 desorption with kinetic energies that vary with initiating state, final state, and interatomic or molecular distances.

  15. Electron Transfer in Ferritin as Probed by Muon Spin Relaxation

    Science.gov (United States)

    Telling, Mark T. F.; Kilcoyne, Susan H.

    Electron-transfer processes play a vital role in many biological phenomena, from energy storage to photosynthesis. Positive muons allow such transfer processes in macromolecules, such as proteins, to be probed on a microscopic level. We have used this probe via muon spin relaxation (?SR) to investigate electron-transfer processes in ferritin; the normal iron storage protein. Data collected at finite fields is well described using the Risch-Kehr model at all measured temperatures with inter and intra-chain diffusion rates of 109 and 1011 rad s-1 being determined respectively. The results are compared to similar measurements on other proteins.

  16. Desensitization of metastable intermolecular composites

    Science.gov (United States)

    Busse, James R. (South Fork, CO); Dye, Robert C. (Los Alamos, NM); Foley, Timothy J. (Los Alamos, NM); Higa, Kelvin T. (Ridgecrest, CA); Jorgensen, Betty S. (Jemez Springs, NM); Sanders, Victor E. (White Rock, NM); Son, Steven F. (Los Alamos, NM)

    2011-04-26

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  17. Pressure versus temperature effects on intramolecular electron transfer in mixed-valence complexes.

    Science.gov (United States)

    Scheins, Stephan; Overgaard, Jacob; Timco, Grigore A; Stash, Adam; Chen, Yu-Sheng; Larsen, Finn K; Christensen, Mogens; Jørgensen, Mads R V; Madsen, Solveig R; Schmøkel, Mette S; Iversen, Bo B

    2013-01-01

    Mixed-valence trinuclear carboxylates, [M(3)O(O(2)CR)(6)L(3)] (M = metal, L = terminal ligand), have small differences in potential energy between the configurations M(II)M(III)M(III)?M(III)M(II)M(III)?M(III)M(III)M(II), which means that small external changes can have large structural effects, owing to the differences in coordination geometry between M(2+) and M(3+) sites (e.g., about 0.2?Å for Fe-O bond lengths). It is well-established that the electron transfer (ET) between the metal sites in these mixed-valence molecules is strongly dependent on temperature and on the specific crystal environment; however, herein, for the first time, we examine the effect of pressure on the electron transfer. Based on single-crystal X-ray diffraction data that were measured at 15, 90, 100, 110, 130, 160, and 298?K on three different crystals, we first unexpectedly found that our batch of Fe(3)O (O(2)CC(CH(3))(3))(6)(C(5)H(5)N)(3) (1) exhibited a different temperature dependence of the ET process than previous studies of compound 1 have shown. We observed a phase transition at around 130?K that was related to complete valence trapping and Hirshfeld surface analysis revealed that this phase transition was governed by a subtle competition between C-H???? and ????? intermolecular interactions. Subsequent high-pressure single-crystal X-ray diffraction at pressures of 0.15, 0.35, 0.45, 0.74, and 0.96?GPa revealed that it was not possible to trigger the phase transition (i.e., valence trapping) by a reduction of the unit-cell volume, owing to this external pressure. We conclude that modulation of the ET process requires anisotropic changes in the intermolecular interactions, which occur when various directional chemical bonds are affected differently by changes in temperature, but not by the application of pressure. PMID:23169277

  18. Reaction of radicals with benzoquinone--addition or electron transfer?

    Energy Technology Data Exchange (ETDEWEB)

    Maroz, A.; Brede, O. E-mail: brede@mpgag.uni-leipzig.de

    2003-06-01

    Pulse radiolysis studies are reported on reactions of radicals of different electronic structure (chloroalkyl-, {alpha}-, {beta}-hydroxyalkyl-) with benzoquinone and its methyl-substituted derivatives in non-polar surroundings. Hence, radical addition onto the quinones resulted in substituted semiquinone radicals, whereas electron transfer reduction generated semiquinone radical anions, which could be clearly identified in cyclohexane solution.

  19. Ultrafast spectroscopy of electron transfer dynamics in liquids; excitation transfer studies of phase transitions

    Science.gov (United States)

    Goun, Alexei A.

    The transfer of an electron from a donor to an acceptor is the fundamental step in a wide range of chemical and biological processes. As a result, electron-transfer reactions have been the focus of numerous theoretical and experimental efforts aimed at understanding the kinetics and mechanism of the transfer event. Liquid solvents are an important medium for electron-transfer processes. The influences of the distance dependence, diffusion, the radial distribution function, and the hydrodynamic effect have been incorporated into the theory of electron transfer in solution, as well as into the theory of electron transfer between donors and acceptors in the head group regions of micelles. The development of new laser system with a pulse duration of tens of femtoseconds, with tunable wavelength allowed us to study these processes on a considerably shorter time scale than previous studies. This allowed us to observe not only the diffusion controlled but also the kinetics of electron transfer for donor/acceptor pairs that are in close proximity. In one set of experiments we have studied the kinetics of electron transfer in electron accepting molecule (rhodamine 3B) dissolved in electron donating solvent (N,N-dimethylaniline). The data for the forward electron transfer and geminate recombination are approximated by the statistical theory of the electron transfer. Optical anisotropy observed in the experiment demonstrates the orientation dependence of the electron transfer rate. In further experiments we investigated the electron transfer in non-hydrogen bonding liquids of increasing viscosity. The effective value of the donor/acceptor electronic coupling was found to decrease with viscosity. Electron transfer experiments were also carried out on the surface of micelles. The systems studied are the hole donor octadecyl-rhodamine B (ODRB) and the hole acceptor N,N-dimethyl-aniline (DMA) in micelles made of dodecyltrimethylammonium bromide (DTAB) and tetradecyltrimethylammonium bromide (TTAB). It was found that the effective coupling is reduced compared to donor/acceptor pairs dissolved in simple liquids. In the 2nd half of thesis we have addressed the question of the dynamics of phase transitions. We have demonstrated the ability to use the fluorescent excitation-transfer technique to study the demixing of liquids specifically, kinetics of demixing water and 2,6-dimethylpyridine. These two liquids possess a low critical temperature point, which allowed us to use a temperature jump from a laser pulse to initiate the process of phase separation. It was found that Coumarin480 laser dye and HPTS (8-Hydroxypyrene-1,3,6-trisulfonic acid) fluorescent dye have significantly different solubilities in the components of the mixture. These dyes undergo excitation transfer from Coumarin480 to HPTS in the uniform state, but not in the phase-separated state. A system with a temperature jump pump and an excitation transfer probe measured the time scale of the initial step of the phase separation.

  20. Heat transfer between adsorbate and laser-heated hot electrons

    Energy Technology Data Exchange (ETDEWEB)

    Ueba, H [Graduate School of Science and Engineering, University of Toyama, Toyama (Japan); Persson, B N J [IFF, FZ-Juelich, Postfach 1913, 52425 Juelich (Germany)], E-mail: ueba@eng.u-toyama.ac.jp

    2008-06-04

    Strong short laser pulses can give rise to a strong increase in the electronic temperature at metal surfaces. Energy transfer from the hot electrons to adsorbed molecules may result in adsorbate reactions, e.g. desorption or diffusion. We point out the limitations of an often used equation to describe the heat transfer process in terms of a friction coupling. We propose a simple theory for the energy transfer between the adsorbate and hot electrons using a newly introduced heat transfer coefficient, which depends on the adsorbate temperature. We calculate the transient adsorbate temperature and the reaction yield for a Morse potential as a function of the laser fluency. The results are compared to those obtained using a conventional heat transfer equation with temperature-independent friction. It is found that our equation of energy (heat) transfer gives a significantly lower adsorbate peak temperature, which results in a large modification of the reaction yield. We also consider the heat transfer between different vibrational modes excited by hot electrons. This mode coupling provides indirect heating of the vibrational temperature in addition to the direct heating by hot electrons. The formula of heat transfer through linear mode-mode coupling of two harmonic oscillators is applied to the recent time-resolved study of carbon monoxide and atomic oxygen hopping on an ultrafast laser-heated Pt(111) surface. It is found that the maximum temperature of the frustrated translation mode can reach high temperatures for hopping, even when direct friction coupling to the hot electrons is not strong enough.

  1. Mechanism for the nonadiabatic photooxidation of benzene to phenol: orientation-dependent proton-coupled electron transfer.

    Science.gov (United States)

    Chang, Xue-Ping; Cui, Ganglong; Fang, Wei-Hai; Thiel, Walter

    2015-04-01

    An efficient catalytic one-step conversion of benzene to phenol was achieved recently by selective photooxidation under mild conditions with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) as the photocatalyst. Herein, high-level electronic structure calculations in the gas phase and in acetonitrile solution are reported to explore the underlying mechanism. The initially populated (1) ??* state of DDQ can relax efficiently through a nearby dark (1) n?* doorway state to the (3) ??* state of DDQ, which is found to be the precursor state involved in the initial intermolecular electron transfer from benzene to DDQ. The subsequent triplet-state reaction between DDQ radical anions, benzene radical cations, and water is computed to be facile. The formed DDQH and benzene-OH radicals can undergo T1 ?S0 intersystem crossing and concomitant proton-coupled electron transfer (PCET) to generate the products DDQH2 and phenol. Two of the four considered nonadiabatic pathways involve an orientation-dependent triplet PCET process, followed by intersystem crossing to the ground state (S0 ). The other two first undergo a nonadiabatic T1 ?S0 transition to produce a zwitterionic S0 complex, followed by a barrierless proton transfer. The present theoretical study identifies novel types of nonadiabatic PCET processes and provides detailed mechanistic insight into DDQ-catalyzed photooxidation. PMID:25630997

  2. Electronic energy transfer on a vibronically coupled quantum aggregate

    Science.gov (United States)

    Roden, Jan; Schulz, Georg; Eisfeld, Alexander; Briggs, John

    2009-07-01

    We examine the transfer of electronic excitation (an exciton) along a chain of electronically coupled monomers possessing internal vibronic structure and which also interact with degrees of freedom of the surrounding environment. Using a combination of analytical and numerical methods, we calculate the time evolution operator or time-dependent Green's function of the system and thereby isolate the physical parameters influencing the electronic excitation transport. Quite generally, we show that coupling to vibrations slows down and inhibits migration of electronic excitation due to dephasing effects on the coherent transfer present without vibrations. In particular, coupling to a continuous spectrum of environment states leads to a complete halting of transfer, i.e., a trapping of the exciton.

  3. Conformational analysis of a Chlamydia-specific disaccharide {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl in aqueous solution and bound to a monoclonal antibody: Observation of intermolecular transfer NOEs

    Energy Technology Data Exchange (ETDEWEB)

    Sokolowski, Tobias; Haselhorst, Thomas; Scheffler, Karoline [Medizinische Universitaet, Institut fuer Chemie (Germany); Weisemann, Ruediger [Bruker Analytik GmbH, Silberstreifen (Germany); Kosma, Paul [Institut fuer Chemie der Universitaet fuer Bodenkultur Wien (Austria); Brade, Helmut; Brade, Lore [Forschungszentrum Borstel, Zentrum fuer Medizin und Biowissenschaften Parkallee 22 (Germany); Peters, Thomas [Medizinische Universitaet, Institut fuer Chemie (Germany)

    1998-07-15

    The disaccharide {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo (Kdo: 3-deoxy-d-manno-oct-2-ulosonic acid) represents a genus-specific epitope of the lipopolysaccharide of the obligate intracellular human pathogen Chlamydia. The conformation of the synthetically derived disaccharide {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl was studied in aqueous solution, and complexed to a monoclonal antibody S25-2. Various NMR experiments based on the detection of NOEs (or transfer NOEs) and ROEs (or transfer ROEs) were performed. A major problem was the extensive overlap of almost all {sup 1}H NMR signals of {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl. To overcome this difficulty, HMQC-NOESY and HMQC-trNOESY experiments were employed. Spin diffusion effects were identified using trROESY experiments, QUIET-trNOESY experiments and MINSY experiments. It was found that protein protons contribute to the observed spin diffusion effects. At 800 MHz, intermolecular trNOEs were observed between ligand protons and aromatic protons in the antibody binding site. From NMR experiments and Metropolis Monte Carlo simulations, it was concluded that {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl in aqueous solution exists as a complex conformational mixture. Upon binding to the monoclonal antibody S25-2, only a limited range of conformations is available to {alpha}-Kdo-(2{sup {yields}}8)-{alpha}-Kdo-(2{sup {yields}}O)-allyl. These possible bound conformations were derived from a distance geometry analysis using transfer NOEs as experimental constraints. It is clear that a conformation is selected which lies within a part of the conformational space that is highly populated in solution. This conformational space also includes the conformation found in the crystal structure. Our results provide a basis for modeling studies of the antibody-disaccharide complex.

  4. Conformational analysis of a Chlamydia-specific disaccharide ?-Kdo-(2?8)-?-Kdo-(2?O)-allyl in aqueous solution and bound to a monoclonal antibody: Observation of intermolecular transfer NOEs

    International Nuclear Information System (INIS)

    The disaccharide ?-Kdo-(2?8)-?-Kdo (Kdo: 3-deoxy-d-manno-oct-2-ulosonic acid) represents a genus-specific epitope of the lipopolysaccharide of the obligate intracellular human pathogen Chlamydia. The conformation of the synthetically derived disaccharide ?-Kdo-(2?8)-?-Kdo-(2?O)-allyl was studied in aqueous solution, and complexed to a monoclonal antibody S25-2. Various NMR experiments based on the detection of NOEs (or transfer NOEs) and ROEs (or transfer ROEs) were performed. A major problem was the extensive overlap of almost all 1H NMR signals of ?-Kdo-(2?8)-?-Kdo-(2?O)-allyl. To overcome this difficulty, HMQC-NOESY and HMQC-trNOESY experiments were employed. Spin diffusion effects were identified using trROESY experiments, QUIET-trNOESY experiments and MINSY experiments. It was found that protein protons contribute to the observed spin diffusion effects. At 800 MHz, intermolecular trNOEs were observed between ligand protons and aromatic protons in the antibody binding site. From NMR experiments and Metropolis Monte Carlo simulations, it was concluded that ?-Kdo-(2?8)-?-Kdo-(2?O)-allyl in aqueous solution exists as a complex conformational mixture. Upon binding to the monoclonal antibody S25-2, only a limited range of conformations is available to ?-Kdo-(2?8)-?-Kdo-(2?O)-allyl. These possible bound conformations were derived frome derived from a distance geometry analysis using transfer NOEs as experimental constraints. It is clear that a conformation is selected which lies within a part of the conformational space that is highly populated in solution. This conformational space also includes the conformation found in the crystal structure. Our results provide a basis for modeling studies of the antibody-disaccharide complex

  5. Effect of proton transfer on the electronic coupling in DNA

    Science.gov (United States)

    Rak, Janusz; Makowska, Joanna; Voityuk, Alexander A.

    2006-06-01

    The effects of single and double proton transfer within Watson-Crick base pairs on donor-acceptor electronic couplings, Vda, in DNA are studied on the bases of quantum chemical calculations. Four dimers [AT,AT], [GC,GC], [GC,AT] and [GC,TA)] are considered. Three techniques - the generalized Mulliken-Hush scheme, the fragment charge method and the diabatic states method - are employed to estimate Vda for hole transfer between base pairs. We show that both single- and double proton transfer (PT) reactions may substantially affect the electronic coupling in DNA. The electronic coupling in [AT,AT] is predicted to be most sensitive to PT. Single PT within the first base pair in the dimer leads to increase in the hole transfer efficiency by a factor of 4, while proton transfer within the second pair should substantially, by 2.7 times, decrease the rate of charge transfer. Thus, directional asymmetry of the PT effects on the electronic coupling is predicted. The changes in the Vda matrix elements correlate with the topological properties of orbitals of donor and acceptor and can be qualitatively rationalized in terms of resonance structures of donor and acceptor. Atomic pair contributions to the Vda matrix elements are also analyzed.

  6. Theory of reversible electron transfer reactions in a condensed phase.

    Science.gov (United States)

    Dhole, Kajal; Modak, Brindaban; Samanta, Alok; Ghosh, Swapan K

    2010-07-01

    We have derived an exact analytical expression for the average forward rate of a reversible electron transfer reaction, modeled through a reaction coordinate undergoing diffusive motion in arbitrary potential wells of the reactant and the product in presence of a localized sink of arbitrary location and strength. The dynamics of diffusive motion is described by employing two coupled generalized diffusion reaction (Smoluchowski) equations with coordinate dependent diffusivity and delta sink. The average forward electron transfer rate constant obtained here for the system, with equilibrium or nonequilibrium distributions as initial condition, is determined by the forward and backward rate constants calculated based on the transition state theory and the weighted average rate for the well dynamics. We also discuss various limiting cases for the rate of electron transfer reactions corresponding to the different experimental situations. As an illustrative example, we have considered back electron transfer (ET) reaction and shown that the present theory can explain the non-Marcus free energy gap dependence of the rate of ET reactions. More importantly, the approach presented here can easily be extended to systems describing the dynamics of diffusive motion in coupled multipotential surfaces associated with electron transfer reactions. PMID:20866692

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

    Directory of Open Access Journals (Sweden)

    PravinMallaShrestha

    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.

  8. 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

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

    DEFF Research Database (Denmark)

    Shrestha, Pravin; 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.

  10. 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 ?-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. PMID:25242485

  11. 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 ?-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.

  12. Vectorial electron transfer in spatially ordered arrays

    Energy Technology Data Exchange (ETDEWEB)

    Fox, M.A.

    1992-01-01

    Progress has been made in four areas: the synthesis of new materials for directional electron; the preparation and characterization of anisotropic composites bearing organic and inorganic components; the elaboration of mechanisms of electrocatalysis; and the development of new methods for surface modification of metals and semiconductors.

  13. 78 FR 6025 - Electronic Fund Transfers (Regulation E) Temporary Delay of Effective Date

    Science.gov (United States)

    2013-01-29

    ...CFPB-2012-0050] RIN 3170-AA33 Electronic Fund Transfers (Regulation...Regulation E, which implements the Electronic Fund Transfer Act (EFTA...remittance transfers in the normal course of business, and...

  14. Photoinduced electron transfer processes in homogeneous and microheterogeneous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Whitten, D.G.

    1991-10-01

    The focus of the work described in this report is on single electron transfer reactions of excited states which culminate in the formation of stable or metastable even electron species. For the most part the studies have involved even electron organic substrates which are thus converted photochemically to odd electron species and then at some stage reconvert to even electron products. These reactions generally fall into two rather different categories. In one set of studies we have examined reactions in which the metastable reagents generated by single electron transfer quenching of an excited state undergo novel fragmentation reactions, chiefly involving C-C bond cleavage. These reactions often culminate in novel and potentially useful chemical reactions and frequently have the potential for leading to new chemical products otherwise unaffordable by conventional reaction paths. In a rather different investigation we have also studied reactions in which single electron transfer quenching of an excited state is followed by subsequent reactions which lead reversibly to metastable two electron products which, often stable in themselves, can nonetheless be reacted with each other or with other reagents to regenerate the starting materials with release of energy. 66 refs., 9 figs., 1 tab.

  15. 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. PMID:24837373

  16. Photoinduced electron transfer in a charge-transfer complex formed between corannulene and Li+@C60 by concave-convex ?-? interactions.

    Science.gov (United States)

    Yamada, Mihoko; Ohkubo, Kei; Shionoya, Mitsuhiko; Fukuzumi, Shunichi

    2014-09-24

    A charge-transfer (CT) complex was formed between corannulene (C20H10) and lithium ion-encapsulated [60]fullerene (Li(+)@C60) with the binding constant KG = 1.9 × 10 M(-1) by concave-convex ?-? CT interactions in benzonitrile at 298 K, exhibiting a broad CT absorption extended to the NIR region. Femotosecond laser excitation of the C20H10/Li(+)@C60 CT complex resulted in the singlet charge-separated (CS) state, (1)(C20H10(•+)/Li(+)@C60(•-)), which decayed with the lifetime of 1.4 ns. Nanosecond laser excitation of Li(+)@C60 resulted in intermolecular electron transfer (ET) from C20H10 to the triplet excited state of Li(+)@C60 [(3)(Li(+)@C60)*] to produce the triplet CS state (3)(C20H10(•+)/Li(+)@C60(•-)). The distance between two electron spins in the triplet CS state was estimated to be 10 Å from the zero-field splitting pattern observed by EPR measurements at 4 K. The triplet CS state decayed to the ground state via intramolecular back electron transfer (BET). The CS lifetime was determined to be 240 ?s in benzonitrile at 298 K. The temperature dependence of the rate constant of BET afforded the reorganization energy (? = 1.04 eV) and the electronic coupling term (V = 0.0080 cm(-1)). The long lifetime of triplet CS state results from the spin-forbidden BET process and a small V value. PMID:25166343

  17. Light-driven microbial dissimilatory electron transfer to hematite.

    Science.gov (United States)

    Li, Dao-Bo; Cheng, Yuan-Yuan; Li, Ling-Li; Li, Wen-Wei; Huang, Yu-Xi; Pei, Dan-Ni; Tong, Zhong-Hua; Mu, Yang; Yu, Han-Qing

    2014-11-14

    The ability of dissimilatory metal-reducing microorganisms (DMRM) to conduct extracellular electron transfer with conductive cellular components grants them great potential for bioenergy and environmental applications. Crystalline Fe(III) oxide, a type of widespread electron acceptor for DMRM in nature, can be excited by light for photocatalysis and microbial culture-mediated photocurrent production. However, the feasibility of direct electron transfer from living cells to light-excited Fe(III) oxides has not been well documented and the cellular physiology in this process has not been clarified. To resolve these problems, an electrochemical system composed of Geobacter sulfurreducens and hematite (?-Fe2O3) was constructed, and direct electron transfer from G. sulfurreducens cells to the light-excited ?-Fe2O3 in the absence of soluble electron shuttles was observed. Further studies evidenced the efficient excitation of ?-Fe2O3 and the dependence of photocurrent production on the biocatalytic activity. Light-induced electron transfer on the cell-?-Fe2O3 interface correlated linearly with the rates of microbial respiration and substrate consumption. In addition, the G. sulfurreducens cells were found to survive on light-excited ?-Fe2O3. These results prove a direct mechanism behind the DMRM respiration driven by photo-induced charge separation in semiconductive acceptors and also imply new opportunities to design photo-bioelectronic devices with living cells as a catalyst. PMID:25238285

  18. Heavy particle interference and diffraction in fast electron transfer collisions

    OpenAIRE

    Gudmundsson, Magnus

    2011-01-01

    This thesis presents experimental results from the synchrotron cooler and storage ring CRYRING on charge transfer processes in fast electron transfer collisions using high-resolution cold target recoil-ion momentum spectroscopy. The main focus of these studies was to investigate a key concept of quantum mechanics: the wave-particle duality. One series of experiments has been dedicated to the study of heavy particle de Broglie wave interference due to scattering on a molecular ’double slit?...

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

    Science.gov (United States)

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

    2013-10-01

    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. PMID:23936901

  20. Electron transfer in ion interactions with chlorine covered silver surfaces

    International Nuclear Information System (INIS)

    The effect of chemical environment on the neutralisation of ions with adsorbate covered surfaces was investigated on the example of H+ and rare gas ion scattering on chlorine covered Ag. Changes in coverage from the submonolayer chemisorption to chloride nucleation stage, strongly affect electron transfer. In the case of H+, Ne+ and Ar+ these changes induce an ''unusual'' non-linear, oscillating, coverage dependence of electron transfer probabilities, due to modifications in the surface electronic structure. In case of the more highly bound He, we assign the observed changes to modifications in quasi-resonant charge transfer rates involving the Cl 3s core level, because of the core level shifts induced by changes in chemical environment

  1. Environment assisted electron capture

    OpenAIRE

    Gokhberg, Kirill; Cederbaum, Lorenz S.

    2009-01-01

    Electron capture by {\\it isolated} atoms and ions proceeds by photorecombination. In this process a species captures a free electron by emitting a photon which carries away the excess energy. It is shown here that in the presence of an {\\it environment} a competing non-radiative electron capture process can take place due to long range electron correlation. In this interatomic (intermolecular) process the excess energy is transferred to neighboring species. The asymptotic ex...

  2. Electron transfer, ionization, and excitation atomic collisions

    International Nuclear Information System (INIS)

    Basic atomic-collision processes at intermediate and high energies are being studied theoretically at Penn State by Alston and Winter. In the high velocity regime, single-electron capture is treated using a high order multiple-scattering approach; extensive comparison with experiment and analysis of mechanisms have been made. Fitting the calculated amplitude with a simple analytic form, the asymptotic velocity dependence of the cross section is obtained. The effect on the capture amplitude of altering the inner part of the internuclear potential has also been explored. In the intermediate velocity regime, earlier work on collisions between protons and hydrogenic-ion targets using a coupled-state approach is being extended to the two-electron helium target. 29 refs

  3. Monitoring sequential electron transfer with EPR

    International Nuclear Information System (INIS)

    A completely general model which treats electron spin polarization (ESP) found in a system in which radical pairs with different magnetic interactions are formed sequentially has been described. This treatment has been applied specifically to the ESP found in the bacterial reaction center. Test cases show clearly how parameters such as structure, lifetime, and magnetic interactions within the successive radical pairs affect the ESP, and demonstrate that previous treatments of this problem have been incomplete. The photosynthetic bacterial reaction center protein is an ideal system for testing the general model of ESP. The radical pair which exhibits ESP, P870+Q- (P870+ is the oxidized, primary electron donor, a bacteriochlorophyll special pair and Q- is the reduced, primary quinone acceptor) is formed via sequential electron transport through the intermediary radical pair P870+I- (I- is the reduced, intermediary electron acceptor, a bacteriopheophytin). In addition, it is possible to experimentally vary most of the important parameters, such as the lifetime of the intermediary radical pair and the magnetic interactions in each pair. It has been shown how selective isotopic substitution (1H or 2H) on P870, I and Q affects the ESP of the EPR spectrum of P870+Q-, observed at two different microwave/sup>, observed at two different microwave frequencies, in Fe2+-depleted bacterial reaction centers of Rhodobacter sphaeroides R26. Thus, the relative magnitudes of the magnetic properties (nuclear hyperfine and g-factor differences) which influence ESP development were varied. The results support the general model of ESP in that they suggest that the P870+Q- radical pair interactions are the dominant source of ESP production in 2H bacterial reaction centers

  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. PMID:25725711

  5. Dynamics of combined electron- and proton transfer at metal electrodes

    International Nuclear Information System (INIS)

    A model for combined electrochemical electron- and proton transfer is proposed, which is based on a second-quantized model Hamiltonian. It allows the calculation of potential energy surfaces for the reactions, which typically show four minima corresponding to the four system states. For the case of adiabatic transitions, reaction rates are obtained from stochastic dynamics simulations. Non-adiabatic proton transfer is examined in greater detail, and the path of the transferring proton is followed explicitly. In addition, the dependence of the reaction rate on the solvent friction and on the characteristics of the proton potential is investigated

  6. A role for excreted quinones in extracellular electron transfer

    Science.gov (United States)

    Newman, Dianne K.; Kolter, Roberto

    2000-05-01

    Respiratory processes in bacteria are remarkable because of their ability to use a variety of compounds, including insoluble minerals, as terminal electron acceptors. Although much is known about microbial electron transport to soluble electron acceptors, little is understood about electron transport to insoluble compounds such as ferric oxides. In anaerobic environments, humic substances can serve as electron acceptors and also as electron shuttles to ferric oxides. To explore this process, we identified mutants in Shewanella putrefaciens that are unable to respire on humic substances. Here we show that these mutants contain disruptions in a gene that is involved in the biosynthesis of menaquinone. During growth, the wild type releases a menaquinone-related redox-active small molecule into the medium that complements the mutants. This finding raises the possibility that electron transfer to a variety of oxidants, including poorly soluble minerals, may be mediated by microbially excreted quinones that have yet to be identified.

  7. Electron Transfer Dissociation Mass Spectrometry of Hemoglobin on Clinical Samples

    Science.gov (United States)

    Coelho Graça, Didia; Lescuyer, Pierre; Clerici, Lorella; Tsybin, Yury O.; Hartmer, Ralf; Meyer, Markus; Samii, Kaveh; Hochstrasser, Denis F.; Scherl, Alexander

    2012-10-01

    A mass spectrometry-based assay combining the specificity of selected reaction monitoring and the protein ion activation capabilities of electron transfer dissociation was developed and employed for the rapid identification of hemoglobin variants from whole blood without previous proteolytic cleavage. The analysis was performed in a robust ion trap mass spectrometer operating at nominal mass accuracy and resolution. Subtle differences in globin sequences, resulting with mass shifts of about one Da, can be unambiguously identified. These results suggest that mass spectrometry analysis of entire proteins using electron transfer dissociation can be employed on clinical samples in a workflow compatible with diagnostic applications.

  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. Photonic modulation of electron transfer with switchable phase inversion.

    Science.gov (United States)

    Frey, Julien; Kodis, Gerdenis; Straight, Stephen D; Moore, Thomas A; Moore, Ana L; Gust, Devens

    2013-01-24

    Photochromes may be reversibly photoisomerized between two metastable states and their properties can influence, and be influenced by, other chromophores in the same molecule through energy or electron transfer. In the photochemically active molecular tetrad described here, a porphyrin has been covalently linked to a fullerene electron acceptor, a quinoline-derived dihydroindolizine photochrome, and a dithienylethene photochrome. The porphyrin first excited singlet state undergoes photoinduced electron transfer to the fullerene to generate a charge-separated state. The quantum yield of charge separation is modulated by the two photochromes: one isomer of each quenches the porphyrin excited state, reducing the quantum yield of electron transfer to near zero. Interestingly, when the molecule is illuminated with white light, the quantum yield decreases as the white light intensity is increased, generating an out-of-phase response of the quantum yield to white light. However, when the same experiment is performed in the presence of additional, steady-state UV illumination, a phase inversion occurs. The quantum yield of electron transfer now increases with increasing white light intensity. Such effects illustrate emergent complexity in a relatively simple system and could find applications in molecular logic, photochemical labeling and drug delivery, and photoprotection for artificial photosynthetic molecules. The photochemistry leading to this behavior is discussed. PMID:23259536

  10. Long-distance photoinitiated electron transfer through polyene molecular wires

    International Nuclear Information System (INIS)

    Long-chain polyenes can be used as molecular wires to facilitate electron transfer between a photo-excited donor and an acceptor in an artificial photosynthetic system. The authors present data here on two Zn-porphyrin-polyene-anthraquinone molecules possessing either 5 or 9 all trans double bonds between the donor and acceptor, 1 and 2. The center-to-center distances between the porphyrin and the quinone in these relatively rigid molecules are 25 angstrom for 1 and 35 angstrom for 2. Selective picosecond laser excitation of the Zn-porphyrin and 1 and 2 results in the very rapid transfer of an electron to the anthraquinone in <2 ps and 10 ps, respectively. The resultant radical ion pairs recombine with ? = 10 ps for 1 and ? = 25 ps for 2. The electron transfer rates remain remarkably rapid over these long distances. The involvement of polyene radical cations in the mechanism of the radical ion pair recombination reaction is clear from the transient absorption spectra of 1 and 2, which show strong absorbances in the near-infrared. The strong electronic coupling between the Zn-porphyrin n the anthraquinone provided by low-lying states of the polyene make it possible to transfer an electron rapidly over very long distances

  11. Electronic structure aspects of the complete O2 transfer reaction between Ni(II) and Mn(II) complexes with cyclam ligands.

    Science.gov (United States)

    Zapata-Rivera, Jhon; Caballol, Rosa; Calzado, Carmen J

    2015-01-28

    This work explores the electronic structure aspects involving the complete intermolecular O2 transfer between Ni(ii) and Mn(ii) complexes, both containing N-tetramethylated cyclams (TMC). The energy of the low-lying states of reactants, intermediates and products is established at the CASSCF level and also the DDCI level when possible. The orthogonal valence bond analysis of the wave functions obtained from CASSCF and DDCI calculations indicates the dominant superoxide nature of all the adducts participating in the reaction, and consequently that the whole reaction can be described as the transfer of the superoxide O2(-) between Ni(ii) and Mn(ii) complexes, without any additional change in the electronic structure of the fragments. PMID:25502350

  12. Role of the electronic properties of azurin active site in the electron-transfer process

    Science.gov (United States)

    Corni, Stefano; de Rienzo, Francesca; di Felice, Rosa; Molinari, Elisa

    Electron transfer proteins, such as azurin (a blue copper protein), are promising candidates for the implementation of biomolecular nanoelectronic devices. To understand the details of electron transfer in redox active azurin molecules, we performed plane-wave pseudo-potential density functional theory (DFT) calculations of the protein active site in the two possible oxidation states Cu(I) and Cu(II). The ab initio results are used to discuss how the electronic spectrum and wavefunctions may mediate the shuttling of electrons through the copper ion. We find that the Cu-ligand hybridization is very similar in the two charge states of the metal center, but the energy spectrum changes substantially. This result might indicate important effects of electronic correlations in the redox activity and consequent electron transfer through the Cu site.

  13. Solvent structure and hydrodynamic effects in photoinduced electron transfer

    International Nuclear Information System (INIS)

    A previously developed statistical mechanical theory describing photo-induced electron transfer and geminate recombination in liquid solutions has been modified to account for realistic finite-volume solvent effects. This work introduces physically important effects caused by the solvent which fundamentally affect the rates and spatial distribution of charge transfer events. The finite volume of solvent molecules gives rise to a nonuniform distribution of particles around an electron donor, which is incorporated into the theory by a two-particle radial distribution function (rdf). The Percus endash Yevick solutions for the rdf can give numerically useful values for the solvent structure, g(R) although any form of g(R) can be used with the method. The nonuniform particle distribution significantly affects the electron transfer rates and the distribution of ion pairs formed by forward electron transfer, particularly at short times. In addition, finite solvent size affects the rate of relative diffusion between any donor endash acceptor pair. These open-quote open-quote hydrodynamic effects close-quote close-quote slow down the interparticle diffusion rates when near contact, resulting in a major change in the long time behavior of photoexcited electron transfer systems. This work formally introduces the mathematical modifications to charge transfer theory necessary to account for the solvent structure and hydrodynamic effect and illustrates the results with model calcul illustrates the results with model calculations. These calculations show that analysis of experiments with theories that do not include the rdf and hydrodynamic effects can result in significant errors in the interpretation of data. copyright 1996 American Institute of Physics

  14. Quality assurance and data collection -- Electronic Data Transfer

    International Nuclear Information System (INIS)

    The Radiological Environmental Monitoring (REM) group at the Fernald Environmental Management Project is involved in an Electronic Data Transfer practice that will result in the improved quality assurance of collected data. This practice focuses on electronic data transfer from the recording instrument to reduce the manpower normally required for manual data entry and improve the quality of the data transferred. The application of this practice can enhance any data collection program where instruments with electronic memories and a signal output are utilized. Organizations employing this practice can strengthen the quality and efficiency of their data collection program. The use of these practices can assist in complying with Quality Assurance requirements under ASME NQA-1, RCRA, CERCLA, and DOE Order activities. Data from Pylon AB-5 instrumentation is typically configured to print data to a tape. The REM group has developed a process to electronically transfer stored data. The data are sent from the Pylon AB-5 field instrument to a HewlettPackard portable hand computer, model HP95LX. Data are recorded and stored on a 128 K-byte RAN card and later transferred to a PC database as an electronic file for analysis. The advantage of this system is twofold: (1) Data entry errors are eliminated and (2) considerable data collection and entry time is eliminated. Checks can then be conducted for data validity between recorded intervals due to light leaks etc. and the detection of outliers. This paper will discuss the interface and connector components that allow this transfer of data from the Pylon to the PC to take place and the process to perform that activity

  15. Multi-electron transfer to and from organic molecules

    OpenAIRE

    Batchelor-mcauley, Christopher; Compton, Richard Guy

    2012-01-01

    Herein, the influence of protonation and adsorption upon the redox and electrocatalysis of quinone species - specifically anthraquinone derivatives – is investigated.Through the comparison of the measured rate constants of one-electron reductions of a family of quinones in acetonitrile at both graphite and gold electrodes, it was confirmed that the redox potential indirectly influences the rate of electron transfer in a manner consistent with the potential-dependence of the density of...

  16. Resonant optical electron transfer in one-dimensional multiwell structures

    OpenAIRE

    Tsukanov, A. V.

    2008-01-01

    We consider coherent single-electron dynamics in the one-dimensional nanostructure under resonant electromagnetic pulse. The structure is composed of two deep quantum wells positioned at the edges of structure and separated by a sequence of shallow internal wells. We show that complete electron transfer between the states localized in the edge wells through one of excited delocalized states can take place at discrete set of times provided that the pulse frequency matches one...

  17. Light-Induced Dynamics in Photosystem I Electron Transfer

    OpenAIRE

    Bender, Shana L.; Barry, Bridgette A.

    2008-01-01

    Protein dynamics are likely to play important, regulatory roles in many aspects of photosynthetic electron transfer, but a detailed description of these coupled protein conformational changes has been unavailable. In oxygenic photosynthesis, photosystem I catalyzes the light-driven oxidation of plastocyanin or cytochrome c and the reduction of ferredoxin. A chlorophyll (chl) a/a? heterodimer, P700, is the secondary electron donor, and the two P700 chl, are designated PA and PB. We used spec...

  18. Inelastic electron photon scattering at moderate four momentum transfers

    International Nuclear Information System (INIS)

    We present new high statistics data on hadron production in photon photon reactions. The data are analyzed in terms of an electron photon scattering formalism. The dependence of the total cross section on Q2, the four momentum transfer squared of the scattered electron, and on the mass W of the hadronic system is investigated. The data are compared to predictions from Vector Dominance and the quark model. (orig.)

  19. Solvation dynamics and solvent-controlled electron transfer

    International Nuclear Information System (INIS)

    This paper discusses traditional descriptions of outer sphere electron transfer (ET) in polar solvents which rest on the implicit assumption that either the microscopic electronic process, rather than the dielectric relaxation, constitutes the rate determining step, or the solvation occurs fast enough, so that the orientational part of solvent polarization is in equilibrium with the charge distribution at any time instant. Solvation kinetics are considered

  20. Carboxylate Shifts Steer Interquinone Electron Transfer in Photosynthesis*

    OpenAIRE

    Chernev, Petko; Zaharieva, Ivelina; Dau, Holger; Haumann, Michael

    2010-01-01

    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-resolu...

  1. Accumulative electron transfer: multiple charge separation in artificial photosynthesis.

    Science.gov (United States)

    Karlsson, Susanne; Boixel, Julien; Pellegrin, Yann; Blart, Errol; Becker, Hans-Christian; Odobel, Fabrice; Hammarström, Leif

    2012-01-01

    To achieve artificial photosynthesis it is necessary to couple the single-electron event of photoinduced charge separation with the multi-electron reactions of fuel formation and water splitting. Therefore, several rounds of light-induced charge separation are required to accumulate enough redox equivalents at the catalytic sites for the target chemistry to occur, without any sacrificial donors or acceptors other than the catalytic substrates. Herein, we discuss the challenges of such accumulative electron transfer in molecular systems. We present a series of closely related systems base on a Ru(II)-polypyridine photosensitizer with appended triaryl-amine or oligo-triaryl-amine donors, linked to nanoporous TiO2 as the acceptor. One of the systems, based on dye 4, shows efficient accumulative electron transfer in high overall yield resulting in the formation of a two-electron charge-separated state upon successive excitation by two photons. In contrast, the other systems do not show accumulative electron transfer because of different competing reactions. This illustrates the difficulties in designing successful systems for this still largely unexplored type of reaction scheme. PMID:22470977

  2. Characterization of photoinduced self-exchange reactions at molecule-semiconductor interfaces by transient polarization spectroscopy: lateral intermolecular energy and hole transfer across sensitized TiO2 thin films.

    Science.gov (United States)

    Ardo, Shane; Meyer, Gerald J

    2011-10-01

    Transient anisotropy measurements are reported as a new spectroscopic tool for mechanistic characterization of photoinduced charge-transfer and energy-transfer self-exchange reactions at molecule-semiconductor interfaces. An anisotropic molecular subpopulation was generated by photoselection of randomly oriented Ru(II)-polypyridyl compounds, anchored to mesoscopic nanocrystalline TiO(2) or ZrO(2) thin films, with linearly polarized light. Subsequent characterization of the photoinduced dichromism change by visible absorption and photoluminescence spectroscopies on the nano- to millisecond time scale enabled the direct comparison of competitive processes: excited-state decay vs self-exchange energy transfer, or interfacial charge recombination vs self-exchange hole transfer. Self-exchange energy transfer was found to be many orders-of-magnitude faster than hole transfer at the sensitized TiO(2) interfaces; for [Ru(dtb)(2)(dcb)](PF(6))(2), where dtb is 4,4'-(C(CH(3))(3))(2)-2,2'-bipyridine and dcb is 4,4'-(COOH)(2)-2,2'-bipyridine, anchored to TiO(2), the energy-transfer correlation time was ?(ent) = 3.3 ?s while the average hole-transfer correlation time was = 110 ms, under identical experimental conditions. Monte Carlo simulations successfully modeled the anisotropy decays associated with lateral energy transfer. These mesoscopic, nanocrystalline TiO(2) thin films developed for regenerative solar cells thus function as active "antennae", harvesting sunlight and transferring energy across their surface. For the dicationic sensitizer, [Ru(dtb)(2)(dcb)](PF(6))(2), anisotropy changes indicative of self-exchange hole transfer were observed only when ions were present in the acetonitrile solution. In contrast, evidence for lateral hole transfer was observed in neat acetonitrile for a neutral sensitizer, cis-Ru(dnb)(dcb)(NCS)(2), where dnb is 4,4'-(CH(3)(CH(2))(8))(2)-2,2'-bipyridine, anchored to TiO(2). The results indicate that mechanistic models of interfacial charge recombination between electrons in TiO(2) and oxidized sensitizers must take into account diffusion of the injected electron and the oxidized sensitizer. The phenomena presented herein represent two means of concentrating potential energy derived from visible light that could be used to funnel energy to molecular catalysts for multiple-charge-transfer reactions, such as the generation of solar fuels. PMID:21861499

  3. Evaluation of the influence of intermolecular electron-nucleus couplings and intrinsic metal binding sites on the measurement of 15N longitudinal paramagnetic relaxation enhancements in proteins by solid-state NMR

    International Nuclear Information System (INIS)

    Magic-angle spinning solid-state NMR measurements of 15N longitudinal paramagnetic relaxation enhancements (PREs) in 13C,15N-labeled proteins modified with Cu2+-chelating tags can yield multiple long-range electron-nucleus distance restraints up to ?20 Å (Nadaud et al. in J Am Chem Soc 131:8108–8120, 2009). Using the EDTA-Cu2+ K28C mutant of B1 immunoglobulin binding domain of protein G (GB1) as a model, we investigate the effects on such measurements of intermolecular electron-nucleus couplings and intrinsic metal binding sites, both of which may potentially complicate the interpretation of PRE data in terms of the intramolecular protein fold. To quantitatively assess the influence of intermolecular 15N-Cu2+ interactions we have determined a nearly complete set of longitudinal 15N PREs for a series of microcrystalline samples containing ?10, 15 and 25 mol percent of the 13C,15N-labeled EDTA-Cu2+-tagged protein diluted in a matrix of diamagnetic natural abundance GB1. The residual intermolecular interactions were found to be minor on the whole and account for only a fraction of the relatively small but systematic deviations observed between the experimental 15N PREs and corresponding values calculated using protein structural models for residues furthest removed from the EDTA-Cu2+ tag. This suggests that these deviationsThis suggests that these deviations are also caused in part by other factors not related to the protein structure, such as the presence in the protein of intrinsic secondary sites capable of binding Cu2+ ions. To probe this issue we performed a Cu2+ titration study for K28C-EDTA GB1 monitored by 2D 15N-1H solution-state NMR, which revealed that while for Cu2+:protein molar ratios of ? 1.0 Cu2+ binds primarily to the high-affinity EDTA tag, as anticipated, at even slightly super-stoichiometric ratios the Cu2+ ions can also associate with side-chains of aspartate and glutamate residues. This in turn is expected to lead to enhanced PREs for residues located in the vicinity of the secondary Cu2+ binding sites, and indeed many of these residues were ones found to display the elevated longitudinal 15N PREs in the solid phase.

  4. Evaluation of the influence of intermolecular electron-nucleus couplings and intrinsic metal binding sites on the measurement of {sup 15}N longitudinal paramagnetic relaxation enhancements in proteins by solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Nadaud, Philippe S.; Sengupta, Ishita; Helmus, Jonathan J.; Jaroniec, Christopher P., E-mail: jaroniec@chemistry.ohio-state.edu [Ohio State University, Department of Chemistry (United States)

    2011-11-15

    Magic-angle spinning solid-state NMR measurements of {sup 15}N longitudinal paramagnetic relaxation enhancements (PREs) in {sup 13}C,{sup 15}N-labeled proteins modified with Cu{sup 2+}-chelating tags can yield multiple long-range electron-nucleus distance restraints up to {approx}20 A (Nadaud et al. in J Am Chem Soc 131:8108-8120, 2009). Using the EDTA-Cu{sup 2+} K28C mutant of B1 immunoglobulin binding domain of protein G (GB1) as a model, we investigate the effects on such measurements of intermolecular electron-nucleus couplings and intrinsic metal binding sites, both of which may potentially complicate the interpretation of PRE data in terms of the intramolecular protein fold. To quantitatively assess the influence of intermolecular {sup 15}N-Cu{sup 2+} interactions we have determined a nearly complete set of longitudinal {sup 15}N PREs for a series of microcrystalline samples containing {approx}10, 15 and 25 mol percent of the {sup 13}C,{sup 15}N-labeled EDTA-Cu{sup 2+}-tagged protein diluted in a matrix of diamagnetic natural abundance GB1. The residual intermolecular interactions were found to be minor on the whole and account for only a fraction of the relatively small but systematic deviations observed between the experimental {sup 15}N PREs and corresponding values calculated using protein structural models for residues furthest removed from the EDTA-Cu{sup 2+} tag. This suggests that these deviations are also caused in part by other factors not related to the protein structure, such as the presence in the protein of intrinsic secondary sites capable of binding Cu{sup 2+} ions. To probe this issue we performed a Cu{sup 2+} titration study for K28C-EDTA GB1 monitored by 2D {sup 15}N-{sup 1}H solution-state NMR, which revealed that while for Cu{sup 2+}:protein molar ratios of {<=} 1.0 Cu{sup 2+} binds primarily to the high-affinity EDTA tag, as anticipated, at even slightly super-stoichiometric ratios the Cu{sup 2+} ions can also associate with side-chains of aspartate and glutamate residues. This in turn is expected to lead to enhanced PREs for residues located in the vicinity of the secondary Cu{sup 2+} binding sites, and indeed many of these residues were ones found to display the elevated longitudinal {sup 15}N PREs in the solid phase.

  5. 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.

  6. Electron transfer between exogenous electron donors and reaction center of photosystem 2.

    Science.gov (United States)

    Mamedov, M D; Kurashov, V N; Petrova, I O; Zaspa, A A; Semenov, A Yu

    2010-05-01

    Transfer of electrons between artificial electron donors diphenylcarbazide (DPC) and hydroxylamine (NH2OH) and reaction center of manganese-depleted photosystem 2 (PS2) complexes was studied using the direct electrometrical method. For the first time it was shown that reduction of redox-active amino acid tyrosine Y(Z)(.) by DPC is coupled with generation of transmembrane electric potential difference (DeltaPsi). The amplitude of this phase comprised ~17% of that of the DeltaPsi phase due to electron transfer between Y(Z) and the primary quinone acceptor Q(A). This phase is associated with vectorial intraprotein electron transfer between the DPC binding site on the protein-water interface and the tyrosine Y(Z)(.). The slowing of DeltaPsi decay in the presence of NH2OH indicates effective electron transfer between the artificial electron donor and reaction center of PS2. It is suggested that NH2OH is able to diffuse through channels with diameter of 2.0-3.0 A visible in PS2 structure and leading from the protein-water interface to the Mn(4)Ca cluster binding site with the concomitant electron donation to Y(Z)(.). Because the dielectrically-weighted distance between the NH2OH binding site and Y(Z)(.) is not determined, the transfer of electrons from NH2OH to Y(Z)(.) could be either electrically silent or contribute negligibly to the observed electrogenicity in comparison with hydrophobic donors. PMID:20632936

  7. Electron Correlation and Charge Transfer Instability in Bilayered Two Dimensional Electron Gas

    OpenAIRE

    Conti, Sergio; Senatore, Gaetano

    1996-01-01

    We prove that the predicted charge transfer state in symmetric bilayers of two dimensional electron gases is always unstable at zero bias voltage, due to interlayer correlation and/or tunneling. This is most easily seen by resorting to a pseudospin formalism and considering coherent states obtained from the charge transfer state through rotations of the pseudospins. Evidently, the charge transfer state is stabilized by a sufficiently strong gate voltage, as found in recent e...

  8. Electronic excitation energy transfer between quasi-zero-dimensional systems.

    Czech Academy of Sciences Publication Activity Database

    Král, Karel; Menšík, Miroslav

    Ostrava : Tanger, 2013. ISBN 978-80-87294-44-4. [International Conference NANOCON 2013 /5./. Brno (CZ), 16.10.2013-18.10.2013] R&D Projects: GA MŠk LH12236; GA MŠk LH12186 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : quantum dots * energy transfer * electron-phonon interaction Subject RIV: BM - Solid Matter Physics ; Magnetism

  9. Cluster transfer matrix method for the single electron box

    OpenAIRE

    Chung, S. G.

    1999-01-01

    With the newly developed cluster transfer matrix method, we calculate the average electron number n vs nx (the polarization charge) for varying junction conductance and its first derivative at nx=0 for finite temperatures, and demonstrate that the new method is as powerful as the Monte Carlo and renormalization group methods.

  10. CORRELATING ELECTRONIC AND VIBRATIONAL MOTIONS IN CHARGE TRANSFER SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    Khalil, Munira

    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.

  11. Heterogeneous electron transfer of pesticides. Current trends and applications.

    Czech Academy of Sciences Publication Activity Database

    Sokolová, Romana; Hromadová, Magdaléna; Pospíšil, Lubomír

    Kerala : Transworld Research Network, 2008 - (Colombini, M.; Tassi, L.), s. 43-76 ISBN 978-81-7895-343-4 R&D Projects: GA AV ?R IAA400400505; GA MŠk LC510; GA MŠk OC 140 Institutional research plan: CEZ:AV0Z40400503 Keywords : heterogeneous electron transfer * pesticides * redox reactions Subject RIV: CF - Physical ; Theoretical Chemistry

  12. Ion and Electron Transfer Reactions at Metal-Solution Interfaces

    Science.gov (United States)

    Schmickler, Wolfgang

    1997-03-01

    An extension of the Anderson-Newns model is used as a unifying framework for both ion and electron transfer reactions on metal electrodes. The model allows the construction of effective free-energy surfaces as functions of a generalized solvent coordinate and of the reactant's separation from the surface. For electron transfer reactions the reaction coordinate is mainly in the direction of the solvent coordinate; for ion transfer the partial loss of the solvation sheath and the accompanying solvent displacement is the rate-determining step, and the reaction coordinate is mainly determined by the separation from the metal surface. Explicit results are presented for the adsorption of an iodide ion on Pt(100), for the deposition of Zn^2+ on Hg, and for the Fe^2+/Fe^3+ reaction. The reaction rates can be calculated from these surfaces with the aid of Kramers theory.

  13. Probing Inhomogeneous Vibrational Reorganization Energy Barriers of Interfacial Electron Transfer

    Energy Technology Data Exchange (ETDEWEB)

    Pan, Duohai; Hu, Dehong; Lu, H. Peter

    2005-09-01

    We report an atomic force microscopy (AFM) and confocal Raman microscopy study on the interfacial electron transfer of a dye-sensitization system, alizarin adsorbed upon TiO2 nanoparticles. Resonance Raman and absorption spectral analyses revealed the distribution of the mode-specific vibrational reorganization energies encompassing different local sites (~250 nm spatial resolution), suggesting spatially inhomogeneous vibrational reorganization energy and different Franck-Condon coupling factors of the interfacial electron transfer. We found that the total vibrational reorganization energy was inhomogeneous from site to site, and specifically, the mode-specific analyses indicated that the energy distributions were inhomogeneous for bridging normal modes and homogeneous for nonbridging normal modes, especially for modes far away from the alizarin- TiO2 coupling hydroxyl modes. Our results demonstrate a significant step forward in characterizing site-specific inhomogeneous interfacial charge transfer dynamics.

  14. pH-Dependent Reduction Potentials and Proton-Coupled Electron Transfer Mechanisms in Hydrogen-Producing Nickel Molecular Electrocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Horvath, Samantha; Fernandez, Laura; Appel, Aaron M.; Hammes-Schiffer, Sharon

    2013-04-01

    The nickel-based Ph Bz 2 2 P N electrocatalysts, which are comprised of a nickel atom and two 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane ligands, have been shown to effectively catalyze H2 production in acetonitrile. Recent electrochemical experiments revealed a linear dependence of the NiII/I reduction potential on pH, suggesting a proton-coupled electron transfer (PCET) reaction. In the proposed mechanism, the catalytic cycle begins with a PCET process involving electrochemical electron transfer to the nickel center and intermolecular proton transfer from an acid to the pendant amine ligand. This paper presents quantum mechanical calculations of this PCET process to examine the thermodynamics of the sequential mechanisms, in which either the electron or the proton transfers first (ET–PT and PT–ET, respectively), and the concerted mechanism (EPT). The favored mechanism depends on a balance among many factors, including the acid strength, association free energy for the acid–catalyst complex, PT free energy barrier, and ET reduction potential. The ET reduction potential is less negative after PT, favoring the PT–ET mechanism, and the association free energy is less positive after reduction, favoring the ET–PT mechanism. The calculations, along with analysis of the experimental data, indicate that the sequential ET–PT mechanism is favored for weak acids because of the substantial decrease in the association free energy after reduction. For strong acids, however, the PT–ET mechanism may be favored because the association free energy is somewhat smaller and PT is more thermodynamically favorable. The concerted mechanism could also occur, particularly for intermediate acid strengths. In the context of the entire catalytic cycle for H2 production, the initial PCET process involving intermolecular PT has a more negative reduction potential than the subsequent PCET process involving intramolecular PT. As a result, the second PCET should occur spontaneously, which is consistent with cyclic voltammogram experiments. 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.

  15. Shewanella secretes flavins that mediate extracellular electron transfer.

    Science.gov (United States)

    Marsili, Enrico; Baron, Daniel B; Shikhare, Indraneel D; Coursolle, Dan; Gralnick, Jeffrey A; Bond, Daniel R

    2008-03-11

    Bacteria able to transfer electrons to metals are key agents in biogeochemical metal cycling, subsurface bioremediation, and corrosion processes. More recently, these bacteria have gained attention as the transfer of electrons from the cell surface to conductive materials can be used in multiple applications. In this work, we adapted electrochemical techniques to probe intact biofilms of Shewanella oneidensis MR-1 and Shewanella sp. MR-4 grown by using a poised electrode as an electron acceptor. This approach detected redox-active molecules within biofilms, which were involved in electron transfer to the electrode. A combination of methods identified a mixture of riboflavin and riboflavin-5'-phosphate in supernatants from biofilm reactors, with riboflavin representing the dominant component during sustained incubations (>72 h). Removal of riboflavin from biofilms reduced the rate of electron transfer to electrodes by >70%, consistent with a role as a soluble redox shuttle carrying electrons from the cell surface to external acceptors. Differential pulse voltammetry and cyclic voltammetry revealed a layer of flavins adsorbed to electrodes, even after soluble components were removed, especially in older biofilms. Riboflavin adsorbed quickly to other surfaces of geochemical interest, such as Fe(III) and Mn(IV) oxy(hydr)oxides. This in situ demonstration of flavin production, and sequestration at surfaces, requires the paradigm of soluble redox shuttles in geochemistry to be adjusted to include binding and modification of surfaces. Moreover, the known ability of isoalloxazine rings to act as metal chelators, along with their electron shuttling capacity, suggests that extracellular respiration of minerals by Shewanella is more complex than originally conceived. PMID:18316736

  16. Electron-transfer reactions at the plasma-liquid interface.

    Science.gov (United States)

    Richmonds, Carolyn; Witzke, Megan; Bartling, Brandon; Lee, Seung Whan; Wainright, Jesse; Liu, Chung-Chiun; Sankaran, R Mohan

    2011-11-01

    Electrochemical reactions are normally initiated in solution by metal electrodes such as Pt, which are expensive and limited in supply. In this Communication, we demonstrate that an atmospheric-pressure microplasma can act as a gaseous, metal-free electrode to mediate electron-transfer reactions in aqueous solutions. Ferricyanide is reduced to ferrocyanide by plasma electrons, and the reduction rate is found to depend on discharge current. The ability to initiate and control electrochemical reactions at the plasma-liquid interface opens a new direction for electrochemistry based on interactions between gas-phase electrons and ionic solutions. PMID:21985430

  17. Electron Transfer in Donor-Acceptor Systems: Many-Particle Effects and Influence of Electronic Correlations

    CERN Document Server

    Tornow, S; Bulla, R; Tornow, Sabine; Tong, Ning-Hua; Bulla, Ralf

    2006-01-01

    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 alpha_c 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.

  18. [Photo-induced electron transfer effects of poly(2-methoxy-5-octyloxy)-p-phenylene vinylene/Y2O3:Eu3+ nano-composites].

    Science.gov (United States)

    Sun, Jian-ping; Ma, Lin-pu; Lin, Ting

    2010-01-01

    The photoelectric nano-composites of poly(2-methoxy-5-octyloxy)-p-phenylene vinylene/Y2O3:Eu3+ (PMOCOPV/Y2O3:Eu3+) were prepared by dehydrochlorination in-situ polymerization. The result of Fourier transform infrared spectroscopy indicates that PMOCOPV is coated on the surface of Y2O3:Eu3+. Compared with PMOCOPV, the absorption of PMOCOPV/Y2O3:Eu3+ is strengthened, and a red shift of the absorption peak can be clearly observed in the UV-Vis spectrum. Photoluminescence spectroscopy indicates that the maximum emission wavelength of the PMOCOPV/Y2O3:Eu3+ is red-shifted and the intensity of photoluminescence increases in comparison with PMOCOPV. PMOCOPV/Y2O3:Eu3+ shows fluorescence increasing, which involved the inter-molecular photo-induced charge transfer process. The optical band gap of PMOCOPV/Y2O3:Eu3+ decreases. The third-order optical nonlinear susceptibility of PMOCOPV/Y2O3:Eu3+ nano-composites was measured by degenerate four wave mixing. The results show that the third-order nonlinear optical responses of PMOCOPV/Y2O3:Eu3+ nano-composites are enhanced in comparison with PMOCOPV, which can be attributed to inter-molecular photo-induced electron transfer and delocalized pi electron coupling between PMOCOPV and Y2O3:Eu3+. PMID:20302070

  19. Electron scattering off simple atoms for large momentum transfer collisions

    International Nuclear Information System (INIS)

    In a previous paper this author examined the Born expansion and isolated those parts of the expansion that contribute most significantly to the scattering amplitude for large momentum transfer collisions in inelastic collisions from the ground state of both hydrogen and helium. It turned out that certain terms where the scattering electron interacts once with the nucleus and once with the other electron dominate. The physical reason is that large momentum transfer collisions require the nucleus to take the bulk of the incident momentum but require an interaction with the one of the bound electrons to change the state of the atom. The arguments are quite general and this paper will extend this analysis by comparing the inelastic results obtained by this method for hydrogen and helium to a close coupling calculation with many intermediate states. Further, we will extend this analysis to the correction to the 1st Born result for elastic electron-hydrogen and electron-helium collisions and provide some results for scattering from the initial metastable states of hydrogen for large momentum transfer collisions. A comparison of the results of this analytic approach will be made to the numerical close coupling approach and experiments where available. The agreement is remarkable

  20. Ab Initio Study of the Electron Transfer in an Ionized Stacked Complex of Guanines

    Science.gov (United States)

    Cauët, Emilie; Liévin, Jacques

    2009-08-01

    The charge transfer process in an ionized stacking of two consecutive guanines (G5'G3')+ has been studied by means of state-averaged CASSCF/MRCI and RASSCF/RASPT2 calculations. The ground and two first excited states of the radical cation have been characterized, and the topology of the corresponding potential energy surfaces (PESs) has been studied as a function of all intermolecular geometrical parameters. The results demonstrate that the charge transfer process in (G5'G3')+ is governed by the avoiding crossing between the ground and first excited states of the complex. Relative translation motions of both guanines in their molecular planes are shown to lead to the charge migration between G5' and G3'. Five stationary points (three minima and two saddle points) have been characterized along the reaction path describing the passage of the positive charge from G5' to G3'. The global minimum on the PES is found to correspond to the charge configuration G5'+G3'. The existence of an intermediate minimum along the reaction path has been established, characterizing a structure where the positive charge is equally distributed between the two guanines. The calculated energy profile allowed us to determine the height of the potential energy barrier (7.33 kcal/mol) and to evaluate the electronic coupling at a geometry close to the avoiding crossing (3.6 kcal/mol). Test calculations showed that the topology of the ground state PES of the complex GG+ is qualitatively conserved upon optimization of the intramolecular geometrical parameters of the stationary points.

  1. Photorelaxation induced by water-chromophore electron transfer.

    Science.gov (United States)

    Barbatti, Mario

    2014-07-23

    Relaxation of photoexcited chromophores is a key factor determining diverse molecular properties, from luminescence to photostability. Radiationless relaxation usually occurs through state intersections caused by distortions in the nuclear geometry of the chromophore. Using excited-state nonadiabatic dynamics simulations based on algebraic diagrammatic construction, it is shown that this is the case of 9H-adenine in water cluster, but not of 7H-adenine in water cluster. 7H-adenine in water cluster relaxes via a state intersection induced by electron transfer from water to the chromophore. This result reveals an unknown reaction pathway, with implications for the assignment of relaxation mechanisms of exciton relaxation in organic electronics. The observation of photorelaxation of 7H-adenine induced by water-chromophore electron transfer is a proof of principle calling for further computational and experimental investigations to determine how common this effect is. PMID:25010652

  2. Syntrophic growth via quinone-mediated interspecies electron transfer

    Science.gov (United States)

    Smith, Jessica A.; Nevin, Kelly P.; Lovley, Derek R.

    2015-01-01

    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 G. 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. Co-cultures 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 further investigation. PMID:25741332

  3. Syntrophic growth via quinone-mediated interspecies electron transfer.

    Science.gov (United States)

    Smith, Jessica A; Nevin, Kelly P; Lovley, Derek R

    2015-01-01

    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 G. 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. Co-cultures 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 further investigation. PMID:25741332

  4. Distance dependence of intramolecular electron transfer through rigid hydrocarbon spacers

    International Nuclear Information System (INIS)

    The effects of energy, distance and molecular structure on rates of electron transfer between molecules are the subjects of continuing investigations in the authors laboratory. The use of rigid molecular spacers between electron donor and acceptor groups facilitates study of the above questions, and is a promising method to obtain energy storage with directed charge separation. Here they present recent results focusing principally on the effects of distance through rigid hydrocarbon spacers. Through-bond interaction is the dominant source of the electronic coupling which enables electron transfer to occur in a series of molecules of the type D-S-A. Pulse radiolysis measurements used molecules D (donor) = biphenyl and A (acceptor) = naphthalene attached to a series of spacer molecules, S, having 3,4,6,7 or 10 saturated hydrocarbon bonds between the D and A groups. The spacer groups were 1,3-cyclohexane (three bonds), 1,4-cyclohexane (four bonds), 2,7-decalin (six bonds), 2,6-decalin (seven bonds) and 3,16-androstance (ten bonds). They attached electrons to these molecules using Argonne's picosecond Linac and measured electron transfer rates (ET) from 3.5 x 109s-1 across three bonds to 1.5 x 106s-1 across ten bonds. The clearest understanding of the rates is obtained by comparing the electronic-coupling interactions. The electronic interactions decrease regularly with increasing number of bonds, but do not correlate very well of bonds, but do not correlate very well with either edge-to-edge or center-to-center distance

  5. Simulations of charge transfer in Electron Multiplying Charge Coupled Devices

    Science.gov (United States)

    Bush, N.; Stefanov, K.; Hall, D.; Jordan, D.; Holland, A.

    2014-12-01

    Electron Multiplying Charge Coupled Devices (EMCCDs) are a variant of traditional CCD technology well suited to applications that demand high speed operation in low light conditions. On-chip signal amplification allows the sensor to effectively suppress the noise introduced by readout electronics, permitting sub-electron read noise at MHz pixel rates. The devices have been the subject of many detailed studies concerning their operation, however there has not been a study into the transfer and multiplication process within the EMCCD gain register. Such an investigation has the potential to explain certain observed performance characteristics, as well as inform further optimisations to their operation. In this study, the results from simulation of charge transfer within an EMCCD gain register element are discussed with a specific focus on the implications for serial charge transfer efficiency (CTE). The effects of operating voltage and readout speed are explored in context with typical operating conditions. It is shown that during transfer, a small portion of signal charge may become trapped at the semiconductor-insulator interface that could act to degrade the serial CTE in certain operating conditions.

  6. Internal electron transfer in cytochrome c oxidase from Rhodobacter sphaeroides.

    Science.gov (United States)

    Adelroth, P; Brzezinski, P; Malmström, B G

    1995-03-01

    Absorbance changes following CO dissociation by flash photolysis from mixed-valence aa3 cytochrome oxidase from Rhodobacter sphaeroides have been followed in the Soret and alpha regions. They reflect internal electron transfer in the partially reduced enzyme, and the kinetics of the reactions has been determined. As with the bovine enzyme, three kinetic phases are found with relaxation time constants at neutral pH of about 3 microseconds, 35 microseconds, and 1 ms. The first reaction phase represents electron transfer from cytochrome a3 to cytochrome a, and the extent of this reaction is about 3 times larger compared to the bovine enzyme. The energetics of the reaction has been analyzed on the basis of measurements of its temperature dependence. The reorganization energy is close to 120 kJ mol-1, and it is suggested that this rather high value is the result of changes in solvation at the cytochrome a3-CuB site. The subsequent electron transfer between cytochrome a and CuA, with a time constant of 35 microseconds, is almost activationless and has a very low reorganization energy. The final phase, with a time constant close to 1 ms at neutral pH, represents a further shift in the equilibrium between cytochrome a3 and cytochrome a, and it is limited by proton-transfer reactions. The pKa values of the groups involved are significantly shifted in the bacterial oxidase compared to the bovine one. The total extent of electron transfer in the three backflow reactions has also been determined by a comparison of the CO-recombination rates in the mixed-valence and fully reduced enzymes.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7893697

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

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Chang, Po-Yao

    2012-01-01

    Smell is a vital sense for animals. The mainstream explanation of smell is based on recognition of the odorant molecules through characteristics of their surface, e.g., shape, but certain experiments suggest that such recognition is complemented by recognition of vibrational modes. According 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 dimensions. In the present paper we introduce the vibrationally assisted mechanism of olfaction and demonstrate for several odorants that, indeed, a strong enhancement of an electron tunneling rate due to odorant vibrations can arise. We discuss in this regard the influence of odorant deuteration and explain, 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 homology modeling.

  8. Electron transfer mechanisms of DNA repair by photolyase.

    Science.gov (United States)

    Zhong, Dongping

    2015-04-01

    Photolyase is a flavin photoenzyme that repairs two DNA base damage products induced by ultraviolet (UV) light: cyclobutane pyrimidine dimers and 6-4 photoproducts. With femtosecond spectroscopy and site-directed mutagenesis, investigators have recently made significant advances in our understanding of UV-damaged DNA repair, and the entire enzymatic dynamics can now be mapped out in real time. For dimer repair, six elementary steps have been characterized, including three electron transfer reactions and two bond-breaking processes, and their reaction times have been determined. A unique electron-tunneling pathway was identified, and the critical residues in modulating the repair function at the active site were determined. The dynamic synergy between the elementary reactions for maintaining high repair efficiency was elucidated, and the biological nature of the flavin active state was uncovered. For 6-4 photoproduct repair, a proton-coupled electron transfer repair mechanism has been revealed. The elucidation of electron transfer mechanisms and two repair photocycles is significant and provides a molecular basis for future practical applications, such as in rational drug design for curing skin cancer. PMID:25830375

  9. Electron transfer, decoherence, and protein dynamics: insights from atomistic simulations.

    Science.gov (United States)

    Narth, Christophe; Gillet, Natacha; Cailliez, Fabien; Lévy, Bernard; de la Lande, Aurélien

    2015-04-21

    Electron transfer in biological systems drives the processes of life. From cellular respiration to photosynthesis and enzymatic catalysis, electron transfers (ET) are chemical processes on which essential biological functions rely. Over the last 40 years, scientists have sought understanding of how these essential processes function in biology. One important breakthrough was the discovery that Marcus theory (MT) of electron transfer is applicable to biological systems. Chemists have experimentally collected both the reorganization energies (?) and the driving forces (?G°), two parameters of Marcus theory, for a large variety of ET processes in proteins. At the same time, theoretical chemists have developed computational approaches that rely on molecular dynamics and quantum chemistry calculations to access numerical estimates of ? and ?G°. Yet another crucial piece in determining the rate of an electron transfer is the electronic coupling between the initial and final electronic wave functions. This is an important prefactor in the nonadiabatic rate expression, since it reflects the probability that an electron tunnels from the electron donor to the acceptor through the intervening medium. The fact that a protein matrix supports electron tunneling much more efficiently than vacuum is now well documented, both experimentally and theoretically. Meanwhile, many chemists have provided examples of the rich physical chemistry that can be induced by protein dynamics. This Account describes our studies of the dynamical effects on electron tunneling. We present our analysis of two examples of natural biological systems through MD simulations and tunneling pathway analyses. Through these examples, we show that protein dynamics sustain efficient tunneling. Second, we introduce two time scales: ?coh and ?FC. The former characterizes how fast the electronic coupling varies with nuclear vibrations (which cause dephasing). The latter reflects the time taken by the system to leave the crossing region. In the framework of open quantum systems, ?FC is a short time approximation of the characteristic decoherence time of the electronic subsystem in interaction with its nuclear environment. The comparison of the respective values of ?coh and ?FC allows us to probe the occurrence of non-Condon effects. We use ab initio MD simulations to analyze how decoherence appears in several biological cofactors. We conclude that we cannot account for its order of magnitude by considering only the atoms or bonds directly concerned with the transfer. Decoherence results from contributions from all atoms of the system appearing with a time delay that increases with the distance from the primarily concerned atoms or bonds. The delay and magnitude of the contributions depend on the chemical nature of the system. Finally, we present recent developments based on constrained DFT for efficient and accurate evaluations of the electronic coupling in ab initio MD simulations. These are promising methods to study the subtle fluctuations of the electronic coupling and the mechanisms of electronic decoherence in biological systems. PMID:25730126

  10. Structures of protein-protein complexes involved in electron transfer.

    Science.gov (United States)

    Antonyuk, Svetlana V; Han, Cong; Eady, Robert R; Hasnain, S Samar

    2013-04-01

    Electron transfer reactions are essential for life because they underpin oxidative phosphorylation and photosynthesis, processes leading to the generation of ATP, and are involved in many reactions of intermediary metabolism. Key to these roles is the formation of transient inter-protein electron transfer complexes. The structural basis for the control of specificity between partner proteins is lacking because these weak transient complexes have remained largely intractable for crystallographic studies. Inter-protein electron transfer processes are central to all of the key steps of denitrification, an alternative form of respiration in which bacteria reduce nitrate or nitrite to N2 through the gaseous intermediates nitric oxide (NO) and nitrous oxide (N2O) when oxygen concentrations are limiting. The one-electron reduction of nitrite to NO, a precursor to N2O, is performed by either a haem- or copper-containing nitrite reductase (CuNiR) where they receive an electron from redox partner proteins a cupredoxin or a c-type cytochrome. Here we report the structures of the newly characterized three-domain haem-c-Cu nitrite reductase from Ralstonia pickettii (RpNiR) at 1.01?Å resolution and its M92A and P93A mutants. Very high resolution provides the first view of the atomic detail of the interface between the core trimeric cupredoxin structure of CuNiR and the tethered cytochrome c domain that allows the enzyme to function as an effective self-electron transfer system where the donor and acceptor proteins are fused together by genomic acquisition for functional advantage. Comparison of RpNiR with the binary complex of a CuNiR with a donor protein, AxNiR-cytc551 (ref. 6), and mutagenesis studies provide direct evidence for the importance of a hydrogen-bonded water at the interface in electron transfer. The structure also provides an explanation for the preferential binding of nitrite to the reduced copper ion at the active site in RpNiR, in contrast to other CuNiRs where reductive inactivation occurs, preventing substrate binding. PMID:23535590

  11. 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. PMID:25224924

  12. Electron transfer and projectile excitation in single collisions

    International Nuclear Information System (INIS)

    Studies of electron transfer (capture) and projectile excitation together in a single encounter are reviewed. This combined capture and excitation can result from either a correlated or an uncorrelated interaction. The correlated process is referred to as resonant transfer and excitation (RTE), while the uncorrelated process is called nonresonant transfer and excitation (NTE). RTE is analogous to dielectronic recombination (DR) which occurs in the interaction between an ion and a free electron. Experimental and theoretical works leading to establishing the existence of RTE are reviewed as well as considerations relevant to distinguishing RTE from NTE. The dependences of RTE on projectile atomic number (14 ? Z ? 23) for Li-like ions, and on projectile charge state for H-like to Ne-like ions have been measured and compared with theory. The effect of the target electron momentum distribution on RTE has been demonstrated by comparing measurements for H2 and He targets. Measurements of RTE involving L-shell excitation have been conducted and compared with K-shell results. All of the measured RTE cross sections to date for H2 and He targets are in reasonable agreement with calculations based on theoretical DR cross sections averaged over the target electron momentum distribution; however, systematic discrepancies between experiment and theory exist. Additionally, is has been found that RTE can contribute considerably to total single-electron capturerably to total single-electron capture cross sections in the region where RTE is important, accounting for nearly half of the total capture events for calcium ions colliding with H2. (orig.)

  13. Electron Transfer in DNA through magnetic bound states

    CERN Document Server

    Cox, D L; Pati, S K

    2000-01-01

    Electron transfer (ET) via quantum mechanical tunneling between well separated donor (D) and acceptor (A) complexes is part of such biological processes as respiration, photosynthesis, and possibly DNA repair or damage. Data and theory for ET in proteins give a typical tunneling length of 0.1 nm. In contrast, fluorescence quenching in DNA at D/A distances of 4 nm or more suggests ET with tunneling lengths of order 1 nm. We show how such long ranged ET can be mediated by rapidly forming magnetic Kondo bound states (KS) arising from: (1) strong electron interactions and magnetic moments on D and/or A complexes satisfying suitable energy requirements, and (2) "quantum deconfinement" of electrons through extended bridge molecular orbitals. Realistic long range Coulomb interaction strengths between bridge electrons and localized D/A charges modestly enhance these ET rates.

  14. Nile blue can photosensitize DNA damage through electron transfer.

    Science.gov (United States)

    Hirakawa, Kazutaka; Ota, Kazuhiro; Hirayama, Junya; Oikawa, Shinji; Kawanishi, Shosuke

    2014-04-21

    The mechanism of DNA damage photosensitized by Nile blue (NB) was studied using (32)P-5'-end-labeled DNA fragments. NB bound to the DNA strand was possibly intercalated through an electrostatic interaction. Photoirradiated NB caused DNA cleavage at guanine residues when the DNA fragments were treated with piperidine. Consecutive guanines, the underlined G in 5'-GG and 5'-GGG, were selectively damaged through photoinduced electron transfer. The fluorescence lifetime of NB was decreased by guanine-containing DNA sequence, supporting this mechanism. Single guanines were also slightly damaged by photoexcited NB, and DNA photodamage by NB was slightly enhanced in D2O. These results suggest that the singlet oxygen mechanism also partly contributes to DNA photodamage by NB. DNA damage photosensitized by NB via electron transfer may be an important mechanism in medicinal applications of photosensitizers, such as photodynamic therapy in low oxygen. PMID:24576317

  15. Solvation-induced one-dimensional polarons and electron transfer.

    Science.gov (United States)

    Ussery, G L; Gartstein, Yu N

    2010-04-28

    When a one-dimensional (1D) semiconductor nanostructure is immersed in a sluggish polar solvent, fluctuations of the medium may result in the appearance of localized electronic levels inside the band gap. An excess charge carrier can occupy such a level and undergo self-localization into a large-radius adiabatic polaron surrounded by a self-consistent medium polarization pattern. Within an appropriately adapted framework of the Marcus theory, we explore the description and qualitative picture of thermally activated electron transfer involving solvation-induced polaroniclike states by considering transfer between small and 1D species as well as between two 1D species. Illustrative calculations are performed for tubular geometries with possible applications to carbon nanotube systems. PMID:20441283

  16. Solvation-induced one-dimensional polarons and electron transfer

    CERN Document Server

    Ussery, G L

    2009-01-01

    When a one-dimensional (1D) semiconductor nanostructure is immersed in a sluggish polar solvent, fluctuations of the medium may result in the appearance of localized electronic levels inside the band gap. An excess charge carrier can occupy such a level and undergo self-localization into a large-radius adiabatic polaron surrounded by a self-consistent medium polarization pattern. Within an appropriately adapted framework of the Marcus theory, we explore the description and qualitative picture of thermally activated electron transfer involving solvation-induced polaronic-like states by considering transfer between small and 1D species as well as between two 1D species. Illustrative calculations are performed for tubular geometries with possible applications to carbon nanotube systems.

  17. Polarization-transfer electron-Zeeman resolved EPR

    Science.gov (United States)

    Eichel, Rüdiger-A.; Schweiger, Arthur

    2002-05-01

    Polarization-transfer electron-Zeeman resolved (EZ) EPR is introduced. In this two-dimensional pulse EPR method, which is based on the stimulated-echo sequence, the magnetic field is changed during the pulse sequence by applying a sinusoidal field of variable amplitude. EZ-EPR can be used to improve the spectral resolution of disordered systems with g anisotropy or to separate overlapping spectra of sites with different g values in single-crystal EPR studies. A theoretical description of the method is given, and model calculations as well as experiments on disordered systems with anisotropic electron Zeeman interactions are presented.

  18. Strongly enhanced backward emission of electrons in transfer and ionization.

    Science.gov (United States)

    Schulz, M; Wang, X; Gundmundsson, M; Schneider, K; Kelkar, A; Voitkiv, A B; Najjari, B; Schöffler, M; Schmidt, L Ph H; Dörner, R; Ullrich, J; Moshammer, R; Fischer, D

    2012-01-27

    We studied three-dimensional angular distributions and longitudinal momentum spectra of electrons ejected in transfer plus ionization (TI), i.e., the ejection of one and the capture of a second target electron, for ion-helium collisions. We observe a pronounced structure strongly focused opposite to the projectile beam direction, which we associate with a new correlated TI mechanism proposed recently. This process contributes significantly to the total cross sections over a broad range of perturbations ?, even at ? as large as 0.5, where uncorrelated TI mechanisms were thought to be dominant. PMID:22400839

  19. Photoinduced electron transfer from phenanthrimidazole to magnetic nanoparticles.

    Science.gov (United States)

    Jayabharathi, J; Arunpandiyan, A; Thanikachalam, V; Ramanathan, P

    2015-01-01

    The dynamics of photoinduced electron injection from (E)-1-(4-methoxyphenyl)-2-styryl-1H-phenanthro [9,10-d]imidazole (MPSPI) synthesised using nano TiO2 as catalyst to Fe2O3 nanocrystal has been studied by FT-IR, absorption, fluorescence and lifetime spectroscopic methods. The binding between nanoparticle and MPSPI is confirmed by binding constant and binding site. The distance between MPSPI and nanoparticle as well as the critical energy transfer distance has been obtained. The free energy change (?Get) for electron injection has also been deduced. PMID:25591997

  20. Microscopic solvation dynamics and solvent-controlled electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Rips, I.; Klafter, J.; Jortner, J. (Tel Aviv Univ. (Israel))

    1990-11-15

    In this paper the authors investigate solvent size effects on solvent-controlled electron transfer (ET) in polar liquids. An interrelationship was established between the solvation time correlation function and the ET rate, which was presented within the first passage time approximation. For the case of activationless ET the ET rate, which is equal to the initial solvation rate, was expressed within the framework of the mean spherical approximation. The theory predicts that the activationless ET times are shorter than the average dipole solvation times, in accord with experimental data for intramolecular ET in electronically excited bianthryl in nonassociated polar solvents.

  1. Probing concerted proton–electron transfer in phenol–imidazoles

    OpenAIRE

    Markle, Todd F.; Rhile, Ian J.; Dipasquale, Antonio G.; Mayer, James M.

    2008-01-01

    A series of seven substituted 4,6-di-tert-butyl-2-(4,5-diarylimidazolyl)-phenols have been prepared and characterized, along with two related benzimidazole compounds. X-ray crystal structures of all of the compounds show that the phenol and imidazole rings are close to coplanar and are connected by an intramolecular ArOH?N hydrogen bond. One-electron oxidation of these compounds occurs with movement of the phenolic proton to the imidazole base by concerted proton–electron transfer (CPET) ...

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

    International Nuclear Information System (INIS)

    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. 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.

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

    OpenAIRE

    Solov’yov, Ilia A.; Chang, Po-yao; Schulten, Klaus

    2012-01-01

    Smell is a vital sense for animals. The mainstream explanation of smell is based on recognition of the odorant molecules through characteristics of their surface, e.g., shape, but certain experiments suggest that such recognition is complemented by recognition of vibrational modes. According 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 recogniz...

  5. Intramolecular electron transfer in single-site-mutated azurins

    DEFF Research Database (Denmark)

    Farver, O; Skov, L K

    1993-01-01

    Single-site mutants of the blue, single-copper protein, azurin, from Pseudomonas aeruginosa were reduced by CO2- radicals in pulse radiolysis experiments. The single disulfide group was reduced directly by CO2- with rates similar to those of the native protein [Farver, O., & Pecht, I. (1989) Proc. Natl. Acad. Sci. U.S.A. 86, 6968-6972]. The RSSR- radical produced in the above reaction was reoxidized in a slower intramolecular electron-transfer process (30-70 s-1 at 298 K) concomitant with a further reduction of the Cu(II) ion. The temperature dependence of the latter rates was determined and used to derive information on the possible effects of the mutations. The substitution of residue Phe114, situated on the opposite side of Cu relative to the disulfide, by Ala resulted in a rate increase by a factor of almost 2. By assuming that this effect is only due to an increase in driving force, lambda = 135 kJ mol-1 for the reorganization energy was derived. When Trp48, situated midway between the donor and the acceptor, was replaced by Leu or Met, only a small change in the rate of intramolecular electron transfer was observed, indicating that the aromatic residue in this position is apparently only marginally involved in electron transfer in wild-type azurin. Pathway calculations also suggest that a longer, through-backbone path is more efficient than the shorter one involving Trp48. The former pathway yields an exponential decay factor, beta, of 6.6 nm-1. Another mutation, raising the electron-transfer driving force, was produced by changing the Cu ligand Met121 to Leu, which increases the reduction potential by 100 mV.(ABSTRACT TRUNCATED AT 250 WORDS)

  6. [Electron transfer, ionization and excitation in atomic collisions

    International Nuclear Information System (INIS)

    The research being carried out at Penn State by Winter and Alston addresses the fundamental atomic-collision processes of electron transfer, ionization, and excitation. Winter has focussed attention on intermediate and, more recently, higher collision energies -- proton energies of at least about 50 keV -- for which coupled-state approaches are appropriate. Alston has concentrated on perturbative approaches to symmetric ion-ion/atom collisions at high energies and to asymmetric collisions at intermediate to high energies

  7. Structures of Protein-Protein Complexes involved in electron transfer

    OpenAIRE

    Antonyuk, Svetlana V.; Cong, Han; Eady, Robert R.; Hasnain, S. Samar

    2013-01-01

    Electron transfer (ET) reactions are essential for life since they underpin oxidative phosphorylation and photosynthesis, processes leading to the generation of ATP, and are involved in many reactions of intermediary metabolism1. Key to these roles is the formation of transient inter-protein ET complexes. The structural basis for the control of specificity between partner proteins is lacking since these weak transient complexes have remained largely intractable for crystallographic studies2,3...

  8. Electron transfer at sensitized TiO/sub 2/ electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Spitler, M.T.; Calvin, M.

    1977-05-15

    Electron transfer from the excited state of tetra-iodo, tetra-chloro fluorescein (rose bengal) to the conduction band of TiO/sub 2/ has been studied through photoelectrochemical techniques. The measured transfer rate was correlated with information from absorbance and adsorption measurements of this dye molecule on the (001) surface of the single crystals used as electrodes. The quantum efficiency for the photoinjection of electrons was determined to be 4.0 x 10/sup -3/ independent of the pH of the electrolyte and the dye surface concentration. With these data, an argument is given supporting the existence of excitation transfer among the dye molecules on the surface. A temperature study of the electron transfer efficiency yielded an activation enthalpy of 3.2 +- 0.3 kcal/mole with a pre-exponential factor of 1.0. A heat of adsorption of 7.6 +- 0.5 kcal/mole for this dye on TiO/sub 2/ single crystals was derived from analysis of adsorption isotherms measured at 21.5 and 36.5degreeC. In addition to the photo-oxidation process, a photoreduction was also observed upon cathodic polarization of the semiconductor. Action spectra revealed participation of solution dye molecules in this reaction; the reduction rate is dependent upon oxygen concentration in solution. It was concluded that the oxidized dye in solution accepts an electron from the TiO/sub 2/ to generate this current. This photoreduction was found with triphenylmethane and thiazine dyes as well as with other fluorescein derivatives.

  9. Intermittent Single-Molecule Interfacial Electron Transfer Dynamics

    International Nuclear Information System (INIS)

    We report on single molecule studies of photosensitized interfacial electron transfer (ET) processes in Coumarin 343 (C343)-TiO2 nanoparticle (NP) and Cresyl Violet (CV+)-TiO2 NP systems, using time-correlated single photon counting coupled with scanning confocal fluorescence microscopy. Fluorescence intensity trajectories of individual dye molecules adsorbed on a semiconductor NP surface showed fluorescence fluctuations and blinking, with time constraints distributed from sub-milliseconds to several seconds

  10. Intermittent Single-Molecule Interfacial Electron Transfer Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Biju, Vasudevan P.; Micic, Miodrag; Hu, Dehong; Lu, H. Peter

    2004-08-04

    We report on single molecule studies of photosensitized interfacial electron transfer (ET) processes in Coumarin 343 (C343)-TiO2 nanoparticle (NP) and Cresyl Violet (CV+)-TiO2 NP systems, using time-correlated single photon counting coupled with scanning confocal fluorescence microscopy. Fluorescence intensity trajectories of individual dye molecules adsorbed on a semiconductor NP surface showed fluorescence fluctuations and blinking, with time constrants distributed from sub-milliseconds to several seconds.

  11. Electron transfer reactions on small CdSe colloids

    International Nuclear Information System (INIS)

    Colloidal CdSe particles were investigated by both laser flash photolysis and pulse radiolysis. Electron transfer reactions were observed from each technique. Transient absorption attributed to trapped excess charge and formation of Cd+ and Se- sites was detected during the laser photolysis. Transient absorption was again detected during pulse radiolysis of the aqueous solution. In the latter case the trapped excess charge is reduced to Cd0 in short order

  12. 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...

  13. 41 CFR 102-118.70 - Must my agency make all payments via electronic funds transfer?

    Science.gov (United States)

    2010-07-01

    ...agency make all payments via electronic funds transfer? 102-118...agency make all payments via electronic funds transfer? Yes...must make all payments for goods and services via EFT (this includes goods and services ordered...

  14. 77 FR 34127 - Financial Management Service; Proposed Collection of Information: Electronic Transfer Account...

    Science.gov (United States)

    2012-06-08

    ...Fiscal Service Financial Management Service; Proposed Collection...Electronic Transfer Account (ETA) Financial Agency...Agreement AGENCY: Financial Management Service, Fiscal Service...notice, the Financial Management Service solicits comments...Electronic Transfer Account (ETA) Financial...

  15. Low activation barriers characterize intramolecular electron transfer in ascorbate oxidase

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1992-01-01

    Anaerobic reduction kinetics of the zucchini squash ascorbate oxidase (AO; L-ascorbate:oxygen oxidoreductase, EC 1.10.3.3) by pulse radiolytically produced CO2- radical ions were investigated. Changes in the absorption bands of type 1 [Cu(II)] (610 nm) and type 3 [Cu(II)] (330 nm) were monitored over a range of reactant concentrations, pH, and temperature. The direct bimolecular reduction of type 1 [Cu(II)] [(1.2 +/- 0.2) x 10(9) M-1.s-1] was followed by its subsequent reoxidation in three distinct phases, all found to be unimolecular processes with the respective specific rates of 201 +/- 8, 20 +/- 4, and 2.3 +/- 0.2 s-1 at pH 5.5 and 298 K. While at this pH no direct bimolecular reduction was resolved in the 330-nm band, at pH 7.0 such a direct process was observed [(6.5 +/- 1.2) x 10(8) M-1.s-1]. In the same slower time domains where type 1 [Cu(I)] reoxidation was monitored, reduction of type 3 [Cu(II)] was observed, which was also concentration independent and with identical rate constants and amplitudes commensurate with those of type 1 [Cu(II)] reoxidation. These results show that after electron uptake by type 1 [Cu(II)], its reoxidation takes place by intramolecular electron transfer to type 3 [Cu(II)]. The observed specific rates are similar to values reported for the limiting-rate constants of AO reduction by excess substrate, suggesting that internal electron transfer is the rate-determining step of AO activity. The temperature dependence of the intramolecular electron transfer rate constants was measured from 275 to 308 K at pH 5.5 and, from the Eyring plots, low activation enthalpies were calculated--namely, 9.1 +/- 1.1 and 6.8 +/- 1.0 kJ.mol-1 for the fastest and slowest phases, respectively. The activation entropies observed for these respective phases were -170 +/- 9 and -215 +/- 16 J.K-1.mol-1. The exceptionally low enthalpy barriers imply the involvement of highly optimized electron transfer pathways for internal electron transfer.

  16. Electron transfer to covalently immobilized Keggin polyoxotungstates on gold.

    Science.gov (United States)

    Yaqub, Mustansara; Walsh, James J; Keyes, Tia E; Proust, Anna; Rinfray, Corentin; Izzet, Guillaume; McCormac, Timothy; Forster, Robert J

    2014-04-22

    Spontaneously adsorbed monolayers have been formed on gold electrodes using a Keggin polyoxotungstate with covalently attached alkanethiol linkers of two different lengths. Films of both polyoxotungstates show two well-defined reduction processes associated with the polyoxotungstate centers where the ionic liquid, [BMIM][BF4], acts as supporting electrolyte. The surface coverages are both less than that expected for a close-packed monolayer. For the short and long linkers, the voltammetric response can be described in terms of the Butler-Volmer response involving a surface confined species using standard heterogeneous electron transfer rate constants of 170 and 140 s(-1) for the first reduction and 150 and 100 s(-1) for the second reduction processes, respectively. The rate of electron transfer to a solution phase redox probe, ferrocyanide, is significantly more sensitive to the length of the linker than the rate of electron transfer to the tungstate centers. This behavior probably arises due to potential-induced changes in the film structure. PMID:24670101

  17. Nanoparticle facilitated extracellular electron transfer in microbial fuel cells.

    Science.gov (United States)

    Jiang, Xiaocheng; Hu, Jinsong; Lieber, Alexander M; Jackan, Charles S; Biffinger, Justin C; Fitzgerald, Lisa A; Ringeisen, Bradley R; Lieber, Charles M

    2014-11-12

    Microbial fuel cells (MFCs) have been the focus of substantial research interest due to their potential for long-term, renewable electrical power generation via the metabolism of a broad spectrum of organic substrates, although the low power densities have limited their applications to date. Here, we demonstrate the potential to improve the power extraction by exploiting biogenic inorganic nanoparticles to facilitate extracellular electron transfer in MFCs. Simultaneous short-circuit current recording and optical imaging on a nanotechnology-enabled platform showed substantial current increase from Shewanella PV-4 after the formation of cell/iron sulfide nanoparticle aggregates. Detailed characterization of the structure and composition of the cell/nanoparticle interface revealed crystalline iron sulfide nanoparticles in intimate contact with and uniformly coating the cell membrane. In addition, studies designed to address the fundamental mechanisms of charge transport in this hybrid system showed that charge transport only occurred in the presence of live Shewanella, and moreover demonstrated that the enhanced current output can be attributed to improved electron transfer at cell/electrode interface and through the cellular-networks. Our approach of interconnecting and electrically contacting bacterial cells through biogenic nanoparticles represents a unique and promising direction in MFC research and has the potential to not only advance our fundamental knowledge about electron transfer processes in these biological systems but also overcome a key limitation in MFCs by constructing an electrically connected, three-dimensional cell network from the bottom-up. PMID:25310721

  18. Photoinduced electron transfer in singly labeled thiouredopyrenetrisulfonate azurin derivatives

    DEFF Research Database (Denmark)

    Borovok, N; Kotlyar, A B

    1999-01-01

    A novel method for the initiation of intramolecular electron transfer reactions in azurin is reported. The method is based on laser photoexcitation of covalently attached thiouredopyrenetrisulfonate (TUPS), the reaction that generates the low potential triplet state of the dye with high quantum 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(II) and the back reaction from Cu(I) to the oxidized dye. For all singly labeled derivatives, the rate constants of copper ion reduction were one or two orders of magnitude larger than for its reoxidation, consistent with the larger thermodynamic driving force for the former process. Using 3-D coordinates 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 rate constants of Cu(II) reduction.

  19. Electron and energy transfer in artificial photosynthesis supermolecules

    Science.gov (United States)

    Kuciauskas, Darius

    1999-12-01

    Photophysical properties of a variety of organic supermolecules were studied in order to elucidate structural and thermodynamic criteria pertinent to the design of artificial photosynthetic structures and molecular electronic devices. These supermolecules were designed using covalently linked porphyrins, carotenoids, C60 fullerenes, quinones, and aromatic imide chromophores. Time-resolved absorption and fluorescence spectroscopy on a femtosecond to millisecond time scale was used to investigate mechanisms of photoinduced electron transfer, singlet and triplet energy transfer, and radical pair dynamics. Several photophysical processes, previously found only in photosynthetic reaction centers, were observed and characterized for the first time in these artificial systems. Molecular dyads, triads, and a hexad were shown to form long-lived charge separated states with high quantum yields, thus efficiently converting electronic excited state energy into (electro) chemical energy. These systems demonstrate that favorable photophysical properties can be conveniently (and predictably) controlled by changes in the molecular structure and the physical characteristics of the medium, such as the solvent polarity or temperature. Molecules studied in this work could be utilized as components of functional supramolecular assemblies. C60 fullerenes were shown to be preferable electron acceptors in molecular structures intended to function in a non-polar media or at low temperatures. This was attributed to the low intramolecular and solvent reorganization energies for C60 fullerenes. The magnetic field dependence of charge recombination in linked organic biradicals was studied. This effect can be used as the basis for a magnetically controlled molecular optical or optoelectronic switch (AND gate).

  20. DNA Damage Induced by Low-Energy Electrons: Electron Transfer and Diffraction

    International Nuclear Information System (INIS)

    Thin films of the short single strand of DNA, GCAT, in which guanine (G) or adenine (A) have been removed, were bombarded under vacuum by 4 to 15 eV electrons. The fragments corresponding to base release and strand breaks (SB) were analyzed by high performance liquid chromatography and their yields compared with those obtained from unmodified GCAT. From such a comparison, it is shown that, using GCAT as a model system (1) most SB result from electron capture by DNA bases followed by electron transfer to the phosphate group and (2) the initial capture probability depends on the coherence of the electron wave within the tetramer

  1. DNA Damage Induced by Low-Energy Electrons: Electron Transfer and Diffraction

    Science.gov (United States)

    Zheng, Yi; Wagner, J. Richard; Sanche, Léon

    2006-05-01

    Thin films of the short single strand of DNA, GCAT, in which guanine (G) or adenine (A) have been removed, were bombarded under vacuum by 4 to 15 eV electrons. The fragments corresponding to base release and strand breaks (SB) were analyzed by high performance liquid chromatography and their yields compared with those obtained from unmodified GCAT. From such a comparison, it is shown that, using GCAT as a model system, (1) most SB result from electron capture by DNA bases followed by electron transfer to the phosphate group and (2) the initial capture probability depends on the coherence of the electron wave within the tetramer.

  2. Charge amplification and transfer processes in the gas electron multiplier

    CERN Document Server

    Bachmann, S; Ropelewski, Leszek; Sauli, Fabio; Sharma, A; Mörmann, D

    1999-01-01

    We report the results of systematic investigations on the operating properties of detectors based on the gas electron multiplier (GEM). The dependence of gain and charge collection efficiency on the external fields has been studied in a range of values for the hole diameter and pitch. The collection efficiency of ionization electrons into the multiplier, after an initial increase, reaches a plateau extending to higher values of drift field the larger the GEM voltage and its optical transparency. The effective gain, fraction of electrons collected ba an electrode following the multiplier, increases almost linearly with the collection field, until entering a steeper parallel plate multiplication regime. The maximum effective gain attainable increases with the reduction in the hole diameter, stabilizing to a constant value at a diameter approximately corresponding to the foil thickness. Charge transfer properties appear to depend only on ratios of fields outside mad and the channels, with no interaction between ...

  3. 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.

  4. Quantum effects in adiabatic electrochemical electron-transfer reactions

    Science.gov (United States)

    Koper, M. T. M.; Mohr, J.-H.; Schmickler, W.

    1997-07-01

    The role of nuclear tunneling in adiabatic electrochemical electron-transfer reactions is studied by applying the WKB approximation and the Quantum Kramers Theory to the ground-state potential energy surface calculated from an extended Anderson-Newns Hamiltonian. Reorganization of both solvent and ligand modes is considered. In the limit of vanishing electronic coupling analytical formulas are obtained for the temperature dependence of the activation parameters, which are valid over a practically unlimited temperature range. In the limit of high temperature, they are shown to be identical to expression derived from the non-adiabatic Levich-Dogonadze theory. The effect of friction and non-vanishing electronic coupling are studied and both are found to suppress the relative contribution of the nuclear tunneling to the overall reaction rate.

  5. The reorganization energy of electron transfer in nonpolar solvents: Molecular level treatment of the solvent

    International Nuclear Information System (INIS)

    The intermolecular electron transfer in a solute pair consisting of pyrene and dimethylaniline is investigated in a nonpolar solvent, n-hexane. The earlier elaborated approach [M. Tachiya, J. Phys Chem. 97, 5911 (1993)] is used; this method provides a physically relevant background for separating inertial and inertialess polarization responses for both nonpolarizable and polarizable molecular level simulations. The molecular-dynamics technique was implemented for obtaining the equilibrium ensemble of solvent configurations. The nonpolar solvent, n-hexane, was treated in terms of OPLS-AA parametrization. Solute Lennard-Jones parameters were taken from the same parametrization. Solute charge distributions of the initial and final states were determined using ab initio level [HF/6-31G(d,p)] quantum-chemical calculations. Configuration analysis was performed explicitly taking into account the anisotropic polarizability of n-hexane. It is shown that the Gaussian law well describes calculated distribution functions of the solvent coordinate, therefore, the rate constant of the ET reaction can be characterized by the reorganization energy. Evaluated values of the reorganization energies are in a range of 0.03-0.11 eV and significant contribution (more then 40% of magnitude) comes from anisotropic polarizability. Investigation of the reorganization energy ? dependence on the solute pair separation distance d revealed unexpected behavior. The dependence has a very sharp peak or. The dependence has a very sharp peak at the distance d=7 A where solvent molecules are able to penetrate into the intermediate space between the solute pair. The reason for such behavior is clarified. This new effect has a purely molecular origin and cannot be described within conventional continuum solvent models

  6. Electron transfer reactions involving acridine and related compounds

    International Nuclear Information System (INIS)

    Acridine is rapidly reduced by e/sub sol/- (k = 3 x 1010 M-1 s-1) and by (CH3)2CO- (k = 3 x 109 M-1 s-1 in water and 1.4 x 109 M-1 s-1 in i-PrOH). Reduction by (CH3)2COH and CO2- is rapid and efficient only when the acridine is protonated (pK/sub a/ = 5.6). With neutral acridine, however, the slow reduction is accompanied by addition of these radicals to acridine. Both forms of acridine are reduced by pyridinyl radicals, although the acid more rapidly than the neutral form. In all these one-electron reductions the anion radical of acridine is produced, which in aqueous and alcoholic solutions undergoes rapid protonation on the nitrogen to form a neutral radical, with a pK/sub a/ apparently above 14. Related heterocyclic compounds, such as 1,10-phenanthroline and phenazine, behave in a similar fashion. The radicals produced by reduction of acridine and other heterocycles can transfer an electron to 9,10-anthraquinone in nonaqueous media or to anthraquinonesulfonate in aqueous solutions (k approx. 109 M-1 s-1). The spectra of the resulting semiquinone radicals were found, in all cases examined, to be identical with those obtained by direct reduction of the quinone under similar conditions without the intermediacy of the heterocycle. This is in contrast w of the heterocycle. This is in contrast with previous findings with a porphyrin-anthraqinone system. It is concluded that, despite the previous suggestion that an intermediate complex is formed upon electron transfer from tetraphenylporphyrin radical to anthraquinone, no such complex appears to be formed in the electron transfer reactions involving acridine and related heterocycles

  7. A structural basis of Equisetum arvense ferredoxin isoform II producing an alternative electron transfer with ferredoxin-NADP+ reductase.

    Science.gov (United States)

    Kurisu, Genji; Nishiyama, Daisuke; Kusunoki, Masami; Fujikawa, Shinobu; Katoh, Midori; Hanke, Guy Thomas; Hase, Toshiharu; Teshima, Keizo

    2005-01-21

    We have determined the crystal structure, at 1.2-A resolution, of Equisetum arvense ferredoxin isoform II (FdII), which lacks residues equivalent to Arg(39) and Glu(28) highly conserved among other ferredoxins (Fds). In other Fds these residues form an intramolecular salt bridge crucial for stabilization of the [2Fe-2S] cluster, which is disrupted upon complex formation with Fd-NADP(+) oxidoreductase (FNR) to form two intermolecular salt bridges. The overall structure of FdII resembles the known backbone structures of E. arvense isoform I (FdI) and other plant-type Fds. Dramatically, in the FdII structure a unique, alternative salt bridge is formed between Arg(22) and Glu(58). This results in a different relative orientation of the alpha-helix formed by Leu(23)-Glu(29) and eliminates the possibility of forming three of the five intermolecular salt bridges identified on formation of a complex between maize FdI and maize FNR. Mutation of FdII, informed by structural differences with FdI, showed that the alternative salt bridge and the absence of an otherwise conserved Tyr residue are important for the alternative stabilization of the FdII [2Fe-2S] cluster. We also investigated FdI and FdII electron transfer to FNR on chloroplast thylakoid membranes. The K(m) and V(max) values of FdII are similar to those of FdI, contrary to previous measurements of the reverse reaction, from FNR to Fd. The affinity between reduced FdI and oxidized FNR is much greater than that between oxidized FdI and reduced FNR, whereas this is not the case with FdII. The pH dependence of electron transfer by FdI, FdII, and an FdII mutant with FdI features was measured and further indicated that the binding mode to FNR differs between FdI and FdII. Based on this evidence, we hypothesize that binding modes with other Fd-dependent reductases may also vary between FdI and FdII. The structural differences between FdI and FdII therefore result in functional differences that may influence partitioning of electrons into different redox metabolic pathways. PMID:15513928

  8. Concerted proton-electron transfers: electrochemical and related approaches.

    Science.gov (United States)

    Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

    2010-07-20

    Proton-coupled electron transfers (PCETs) are omnipresent in natural and artificial chemical processes. Given the contemporary challenges associated with energy conversion, pollution abatement, and the development of high-performance sensors, a greater understanding of the mechanisms that underlie the practical efficiency of PCETs is a timely research topic. In contrast to hydrogen-atom transfers, proton and electron transfers involve different centers in PCET reactions. The reaction may go through an electron- or proton-transfer intermediate, giving rise to the electron-proton transfer (EPT) and the proton-electron transfer (PET) pathways. When the proton and electron transfers are concerted (the CPET pathway), the high-energy intermediates of the stepwise pathways are bypassed, although this thermodynamic benefit may have a kinetic cost. The primary task of kinetics-based mechanism analysis is therefore to distinguish the three pathways, quantifying the factors that govern the competition between them, which requires modeling of CPET reactivity. CPET models of varying sophistication have appeared, but the large number of parameters involved and the uncertainty of the quantum chemical calculations they may have to resort to make experimental confrontation and inspiration a necessary component of model testing and refinement. Electrochemical PCETs are worthy of particular attention, if only because most applications in which PCET mechanisms are operative involve collection or injection of electricity through electrodes. More fundamentally, changing the electrode potential is an easy and continuous means of varying the driving force of the reaction, whereas the current flowing through the electrode is a straightforward measure of its rate. Consequently, the current-potential response in nondestructive techniques (such as cyclic voltammetry) can be read as an activation-driving force relationship, provided the contribution of diffusion has been taken into account. Intrinsic properties (properties at zero driving force) are consequently a natural outcome of the electrochemical approach. In this Account, we begin by examining the modeling of CPET reactions and then describe illustrating experimental examples inspired by two biological systems, photosystem II and superoxide dismutase. One series of studies examined the oxidation of phenols with, as proton acceptor, either an attached nitrogen base or water (in water as solvent). Another addressed interconversion of aquo-hydroxo-oxo couples of transition metal complexes, using osmium complexes as prototypes. Finally, the reduction of superoxide ion, which is closely related to its dismutation, allowed the observation and rationalization of the remarkable properties of water as a proton donor. Water is also an exceptional proton acceptor in the oxidation of phenols, requiring very small reorganization energies, both in the electrochemical and homogeneous cases. These varied examples reveal general features of PCET reactions that may serve as guidelines for future studies, suggesting that research emphasis might be profitably directed toward new biological systems on the one hand and on the role of hydrogen bonding and hydrogen-bonded environments (such as water or proteins) on the other. PMID:20232879

  9. Electron-transfer reactions of tryptophan and tyrosine derivatives

    International Nuclear Information System (INIS)

    Oxidation of tryptophan, tyrosine, and derivatives by oxidizing radicals was studied by pulse radiolysis in aqueous solutions at 20 0C. Rate constants for the oxidation of tryptophan derivatives with .N3 and Br2-. radicals vary from 8 x 108 to 4.8 and 109 M-1 s-1 and oxidation goes to completion; no pH dependence was observed. Oxidation rate constants for tyrosine derivatives increase upon deprotonation of the phenolic residue at higher pH. Redox potentials for the indolyl and phenoxyl radicals were derived from the measured equilibrium constants by using p-methoxyphenol (E/sub 7.5/ = 0.6 and E13 = 0.4 V), bisulfite (E3 = 0.84 V), and guanosine (E7 = 0.91 V) redox couples as reference systems. Redox potentials of tryptophan derivatives were found to be in dependent on the nature of the side chain and higher than the redox potentials of tryptophan derivatives. Electron transfer from tyrosine to tryptophyl radical was found to be slow in neutral media and is suggested to proceed via multiple steps, one of which is proton transfer from tyrosine to tryptophyl radical followed by electron transfer. 26 references, 2 figures, 4 tables

  10. Angular momentum transfer and polarization degree of ions with one-valence electron by electron impact

    International Nuclear Information System (INIS)

    We carry out the R-matrix calculations for electron-impact excitations of ions with one valence electron. The integral cross sections and polarization degree are obtained for the excitation process from the ground state to the first 2P0 state of Li2+, B2+ and Al2+ as functions of electron incident energy. The differential cross sections and angular momentum transfer are also shown at non-resonant low-energy points. As for the angular momentum transfer (Lperpendicular) at small scattering angles, they are negative for B2+ and Al2+, while it is positive for Li2+. Thus Lperpendicular of doubly charged ions with one-valence electron is not simple.

  11. Experimental Proof of Resonant Auger Decay Driven Intermolecular Coulombic Decay

    Science.gov (United States)

    Trinter, F.; Schöffler, M. S.; Kim, H.-K.; Sturm, F.; Cole, K.; Neumann, N.; Vredenborg, A.; Williams, J.; Bocharova, I.; Guillemin, R.; Simon, M.; Belkacem, A.; Landers, A. L.; Weber, Th; Schmidt-Böcking, H.; Dörner, R.; Jahnke, T.

    2014-04-01

    Resonant Auger decay driven Intermolecular Coulombic Decay through synchrotron radiation in gas phase carbon monoxided dimers and nitrogen dimers has been studied. We report the first experiment where the low-energy ICD-electron has been measured in coincidence with the ionic fragments and Resonant Auger ICD has been proved experimentally.

  12. Ultrafast intramolecular electron transfer from a ferrocene donor moiety to a nile blue acceptor

    Science.gov (United States)

    Baigar, E.; Gilch, P.; Zinth, W.; Stöckl, M.; Härter, P.; von Feilitzsch, T.; Michel-Beyerle, M. E.

    2002-01-01

    The fastest electron transfer processes between molecular donor/acceptor systems have been observed for solvent to solute type reactions, where the number of solvent molecules participating could be high. This might explain the very short electron transfer times of ?100 fs observed. Here the photo-induced electron transfer in a bridged donor/acceptor system was studied by femtosecond pump-probe spectroscopy with a time resolution of 15 fs. After photoexcitation of the acceptor (nile blue) an electron is transferred from the donor (ferrocene) with a time constant of 90 fs, i.e. close to fastest electron transfer times in the solute/solvent systems.

  13. Theory of electron transfer in the presence of dissipation

    International Nuclear Information System (INIS)

    An analytic study of the density matrix and Wigner representation equations for dissipative electron transfer is presented. An explicit expression is derived for the off-diagonal Green's function, which shows a very fast relaxation in time if the barrier to reaction is greater than the thermal energy. This fast relaxation invalidates previous attempts to derive coupled equations for the density in the large friction limit. The fast off-diagonal relaxation disallows an adiabatic elimination of the momentum even in the large friction limit. We then show, with the aid of the boundary layer method, how one can use the same analysis to derive a set of two coupled equations for the diagonal densities. These equations are a generalization to phase space of the large friction Zusman equations [Chem. Phys. 49, 295 (1980)]. Adiabatic elimination of the momentum from these generalized Zusman equations is correct in the large friction limit and naturally leads back to the Zusman equations. Numerical solution of the generalized Zusman equations is presented for symmetric electron transfer for weak and strong electronic coupling, moderate and high barriers, and a large range of damping. The numerical results provide new insight into the friction dependence of the rate in the weak damping regime and show that previous analytic expressions for the rate are only qualitative in nature

  14. Modeling biofilms with dual extracellular electron transfer mechanisms

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-11-28

    Electrochemically active biofilms have a unique form of respiration in which they utilize solid external materials as their terminal electron acceptor for 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 components requisite for both mechanisms. In this study, a generic model is presented that incorporates both diffusion- and conduction-based mechanisms and allows electrochemically active biofilms to utilize both simultaneously. The model was applied to Shewanella oneidensis and Geobacter sulfurreducens biofilms using experimentally generated data found the literature. Our simulation results showed that 1) biofilms having both mechanisms available, especially if they can interact, may have metabolic advantage over biofilms that can use only a single mechanism; 2) the thickness of Geobacter 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 measurements and cannot be assumed to have identical values. Finally, we determined that cyclic and squarewave voltammetry are currently not good tools to determine the specific percentage of extracellular electron transfer mechanisms used by biofilms. The developed model will be a critical tool in designing experiments to explain EET mechanisms.

  15. Advances in Enhanced Boiling Heat Transfer From Electronic Components

    Science.gov (United States)

    Honda, Hiroshi; Wei, Jinjia

    This paper reviews recent advances in enhancing boiling heat transfer from electronic components immersed in dielectric liquids by use of surface microstructures. The microstructures developed include rough surfaces produced by sanding, vapor blasting hard particles, sputtering of SiO2 followed by wet etching of the surface, chemical vapor deposition of SiO2 film etc., laser-drilled cavities, a brush-like structure (dendritic structure), reentrant and micro-reentrant cavities, microfins, and porous structures fabricated by alumina particle spraying and painting of silver flakes, diamond particles, aluminum particles and copper particles. Heat sink studs with drilled holes, microfins, multi-layered micro-channels and pores, and pin fins with and without microporous coating have also been developed. The height of microstructure ranges from 0 to 12mm. The primary issues discussed are the mitigation of temperature overshoot at boiling incipience, enhancement of nucleate boiling heat transfer and increasing the critical heat flux.

  16. Single Electron Transfer Living Radical Polymerization via a New Initiator

    Science.gov (United States)

    Bai, Xiongxiong; Hu, Ying; Zhang, Xu; Ai, Lingling; Cheng, Chuanjie

    2014-08-01

    Research and development of novel initiating system such as single electron transfer living radical polymerization (SET-LRP) is of high importance in polymer chemistry. A new SET-LRP initiator was synthesized and applied to prepare end-functionalized poly(methyl methacrylate) (PMMA) in this study. ?-Trichloromethyl benzyl alcohol was firstly synthesized, followed by preparation of PMMA under SET-LRP conditions. Conversion of MMA was 81.9%, and the molecular weight of PMMA was about 2.5 kDa at 60 °C for 1 h. Consistency of the number-average molecular weight of PMMA from NMR, GPC and theoretical calculation indicated that the polymerization featured controllable property. Broad molecular weight distribution (MWD) may be ascribed to branched polymers formed by initiation and chain transfer.

  17. Covalent electron transfer chemistry of graphene with diazonium salts.

    Science.gov (United States)

    Paulus, Geraldine L C; Wang, Qing Hua; Strano, Michael S

    2013-01-15

    Graphene is an atomically thin, two-dimensional allotrope of carbon with exceptionally high carrier mobilities, thermal conductivity, and mechanical strength. From a chemist's perspective, graphene can be regarded as a large polycyclic aromatic molecule and as a surface without a bulk contribution. Consequently, chemistries typically performed on organic molecules and surfaces have been used as starting points for the chemical functionalization of graphene. The motivations for chemical modification of graphene include changing its doping level, opening an electronic band gap, charge storage, chemical and biological sensing, making new composite materials, and the scale-up of solution-processable graphene. In this Account, we focus on graphene functionalization via electron transfer chemistries, in particular via reactions with aryl diazonium salts. Because electron transfer chemistries depend on the Fermi energy of graphene and the density of states of the reagents, the resulting reaction rate depends on the number of graphene layers, edge states, defects, atomic structure, and the electrostatic environment. We limit our Account to focus on pristine graphene over graphene oxide, because free electrons in the latter are already bound to oxygen-containing functionalities and the resulting chemistries are dominated by localized reactivity and defects. We describe the reaction mechanism of diazonium functionalization of graphene and show that the reaction conditions determine the relative degrees of chemisorption and physisorption, which allows for controlled modulation of the electronic properties of graphene. Finally we discuss different applications for graphene modified by this chemistry, including as an additive in polymer matrices, as biosensors when coupled with cells and biomolecules, and as catalysts when combined with nanoparticles. PMID:22946516

  18. Comparison of dynamical aspects of nonadiabatic electron, proton, and proton-coupled electron transfer reactions

    International Nuclear Information System (INIS)

    The dynamical aspects of a model proton-coupled electron transfer (PCET) reaction in solution are analyzed with molecular dynamics simulations. The rate for nonadiabatic PCET is expressed in terms of a time-dependent probability flux correlation function. The impact of the proton donor-acceptor and solvent dynamics on the probability flux is examined. The dynamical behavior of the probability flux correlation function is dominated by a solvent damping term that depends on the energy gap correlation function. The proton donor-acceptor motion does not impact the dynamical behavior of the probability flux correlation function but does influence the magnitude of the rate. The approximations previously invoked for the calculation of PCET rates are tested. The effects of solvent damping on the proton donor-acceptor vibrational motion are found to be negligible, and the short-time solvent approximation, in which only equilibrium fluctuations of the solvent are considered, is determined to be valid for these types of reactions. The analysis of PCET reactions is compared to previous analyses of single electron and proton transfer reactions. The dynamical behavior is qualitatively similar for all three types of reactions, but the time scale of the decay of the probability flux correlation function is significantly longer for single proton transfer than for PCET and single electron transfer due to a smaller solvent reorganization energy for proton transferfor proton transfer

  19. Transcriptomic and Genetic Analysis of Direct Interspecies Electron Transfer

    Science.gov (United States)

    Rotaru, Amelia-Elena; Summers, Zarath M.; Shrestha, Minita; Liu, Fanghua; Lovley, Derek R.

    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 electron-accepting partner for either Geobacter metallireducens, which performs DIET, or Pelobacter carbinolicus, which relies on HIT. Transcript abundance for G. sulfurreducens uptake hydrogenase genes was 7-fold lower in cocultures with G. metallireducens than in cocultures with P. carbinolicus, consistent with DIET and HIT, respectively, in the two cocultures. Transcript abundance for the pilus-associated cytochrome OmcS, which is essential for DIET but not for HIT, was 240-fold higher in the cocultures with G. metallireducens than in cocultures with P. carbinolicus. The pilin gene pilA was moderately expressed despite a mutation that might be expected to repress pilA expression. Lower transcript abundance for G. sulfurreducens genes associated with acetate metabolism in the cocultures with P. carbinolicus was consistent with the repression of these genes by H2 during HIT. Genes for the biogenesis of pili and flagella and several c-type cytochrome genes were among the most highly expressed in G. metallireducens. Mutant strains that lacked the ability to produce pili, flagella, or the outer surface c-type cytochrome encoded by Gmet_2896 were not able to form cocultures with G. 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. PMID:23377933

  20. Transcriptomic and genetic analysis of direct interspecies electron transfer

    DEFF Research Database (Denmark)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena

    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 electron-accepting partner for either Geobacter metallireducens, which performs DIET, or Pelobacter carbinolicus, which relies on HIT. Transcript abundance for G. sulfurreducens uptake hydrogenase genes was 7-fold lower in cocultures with G. metallireducens than in cocultures with P. carbinolicus, consistent with DIET and HIT, respectively, in the two cocultures. Transcript abundance for the pilus-associated cytochrome OmcS, which is essential for DIET but not for HIT, was 240-fold higher in the cocultures with G. metallireducens than in cocultures with P. carbinolicus. The pilin gene pilA was moderately expressed despite a mutation that might be expected to repress pilA expression. Lower transcript abundance for G. sulfurreducens genes associated with acetate metabolism in the cocultures with P. carbinolicus was consistent with the repression of these genes by H2 during HIT. Genes for the biogenesis of pili and flagella and several c-type cytochrome genes were among the most highly expressed in G. metallireducens. Mutant strains that lacked the ability to produce pili, flagella, or the outer surface c-type cytochrome encoded by Gmet_2896 were not able to form cocultures with G. 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.

  1. Transcriptomic and genetic analysis of direct interspecies electron transfer.

    Science.gov (United States)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena; Summers, Zarath M; Shrestha, Minita; Liu, Fanghua; Lovley, Derek R

    2013-04-01

    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 electron-accepting partner for either Geobacter metallireducens, which performs DIET, or Pelobacter carbinolicus, which relies on HIT. Transcript abundance for G. sulfurreducens uptake hydrogenase genes was 7-fold lower in cocultures with G. metallireducens than in cocultures with P. carbinolicus, consistent with DIET and HIT, respectively, in the two cocultures. Transcript abundance for the pilus-associated cytochrome OmcS, which is essential for DIET but not for HIT, was 240-fold higher in the cocultures with G. metallireducens than in cocultures with P. carbinolicus. The pilin gene pilA was moderately expressed despite a mutation that might be expected to repress pilA expression. Lower transcript abundance for G. sulfurreducens genes associated with acetate metabolism in the cocultures with P. carbinolicus was consistent with the repression of these genes by H2 during HIT. Genes for the biogenesis of pili and flagella and several c-type cytochrome genes were among the most highly expressed in G. metallireducens. Mutant strains that lacked the ability to produce pili, flagella, or the outer surface c-type cytochrome encoded by Gmet_2896 were not able to form cocultures with G. 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. PMID:23377933

  2. Photoinduced Electron Transfer Based Ion Sensing within an Optical Fiber

    Directory of Open Access Journals (Sweden)

    Tanya M. Monro

    2011-10-01

    Full Text Available We combine suspended-core microstructured optical fibers with the photoinduced electron transfer (PET effect to demonstrate a new type of fluorescent optical fiber-dip sensing platform for small volume ion detection. A sensor design based on a simple model PET-fluoroionophore system and small core microstructured optical fiber capable of detecting sodium ions is demonstrated. The performance of the dip sensor operating in a high sodium concentration regime (925 ppm Na+ and for lower sodium concentration environments (18.4 ppm Na+ is explored and future approaches to improving the sensor’s signal stability, sensitivity and selectivity are discussed.

  3. Long-range intramolecular electron transfer in azurins

    DEFF Research Database (Denmark)

    Farver, O; Pecht, I

    1989-01-01

    The Cu(II) sites of azurins, the blue single copper proteins, isolated from Pseudomonas aeruginosa and Alcaligenes spp. (Iwasaki) are reduced by CO2- radicals, produced by pulse radiolysis, in two distinct reaction steps: (i) a fast bimolecular phase, at the rates (5.0 +/- 0.8) x 10(8) M-1.s-1 (P. aeruginosa) and (6.0 +/- 1.0) x 10(8) M-1.s-1 (Alcaligenes); (ii) a slow unimolecular phase with specific rates of 44 +/- 7 s-1 in the former and 8.5 +/- 1.5 s-1 for the latter (all at 298 K, 0.1 M ionic strength). Concomitant with the fast reduction of Cu(II), the single disulfide bridge linking cysteine-3 to -26 in these proteins is reduced to the RSSR- radical ion as evidenced by its characteristic absorption band centered at 410 nm. This radical ion decays in a unimolecular process with a rate identical to that of the slow Cu(II) reduction phase in the respective protein, thus clearly suggesting that a long-range intramolecular electron transfer occurs between the RSSR- radicals and the Cu(II) site. The temperature dependence of the internal electron transfer process in both proteins was measured over the 4 degrees C to 42 degrees C range. The activation parameters derived are delta H* = 47.5 +/- 4.0 and 16.7 +/- 1.5 kJ.mol-1; and delta S not equal to = -56.5 +/- 7.0 and -171 +/- 18 J.K-1.mol-1, respectively. Using the Marcus theory, we found that the intramolecular electron transfer rates and their activation parameters observed for the two azurins correlate well with the distances between the reactive sites, their redox potential, and the nature of the separating medium. Thus, azurins with distinct structural and reactivity characteristics isolated from different bacteria or modified by site-directed mutagenesis can be used in comparing long-range electron transfer process between their conserved disulfide bridge and the Cu(II) sites.

  4. Artificial photosynthesis: from nanosecond electron transfer to catalytic water oxidation.

    Science.gov (United States)

    Kärkäs, Markus D; Johnston, Eric V; Verho, Oscar; Akermark, Björn

    2014-01-21

    Human society faces a fundamental challenge as energy consumption is projected to increase due to population and economic growth as fossil fuel resources decrease. Therefore the transition to alternative and sustainable energy sources is of the utmost importance. The conversion of solar energy into chemical energy, by splitting H2O to generate molecular O2 and H2, could contribute to solving the global energy problem. Developing such a system will require the combination of several complicated processes, such as light-harvesting, charge separation, electron transfer, H2O oxidation, and reduction of the generated protons. The primary processes of charge separation and catalysis, which occur in the natural photosynthetic machinery, provide us with an excellent blueprint for the design of such systems. This Account describes our efforts to construct supramolecular assemblies capable of carrying out photoinduced electron transfer and to develop artificial water oxidation catalysts (WOCs). Early work in our group focused on linking a ruthenium chromophore to a manganese-based oxidation catalyst. When we incorporated a tyrosine unit into these supramolecular assemblies, we could observe fast intramolecular electron transfer from the manganese centers, via the tyrosine moiety, to the photooxidized ruthenium center, which clearly resembles the processes occurring in the natural system. Although we demonstrated multi-electron transfer in our artificial systems, the bottleneck proved to be the stability of the WOCs. Researchers have developed a number of WOCs, but the majority can only catalyze H2O oxidation in the presence of strong oxidants such as Ce(IV), which is difficult to generate photochemically. By contrast, illumination of ruthenium(II) photosensitizers in the presence of a sacrificial acceptor generates [Ru(bpy)3](3+)-type oxidants. Their oxidation potentials are significantly lower than that of Ce(IV), but our group recently showed that incorporating negatively charged groups into the ligand backbone could decrease the oxidation potential of the catalysts and, at the same time, decrease the potential for H2O oxidation. This permitted us to develop both ruthenium- and manganese-based WOCs that can operate under neutral conditions, driven by the mild oxidant [Ru(bpy)3](3+). Many hurdles to the development of viable systems for the production of solar fuels remain. However, the combination of important features from the natural photosynthetic machinery and novel artificial components adds insights into the complicated catalytic processes that are involved in splitting H2O. PMID:23957573

  5. Light induced electron transfer reactions of metal complexes

    International Nuclear Information System (INIS)

    Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed

  6. Parton models of high momentum transfer electron-nuclear scattering

    International Nuclear Information System (INIS)

    High-energy electron-nuclear scattering processes are discussed from the point of view of a parton model description. The light-cone formalism is introduced in a schematic presentation emphasizing: (i) the connection to relativistic dynamics, (ii) the phenomenological construction of the far off-shell components of wave functions, and (iii) asymptotic scaling laws. A survey is made of some of the recent calculations based on a nucleon constituent parton model and their comparison with data for momentum transfers Q22. A prospective discussion is also made on multiquark nuclear components and the quark parton model in QCD

  7. Electronic excitation energy transfer between quasi-zero-dimensional systems.

    Czech Academy of Sciences Publication Activity Database

    Král, Karel; Menšík, Miroslav; Mao, H.

    Tokyo : The Surface Science Society of Japan, 2014, s. 11-17. ISSN 1348-0391. [International Conference on Atomically Controlled Surfaces, Interfaces and Nanostructures /12/ - International Colloquium on Scanning Probe Microscopy /21./. Tsukuba (JP), 04.11.2013-08.11.2013] R&D Projects: GA MŠk LH12236; GA MŠk LH12186 Institutional support: RVO:68378271 ; RVO:61389013 Keywords : quantum dots * energy transfer * electron-phonon interaction Subject RIV: BM - Solid Matter Physics ; Magnetism https://www.jstage.jst.go.jp/result?item1=4&word1=Atomically+Controlled+Surfaces+ AND +kral

  8. 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

    2014-08-01

    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 Co2+ promotes ATP-dependent electron transfer; an efficient strategy not seen in other electron-transferring ATPases.

  9. 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.

  10. Generalized Holstein model for spin-dependent electron transfer reaction

    CERN Document Server

    Yang, Li-Ping; Sun, C P

    2011-01-01

    Some chemical reactions are described by electron transfer (ET) processes. The underlying mechanism could be modeled as a polaron motion in the molecular crystal-the Holstein model. By taking spin degrees of freedom into consideration, we generalize the Holstein model (molecular crystal model) to microscopically describe an ET chemical reaction. In our model, the electron spins in the radical pair simultaneously interact with a magnetic field and their nuclear-spin environments. By virtue of the perturbation approach, we obtain the chemical reaction rates for different initial states. It is discovered that the chemical reaction rate of the triplet state demonstrates its dependence on the direction of the magnetic field while the counterpart of the singlet state does not. This difference is attributed to the explicit dependence of the triplet state on the direction when the axis is rotated. Our model may provide a possible candidate for the microscopic origin of avian compass.

  11. 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. PMID:25485993

  12. Picosecond Raman investigation of interligand electron transfer in Ruthenium(II) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Yabe, T.; Orman, L.K.; Anderson, D.R.; Yu, Soochang; Xu, Xiaobing; Hopkins, J.B. (Louisiana State Univ., Baton Rouge (USA))

    1990-09-06

    Interligand electron transfer has been investigated in the excited MLCT electronic states of mixed ligand ruthenium(II) polypyridine complexes containing bipyridine, bipyrimidine, and carboxybipyridine. Two-color picosecond Raman spectroscopy has been used to unambiguously establish the vibrational spectrum corresponding to the ligand-localized MLCT states. With these data direct measurements of electron-transfer dynamics are obtained. It is found that interligand electron transfer is complete on a time scale significantly faster than the 30-ps experimental time resolution.

  13. Photoinduced electron transfer in rhenium(I)-oligotriarylamine molecules.

    Science.gov (United States)

    Bonn, Annabell G; Neuburger, Markus; Wenger, Oliver S

    2014-10-20

    Two molecular triads with an oligotriarylamine multielectron donor were synthesized and investigated with a view to obtaining charge-separated states in which the oligotriarylamine is oxidized 2-fold. Such photoinduced accumulation of multiple redox equivalents is of interest for artificial photosynthesis. The first triad was comprised of the oligotriarylamine and two rhenium(I) tricarbonyl diimine photosensitizers each of which can potentially accept one electron. In the second triad the oligotriarylamine was connected to anthraquinone, in principle an acceptor of two electrons, via a rhenium(I) tricarbonyl diimine unit. With nanosecond transient absorption spectroscopy (using an ordinary pump-probe technique) no evidence for the generation of 2-fold oxidized oligotriarylamine or 2-fold reduced anthraquinone was found. The key factors limiting the photochemistry of the new triads to simple charge separation of one electron and one hole are discussed, and the insights gained from this study are useful for further research in the area of charge accumulation in purely molecular (nanoparticle-free) systems. An important problem of the rhenium-based systems considered here is the short wavelength required for photoexcitation. In the second triad, photogenerated anthraquinone monoanion is protonated by organic acids, and the resulting semiquinone species leads to an increase in lifetime of the charge-separated state by about an order of magnitude. This shows that the proton-coupled electron transfer chemistry of quinones could be beneficial for photoinduced charge accumulation. PMID:25271567

  14. Charge amplification and transfer processes in the gas electron multiplier

    International Nuclear Information System (INIS)

    We report the results of systematic investigations on the operating properties of detectors based on the gas electron multiplier (GEM). The dependence of gain and charge collection efficiency on the external fields has been studied in a range of values for the hole diameter and pitch. The collection efficiency of ionization electrons into the multiplier, after an initial increase, reaches a plateau extending to higher values of drift field the larger the GEM voltage and its optical transparency. The effective gain, fraction of electrons collected by an electrode following the multiplier, increases almost linearly with the collection field, until entering a steeper parallel plate multiplication regime. The maximum effective gain attainable increases with the reduction in the hole diameter, stabilizing to a constant value at a diameter approximately corresponding to the foil thickness. Charge transfer properties appear to depend only on ratios of fields outside and within the channels, with no interaction between the external fields. With proper design, GEM detectors can be optimized to satisfy a wide range of experimental requirements: tracking of minimum ionizing particles, good electron collection with small distortions in high magnetic fields, improved multi-track resolution and strong ion feedback suppression in large volume and time-projection chambers

  15. 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...

  16. Intermolecular Diels-Alder reactions of brominated masked o-benzoquinones with electron-deficient dienophiles. A detour method to synthesize bicyclo[2.2.2]octenones from 2-methoxyphenols.

    Science.gov (United States)

    Lai, Chien-Hsun; Shen, Yi-Ling; Wang, Min-Nen; Kameswara Rao, N S; Liao, Chun-Chen

    2002-09-01

    Intermolecular Diels-Alder reactions of masked o-benzoquinones, i.e., 6,6-dimethoxy-2,4-cyclohexadienones 5-7 and 21-24 generated from 2-methoxyphenols 1-3 and 17-20, respectively, with electron-deficient dienophiles leading to highly functionalized bicyclo[2.2.2]octenones are described. The masked o-benzoquinones (MOBs) 5-7 underwent Diels-Alder cycloadditions with methyl acrylate, methyl methacrylate, and methyl vinyl ketone to provide bicyclo[2.2.2]octenones 13a-c to 15a-c (direct method) in low to moderate yields with the concomitant formation of considerable amounts of dimers 9-11. To retard dimerization and to improve the yields of the requisite bicyclo[2.2.2]octenones, a detour method comprised of sequential bromination of 2-methoxyphenols 1-4, oxidation and Diels-Alder reaction, and debromination has been developed. The oxidation of bromophenols 17-20 produced MOBs 21-24 which are stable enough to be isolated. The MOBs 21-24 underwent cycloaddition with electron-deficient dienophiles in a very efficient manner to afford the corresponding cycloadducts 25a-c to 28a-c in good to high yields without self-dimerization. When the cycloadducts 25a-c to 28a-c were treated with either Bu(3)SnH/AIBN or tributylammonium formate-palladium reagent, the corresponding debrominated products 13a-cto 16a-c were obtained in high to excellent yields. In general, the cycloadducts 13a-c to 15a-c were obtained in 20-40% higher yields via the detour method than those via the direct method. In both routes, the Diels-Alder reactions proceeded in a highly regio- and stereoselective manner to furnish a single cycloadduct in each case. PMID:12201772

  17. Electron-transfer functionality of synthetic coiled-coil metalloproteins

    Scientific Electronic Library Online (English)

    Michael Y., Ogawa; Jiufeng, Fan; Anna, Fedorova; Jing, Hong; Olesya A., Kharenko; Anna Y., Kornilova; Robin C., Lasey; Fei, Xie.

    1516-15-01

    Full Text Available SciELO Brazil | Language: English Abstract in portuguese O campo emergente da engenharia molecular de metaloproteínas visa preparar proteínas artificiais, cujas propriedades podem imitar e talvez até mesmo melhorar várias características encontradas nas metaloenzimas naturais. Este artigo de revisão resume nossos esforços recentes na preparação de metalop [...] roteínas sintéticas, construídas a partir de "coiled-coils" alfa-hélices, e na incorporação de grupos de transferência de elétrons nesses sistemas. Recentemente, concebemos uma cisteína contendo um peptídeo com hélice randômica, o qual forma uma estrutura "coiled-coil" alfa-helicoidal ao se ligar a vários metais. O aduto de CuI pode atuar como agente fotoindutor de transferência de elétrons para receptores exógenos, e transfere elétrons por colisão na região invertida de Marcus para várias aminas de rutênio, as quais atuam como receptores. Especula-se que este resultado inesperado advenha do posicionamento do cofator de CuI no interior da porção hidrofóbica da proteína, o qual proíbe a aproximação entre o doador e o receptor, diminuindo a velocidade de transferência eletrônica daquelas reações termodinamicamente muito favorecidas, para velocidades inferiores à do limite difusional. Abstract in english The emerging field of metalloprotein design seeks to prepare artificial proteins whose properties can mimic, enhance, and perhaps improve upon many features found in natural metalloenzymes. This review summarizes our recent efforts to prepare synthetic metalloproteins built from alpha-helical coiled [...] -coils and to incorporate electron-transfer functionality within these systems. We have recently designed a cysteine-containing random-coil peptide which forms a alpha-helical coiled-coil upon binding various metals. The CuI adduct can serve as photoinduced electron-transfer agent to exogenous acceptors and undergoes collisional electron-transfer in the inverted Marcus region to various ruthenium ammine acceptors. It is speculated that this unexpected result might be due to the positioning of the CuI cofactor within the hydrophobic core of the protein which prohibits close approach between the donor and acceptor to slow the high driving force reaction rates below the diffusion limit.

  18. Coincidence spectroscopy of continuum electron transfer in heavy ion collisions

    International Nuclear Information System (INIS)

    This paper is devoted to review on the continuum transfer process of heavy ions. The recent experiments at University of Tennessee revealed that the projectile Z dependence for the electron capture to continuum states (ECC) by bare C6+. O8+ and Si14+ in Ne and Ar appeared to follow a velocity independent power law of Z with the exponent of 2.3. The characteristic asymmetry for ECC in bare ions was observed, and the interesting interpretation was presented. Two experimental efforts to test this conjecture are under way. Core shift Rydberg state Auger structure was seen in the energy spectrum of electrons emitted in the forward direction in the collision of O4+ ion on Ar. By means of examining the final charge state of scattered ions in coincidence with ECC electrons, it was found to be possible to quantitatively examine the relative importance of simultaneous, coincidence bound and continuum state capture channels, as compared to the process of continuum state capture alone. A high degree of the correlation between the processes of multiple electron capture into bound and continuum states at the velocity used is suggested. Efforts to provide an answer for a question raised from this suggestion are under way at University of Tennessee. Coincidence experiments concerning K-ionizing ion-atom collision and multiple electron loss to discrete continuum states were performed with the same apparatus as that used for the studies on ECparatus as that used for the studies on ECC and electron loss to the continuum (ELC). (Kato, T.)

  19. Promoting direct interspecies electron transfer with activated carbon

    DEFF Research Database (Denmark)

    Liu, Fanghua; Rotaru, Amelia-Elena

    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 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 in the presence of GAC did not require the electrically conductive pili and associated c-type cytochrome involved in biological interspecies electrical connections. GAC also greatly stimulated ethanol metabolism and methane production in co-cultures of G. metallireducens and Methanosarcina barkeri. Cells were attached to GAC, but not closely aggregated, suggesting little opportunity for biological electrical contacts between the species. GAC also enhanced methane production in samples from a methanogenic digester in which Methanosaeta were the predominant methanogens. The results demonstrate that GAC can promote DIET and suggest that stimulation of metabolism in methanogenic digesters can be attributed, at least in part, to the high conductivity of GAC providing better interspecies electrical connections than those that can be forged biologically.

  20. Low temperature free energy relations for electron transfer reactions

    International Nuclear Information System (INIS)

    Using the multiphonon theory of electron transfer reactions we present calculations and simple expressions for the rate of electron transfer between molecules in a medium as a function of the free energy changes, especially in the exothermic region. We include effects of the medium modes as well as higher frequency modes which are allowed to change during the reaction. We find that there are activated as well as nonactivated regions depending on the free energy change and the temperature. The rate in the so called ''anomalous'' (or nonactivated) region decreases much more slowly with free energy than it does in the activated region. In fact, the logorithm of the rate depends roughly linearly on the free energy change in that region. Fortunately the rate is most dependent on the frequency of the high energy modes and less on the coupling strength about which we know the least. In addition we have studied uses of frequency averaging to reproduce the results of a multimode case

  1. Long-range electron transfer in biomolecules. Tunneling or hopping?

    Science.gov (United States)

    Voityuk, Alexander A

    2011-10-27

    Two competing mechanisms are relevant for long-range electron transfer (ET) in biomolecules: direct electron tunneling between donor (D) and acceptor (A), D ? A, and multistep hopping D ? X ? A, where an electron or an electron hole is transiently localized on intermediate sites X. Which of these mechanisms dominates the ET reaction is determined by the arrangement and electronic properties of the redox centers. For thermal ET, it is shown that single-step tunneling is overcome by hopping when the energy gap E between D and X is smaller than the crossover barrier E(C), E(C) = (?G/2) + (3/4)k(B)T?R(DA), where ?G is the driving force, ? the decay parameter, and R(DA) the donor-acceptor distance. In proteins at T = 300 K, hopping will dominate when E E(C). Thus, one can explore the ET mechanism using three quantities E, ?G, and R(DA). When ?G = 0 and E = 0.5 eV (the difference in redox potentials of D and X is 0.5 V), two-step hopping D ? X ? A will be favored at R(DA) >25 Å. In protein ET chains, the distance between redox cofactors is often smaller than 20 Å, but the gap E between the cofactors and surrounding amino acid residues is larger than 0.5 eV. Therefore, ET in the systems should occur by single-step tunneling D ? A. In the activationless regime (?G ? -?, ? is the reorganization energy) often observed for photoinduced ET, the crossing point energy is determined by E(C) = (2?kT?R(DA))(1/2) - ?. The suggested expressions for the threshold barrier may be useful to predict the ET mechanism in natural and artificial redox systems. PMID:21923189

  2. Collisional electron transfer to photoexcited acceptor radical anions

    DEFF Research Database (Denmark)

    Wyer, Jean Ann; StØchkel, Kristian

    2012-01-01

    In this article, we show that photoexcitation of radical anions facilitates electron transfer from sodium atoms in femtosecond encounters. Thus, excitation of 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) and fluorinated TCNQ (TCNQ-F(4)) anions to the second optically active state at 478 nm led to increases in the yields of dianions of about 20% and 10%, respectively. Photoexcitation with a nanosecond-long laser pulse was done a few microseconds before the ions entered the sodium collision cell so that none of the ions would be in any of the initially reached doublet-excited states. We suggest an explanation for the higher electron capture cross section based on the formation of long-lived quartet state anions. Excitation of TCNQ anions within the lowest-energy absorption band, where there are no accessible quartet states, led instead to a lower yield of dianions. There are at least three explanations for the lower dianion yields: (1) Depletion of the monoanion beam due to photodetachment after the absorption ofminimum two photons; (2) Formation of short-lived vibrationally excited dianions that decay by electron autodetachment prior to identification; and (3) Lower electron capture cross sections of vibrationally excited monoanions. Similar losses in dianion signal can occur at 478 nm so the actual yield of dianions at this wavelength due to the population of quartet states is therefore greater than that observed. Our methodology devises a more efficient route for the production of molecular dianions, and at the same time it may provide information on long-lived electronic states.

  3. Competition between electron transfer, trapping, and recombination in CdS nanorod-hydrogenase complexes.

    Science.gov (United States)

    Utterback, James K; Wilker, Molly B; Brown, Katherine A; King, Paul W; Eaves, Joel D; Dukovic, Gordana

    2015-02-10

    Electron transfer from photoexcited CdS nanorods to [FeFe]-hydrogenase is a critical step in photochemical H2 production by CdS-hydrogenase complexes. By accounting for the distributions in the numbers of electron traps and enzymes adsorbed, we determine rate constants and quantum efficiencies for electron transfer from transient absorption measurements. PMID:25623885

  4. Correlation properties of surface and percolation transfer of electrons

    International Nuclear Information System (INIS)

    In this work was received equation, connecting correlatively properties of surface with electrons distribution function. Usually for equilibrium is necessary a large number of collisions. Collisions are 'destroying' correlations. In case rare collisions large importance have correlations and 'memory' effects. Non-Markov's character of emitting particles by surface lead to strongly nonequilibrium condition of 'gas'. Here kinetic equation of diffusive form does not apply. Classical kinetic equation are described only conditions near to equilibrium. This work offers to use ideas anomal diffusion in phase-space. The correlation properties of surface describe by correlations of velocities of emitting electrons: B(t). We offer to use functional equation for probability collision instead of kinetic equation: ?0?0WnoncollF(?) dv = 1 - B(t). This functional allow to consider 'memory' effects. It is important for consideration of electrons and clusters near surfaces. Distribution function become direct connected with correlations. In classical Kubo-Mory theory of transfer is necessary to get nondivergences integral: D ? ?0?B(t). In considering case we can use even 'power function'. It was used 'slow' correlation function as Kohlraush in calculations. The information about kinetics and correlations properties are containing in one functional equation. It was received solution of this equation in form Levy function: F(?) ? 1/?? exp(-1/?). The solution of this form can not be get with help asymptotic methods of kinetic theory. Asymptotics of solution have scale-invariant character F(V) ? 1/V?. This indicate on fractal properties phase-space. (author)

  5. Electric field effects on photoinduced electron transfer processes of methylene-linked compounds of pyrene and N,N-dimethylaniline in a polymer film

    International Nuclear Information System (INIS)

    Time-resolved measurements of the electric-field-induced change in fluorescence intensity have been made for methylene-linked compounds of pyrene and N,N-dimethylaniline (DMA) doped in a polymer film. The lifetime of the fluorescence emitted from the locally excited state of pyrene chromophore becomes shorter in the presence of electric field (F), when the dopant concentration is high. The lifetime of the excipelx fluorescence resulting from the photoinduced electron transfer (PIET) from DMA to the excited state of pyrene chromophore between different molecules also becomes shorter in the presence of F. Based on the simulation of the electric field effect on fluorescence decay, the mechanism of intermolecular PIET between DMA and pyrene chromophore in a polymer film is discussed

  6. 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 (?E) 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 ?E values being calculated. This study can provide a comprehensive understanding of the role of ESs in EET. PMID:25058026

  7. Electron Transfer within Self-Assembling Cyclic Tetramers Using Chlorophyll-Based Donor?Acceptor Building Blocks

    Energy Technology Data Exchange (ETDEWEB)

    Gunderson, Victoria L.; Smeigh, Amanda L.; Kim, Chul Hoon; Co, Dick T.; Wasielewski, Michael R. (NWU)

    2012-05-09

    The synthesis and photoinduced charge transfer properties of a series of Chl-based donor-acceptor triad building blocks that self-assemble into cyclic tetramers are reported. Chlorophyll a was converted into zinc methyl 3-ethylpyrochlorophyllide a (Chl) and then further modified at its 20-position to covalently attach a pyromellitimide (PI) acceptor bearing a pyridine ligand and one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) secondary electron acceptors to give Chl-PI-NDI and Chl-PI-NDI2. The pyridine ligand within each ambident triad enables intermolecular Chl metal-ligand coordination in dry toluene, which results in the formation of cyclic tetramers in solution, as determined using small- and wide-angle X-ray scattering at a synchrotron source. Femtosecond and nanosecond transient absorption spectroscopy of the monomers in toluene-1% pyridine and the cyclic tetramers in toluene shows that the selective photoexcitation of Chl results in intramolecular electron transfer from 1*Chl to PI to form Chl+{lg_bullet}-PI-{lg_bullet}-NDI and Chl+{lg_bullet}-PI-{lg_bullet}-NDI2. This initial charge separation is followed by a rapid charge shift from PI-{lg_bullet} to NDI and subsequent charge recombination of Chl+{lg_bullet}-PI-NDI-{lg_bullet} and Chl+{lg_bullet}-PI-(NDI)NDI-{lg_bullet} on a 5-30 ns time scale. Charge recombination in the Chl-PI-NDI2 cyclic tetramer ({tau}CR = 30 {+-} 1 ns in toluene) is slower by a factor of 3 relative to the monomeric building blocks ({tau}CR = 10 {+-} 1 ns in toluene-1% pyridine). This indicates that the self-assembly of these building blocks into the cyclic tetramers alters their structures in a way that lengthens their charge separation lifetimes, which is an advantageous strategy for artificial photosynthetic systems.

  8. Electron transfer within self-assembling cyclic tetramers using chlorophyll-based donor-acceptor building blocks.

    Science.gov (United States)

    Gunderson, Victoria L; Smeigh, Amanda L; Kim, Chul Hoon; Co, Dick T; Wasielewski, Michael R

    2012-03-01

    The synthesis and photoinduced charge transfer properties of a series of Chl-based donor-acceptor triad building blocks that self-assemble into cyclic tetramers are reported. Chlorophyll a was converted into zinc methyl 3-ethylpyrochlorophyllide a (Chl) and then further modified at its 20-position to covalently attach a pyromellitimide (PI) acceptor bearing a pyridine ligand and one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) secondary electron acceptors to give Chl-PI-NDI and Chl-PI-NDI(2). The pyridine ligand within each ambident triad enables intermolecular Chl metal-ligand coordination in dry toluene, which results in the formation of cyclic tetramers in solution, as determined using small- and wide-angle X-ray scattering at a synchrotron source. Femtosecond and nanosecond transient absorption spectroscopy of the monomers in toluene-1% pyridine and the cyclic tetramers in toluene shows that the selective photoexcitation of Chl results in intramolecular electron transfer from (1*)Chl to PI to form Chl(+•)-PI(-•)-NDI and Chl(+•)-PI(-•)-NDI(2). This initial charge separation is followed by a rapid charge shift from PI(-•) to NDI and subsequent charge recombination of Chl(+•)-PI-NDI(-•) and Chl(+•)-PI-(NDI)NDI(-•) on a 5-30 ns time scale. Charge recombination in the Chl-PI-NDI(2) cyclic tetramer (?(CR) = 30 ± 1 ns in toluene) is slower by a factor of 3 relative to the monomeric building blocks (?(CR) = 10 ± 1 ns in toluene-1% pyridine). This indicates that the self-assembly of these building blocks into the cyclic tetramers alters their structures in a way that lengthens their charge separation lifetimes, which is an advantageous strategy for artificial photosynthetic systems. PMID:22329812

  9. Facile direct electron transfer in glucose oxidase modified electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Wang Dan [Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701 (United States); Chen Liwei [Department of Chemistry and Biochemistry, Ohio University, Athens, OH 45701 (United States); Suzhou Institute of Nano Tech and Nano Bionics, Chinese Academy of Sciences, 398 Ruoshui Road, Suzhou Industrial Park, Suzhou, Jiangsu 215125 (China)], E-mail: lwchen2008@sinano.ac.cn

    2009-07-15

    Glucose oxidase (GOx) is widely used in the glucose biosensor industry. However, mediatorless direct electron transfer (DET) from GOx to electrode surfaces is very slow. Recently, mediatorless DET has been reported via the incorporation of nanomaterials such as carbon nanotubes and nanoparticles in the modification of electrodes. Here we report GOx electrodes showing DET without the need for any nanomaterials. The enzyme after immobilization with poly-L-lysine (PLL) and Nafion retains the biocatalytic activities and oxidizes glucose efficiently. The amperometric response of Nafion-PLL-GOx modified electrode is linearly proportional to the concentration of glucose up to 10 mM with a sensitivity of 0.75 {mu}A/mM at a low detection potential (-0.460 V vs. Ag/AgCl). The methodology developed in this study will have impact on glucose biosensors and biofuel cells and may potentially simplify enzyme immobilization in other biosensing systems.

  10. Reorganization energy of electron transfer at the solvent glass transition

    CERN Document Server

    Ghorai, P K; Ghorai, Pradip K.; Matyushov, Dmitry V.

    2005-01-01

    We present a molecular-dynamics study of the solvent reorganization energy of electron transfer in supercooled water. We observe a sharp decrease of the reorganization energy at a temperature identified as the temperature of structural arrest due to cage effect as discussed by the mode coupling theory. Both the heat capacity and dielectric susceptibility of the pure water show sharp drops at about the same temperature. This temperature also marks the onset of the enhancement of translational diffusion relative to rotational relaxation signaling the break-down of the Stokes-Einstein relation. The change in the reorganization energy at the transition temperature reflects the dynamical arrest of the slow, collective relaxation of the solvent related to Debye relaxation of the solvent dipolar polarization.

  11. Facile direct electron transfer in glucose oxidase modified electrodes

    International Nuclear Information System (INIS)

    Glucose oxidase (GOx) is widely used in the glucose biosensor industry. However, mediatorless direct electron transfer (DET) from GOx to electrode surfaces is very slow. Recently, mediatorless DET has been reported via the incorporation of nanomaterials such as carbon nanotubes and nanoparticles in the modification of electrodes. Here we report GOx electrodes showing DET without the need for any nanomaterials. The enzyme after immobilization with poly-L-lysine (PLL) and Nafion retains the biocatalytic activities and oxidizes glucose efficiently. The amperometric response of Nafion-PLL-GOx modified electrode is linearly proportional to the concentration of glucose up to 10 mM with a sensitivity of 0.75 ?A/mM at a low detection potential (-0.460 V vs. Ag/AgCl). The methodology developed in this study will have impact on glucose biosensors and biofuel cells and may potentially simplify enzyme immobilization in other biosensing systems.

  12. Quantum Dynamics of Electron Transfer from Bacteriochlorophyll to Pheophytin in Bacterial Reaction Centers

    OpenAIRE

    Borrelli, R.; Di Donato, M.; Peluso, A.

    2007-01-01

    Abstract: We extend our previous works on the early electron-transfer steps in bacterial photosynthetic reaction centers to the dynamics of electron transfer from the bacteriochlorophyll anion to pheophytin. The approach employed here takes into account the whole set of normal coordinates of the acceptor and donor groups, in order to reliably account both for shifts and mixing of the normal coordinates and for changes in vibrational frequencies upon electron transfer. It is shown that intramo...

  13. Characterization of electron transfer dissociation in the Orbitrap Velos HCD cell.

    OpenAIRE

    Frese, Ck; Nolting, D.; Altelaar, Af; Griep-raming, J.; Mohammed, S.; Heck, Aj

    2013-01-01

    Electron transfer dissociation (ETD) is commonly employed in ion traps utilizing rf fields that facilitate efficient electron transfer reactions. Here, we explore performing ETD in the HCD collision cell on an Orbitrap Velos instrument by applying a static DC gradient axially to the rods. This gradient enables simultaneous three dimensional, charge sign independent, trapping of cations and anions, initiating electron transfer reactions in the center of the HCD cell where oppositely charged io...

  14. A stochastic reorganizational bath model for electronic energy transfer

    Energy Technology Data Exchange (ETDEWEB)

    Fujita, Takatoshi, E-mail: tfujita@fas.harvard.edu, E-mail: aspuru@chemistry.harvard.edu; Huh, Joonsuk; Aspuru-Guzik, Alán, E-mail: tfujita@fas.harvard.edu, E-mail: aspuru@chemistry.harvard.edu [Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138 (United States)

    2014-06-28

    Environmentally induced fluctuations of the optical gap play a crucial role in electronic energy transfer dynamics. One of the simplest approaches to incorporate such fluctuations in energy transfer dynamics is the well known Haken-Strobl-Reineker (HSR) model, in which the energy-gap fluctuation is approximated as white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to account for excitation energies’ thermal fluctuations. On the other hand, since the original work of HSR, many groups have employed stochastic models to simulate the same transfer dynamics. Here, we discuss a rigorous connection between the stochastic and the atomistic bath models. If the phonon bath is treated classically, time evolution of the exciton-phonon system can be described by Ehrenfest dynamics. To establish the relationship between the stochastic and atomistic bath models, we employ a projection operator technique to derive the generalized Langevin equations for the energy-gap fluctuations. The stochastic bath model can be obtained as an approximation of the atomistic Ehrenfest equations via the generalized Langevin approach. Based on this connection, we propose a novel scheme to take account of reorganization effects within the framework of stochastic models. The proposed scheme provides a better description of the population dynamics especially in the regime of strong exciton-phonon coupling. Finally, we discuss the effect of the bath reorganization in the absorption and fluorescence spectra of ideal J-aggregates in terms of the Stokes shifts. We find a simple expression that relates the reorganization contribution to the Stokes shifts – the reorganization shift – to the ideal or non-ideal exciton delocalization in a J-aggregate. The reorganization shift can be described by three parameters: the monomer reorganization energy, the relaxation time of the optical gap, and the exciton delocalization length. This simple relationship allows one to understand the physical origin of the Stokes shifts in molecular aggregates.

  15. A stochastic reorganizational bath model for electronic energy transfer

    International Nuclear Information System (INIS)

    Environmentally induced fluctuations of the optical gap play a crucial role in electronic energy transfer dynamics. One of the simplest approaches to incorporate such fluctuations in energy transfer dynamics is the well known Haken-Strobl-Reineker (HSR) model, in which the energy-gap fluctuation is approximated as white noise. Recently, several groups have employed molecular dynamics simulations and excited-state calculations in conjunction to account for excitation energies’ thermal fluctuations. On the other hand, since the original work of HSR, many groups have employed stochastic models to simulate the same transfer dynamics. Here, we discuss a rigorous connection between the stochastic and the atomistic bath models. If the phonon bath is treated classically, time evolution of the exciton-phonon system can be described by Ehrenfest dynamics. To establish the relationship between the stochastic and atomistic bath models, we employ a projection operator technique to derive the generalized Langevin equations for the energy-gap fluctuations. The stochastic bath model can be obtained as an approximation of the atomistic Ehrenfest equations via the generalized Langevin approach. Based on this connection, we propose a novel scheme to take account of reorganization effects within the framework of stochastic models. The proposed scheme provides a better description of the population dynamics especially in the regime of strong exciton-phonon coupling. Finally, we discuss the effect of the bath reorganization in the absorption and fluorescence spectra of ideal J-aggregates in terms of the Stokes shifts. We find a simple expression that relates the reorganization contribution to the Stokes shifts – the reorganization shift – to the ideal or non-ideal exciton delocalization in a J-aggregate. The reorganization shift can be described by three parameters: the monomer reorganization energy, the relaxation time of the optical gap, and the exciton delocalization length. This simple relationship allows one to understand the physical origin of the Stokes shifts in molecular aggregates

  16. Strong electronic correlations in superconducting organic charge transfer salts

    CERN Document Server

    Powell, B J; Kenzie, Ross H. Mc

    2006-01-01

    We review the role of strong electronic correlations in quasi--two-dimensional organic charge transfer salts such as (BEDT-TTF)$_2X$, (BETS)$_2Y$ and $\\beta'$-[Pd(dmit)$_2$]$_2Z$. We begin by defining minimal models for these materials. It is necessary to identify two classes of material: the first class is strongly dimerised and is described by a half-filled Hubbard model; the second class is not strongly dimerised and is described by a quarter filled extended Hubbard model. We argue that these models capture the essential physics of these materials. We explore the phase diagram of the half-filled quasi--two-dimensional organic charge transfer salts, focusing on the metallic and superconducting phases. We review work showing that the metallic phase, which has both Fermi liquid and `bad metal' regimes, is described both quantitatively and qualitatively by dynamical mean field theory (DMFT). The phenomenology of the superconducting state is still a matter of contention. We critically review the experimental si...

  17. Mechanism of phase transitions affecting intramolecular electron transfer in trinuclear mixed-valence transition-metal compounds

    Science.gov (United States)

    Kambara, Takeshi; Hendrickson, David N.; Sorai, Michio; Oh, Seung M.

    1986-09-01

    Intramolecular electron delocalization in discrete mixed-valence transition metal complexes in the condensed phase depends not only on the electronic structure of a single complex but also sensitively on the details of the packing arrangement [D. N. Hendrickson, S. M. Oh, T.-Y. Dong, T. Kambara, M. J. Cohn, and M. F. Moore, Comments Inorg. Chem. 4, 329 (1985)]. The problem of how the cooperative properties of mixed-valence complexes in the solid state depend on the electron localization and/or delocalization in a single complex is studied theoretically. A phenomenological intermolecular interaction which depends on the sense and the magnitude of molecular distortion arising from the electron localization is introduced. A theoretical model is developed based on molecular field theory in order to show what types of phase transitions relating to the electron delocalization are possible in the trinuclear mixed-valence compounds and how the electronic structure of constituent molecules determines the type of phase transition. There are three types of phase transitions: (1) Order-disorder transition with respect to the alignment of the sense of molecular distortion associated with the electron localization; (2) static localization-delocalization transition, where the molecular distortion disappears above the transition temperature and electrons are coherently delocalized on three transition metal ions; (3) dynamical localization-delocalization transition in which the delocalization comes from fast electron transfer between three transition-metal ions and the molecular structure is changed from a static distortion to a dynamical distortion. The theoretical model is used to explain the observed temperature dependencies of heat capacity and Mössbauer spectra for the trinuclear mixed-valence complex [Fe3O(O2CCH3)6(py)3](py), where (py) is pyridine [S. M. Oh. T. Kambara, D. N. Hendrickson, M. Sorai, K. Kaji, S. E. Woehler, and R. J. Wittebort, J. Am. Chem. Soc. 107, 5540 (1985); M. Sorai, K. Kaji, D. N. Hendrickson, and S. M. Oh, ibid. 108, 702 (1986)]. The first-order phase transition at ˜112 K is assigned as an order-disorder transition and the higher-order transition at ˜190 K is assigned as a dynamical localization-delocalization transition.

  18. Dynamic modulation of electron correlation by intramolecular modes in charge transfer compounds

    OpenAIRE

    Meneghetti, M.

    1999-01-01

    Electron-phonon and electron-electron interactions are in competition in determining the properties of molecular charge transfer conductors and superconductors. The direct influence of phonons on the electron-electron interaction was not before considered and in the present work the coupling of intramolecular modes to electron-electron interaction (U-vib interaction) is investigated.The effect of this coupling on the frequency of the normal modes of a dimer model is obtained...

  19. Photoinduced tautomerism of 2,6-dicarbomethoxyphenol in DMF–water mixtures: Perturbation from intermolecular processes

    International Nuclear Information System (INIS)

    In this paper, we report the spectral signatures of photoinduced tautomerism of 4-methyl-2,6-dicarbomethoxyphenol (CMOH) in DMF–water mixtures with varying compositions. Excited state intramolecular proton transfer (ESIPT) reaction of CMOH has been observed in bulk DMF, indicated by dual fluorescence from its normal and tautomeric forms while only a single emission peak is observed in water from its anionic species. Binary mixture of a polar aprotic (DMF) and a polar protic (water) solvent gives rise to a competition between intramolecular and intermolecular hydrogen bonding (with media) processes of the probe. This competition is found to be largely dependent on the proton affinity of the media and also on the excitation energy. Solvent separated ion pair and intermolecularly H-bonded CMOH–Solvent complex have been detected in the excited state at specific solvent compositions that are converted to the anionic form due to the change in excitation wavelengths. The formation of hydrogen bonded 1:1 molecular clusters of different rotamers of CMOH with DMF and water in the ground state has been investigated using quantum chemical calculations. A combined experimental and theoretical analysis indicates that the HOMO to LUMO transitions dictate the electronic absorption profiles of the CMOH–DMF and CMOH–water clusters. These findings are expected to shed light on the mechanism of acid–base reactions of several hydrogen bonded systems that are part of many biologically relevant processes. -- Highlights: •Photoinduced tautomerization of CMOH has been studied in DMF–water mixture. •CMOH forms 1:1 molecular clusters with DMF and water. •The competition between intra- and intermolecular hydrogen bonding is revealed. •HOMO to LUMO transition dictates the absorption spectra of CMOH in DMF and water

  20. Electron transfer in peptides: on the formation of silver nanoparticles.

    Science.gov (United States)

    Kracht, Sonja; Messerer, Matthias; Lang, Matthieu; Eckhardt, Sonja; Lauz, Miriam; Grobéty, Bernard; Fromm, Katharina M; Giese, Bernd

    2015-03-01

    Some microorganisms perform anaerobic mineral respiration by reducing metal ions to metal nanoparticles, using peptide aggregates as medium for electron transfer (ET). Such a reaction type is investigated here with model peptides and silver as the metal. Surprisingly, Ag(+) ions bound by peptides with histidine as the Ag(+) -binding amino acid and tyrosine as photoinducible electron donor cannot be reduced to Ag nanoparticles (AgNPs) under ET conditions because the peptide prevents the aggregation of Ag atoms to form AgNPs. Only in the presence of chloride ions, which generate AgCl microcrystals in the peptide matrix, does the synthesis of AgNPs occur. The reaction starts with the formation of 100?nm Ag@AgCl/peptide nanocomposites which are cleaved into 15?nm AgNPs. This defined transformation from large nanoparticles into small ones is in contrast to the usually observed Ostwald ripening processes and can be followed in detail by studying time-resolved UV/Vis spectra which exhibit an isosbestic point. PMID:25663127

  1. Photoinduced electron transfer processes in homogeneous and microheterogeneous solutions

    Science.gov (United States)

    Whitten, D. G.

    1990-10-01

    Chemical electron transfer-induced fragmentation of a variety of electron donors was shown to be a quite general process. In previous studies, attention was focused on alpha-Beta aminoalcohols and 1,2-ditertiary amines. In the present year, studies were extended to include pinacols, an richer variety of diamines and amino-ketones. The mechanisms, intermediates involved in these fragmentation reactions, and medium effects were also studied. Studies of pinacols and a variety of diamines show that photooxidative cleavage of 1,2-diheteroatom-containing molecules is a very general process which can occur for several different types of molecules. In order to demonstrate clearly that cation radicals of the heteroatom containing donor can be intermediates in these reactions, the reaction was studied of several different donors with the acceptors, dicyanoanthracene (DCA) and tetracyanoanthracene (TCA) using biphenyl (BP) as a cosensitizer. The second major focus of the work was to look at donors which, undergo reversible redox reactions to give relatively high energy products which are capable of undergoing clean thermal reverse redox reactions but which survive long enough to be potentially useful for other purposes. The reaction explored extensively is the oxidation of tertiary amines to enamines by quinone type molecules such as beta-lapachone. These studies are continued and other reactions are examined which may be more promising in terms of finding a photochemical-thermal redox cycle which can be carried out with little loss of material through competing side reactions.

  2. Ions interacting with planar aromatic molecules: Modeling electron transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Forsberg, B. O.; Alexander, J. D.; Chen, T.; Pettersson, A. T.; Gatchell, M.; Cederquist, H.; Zettergren, H. [Department of Physics, Stockholm University, SE-106 91 Stockholm (Sweden)

    2013-02-07

    We present theoretical absolute charge exchange cross sections for multiply charged cations interacting with the Polycyclic Aromatic Hydrocarbon (PAH) molecules pyrene C{sub 14}H{sub 10}, coronene C{sub 24}H{sub 12}, or circumcoronene C{sub 54}H{sub 18}. These planar, nearly circular, PAHs are modelled as conducting, infinitely thin, and perfectly circular discs, which are randomly oriented with respect to straight line ion trajectories. We present the analytical solution for the potential energy surface experienced by an electron in the field of such a charged disc and a point-charge at an arbitrary position. The location and height of the corresponding potential energy barrier from this simple model are in close agreement with those from much more computationally demanding Density Functional Theory (DFT) calculations in a number of test cases. The model results compare favourably with available experimental data on single- and multiple electron transfer reactions and we demonstrate that it is important to include the orientation dependent polarizabilities of the molecules (model discs) in particular for the larger PAHs. PAH ionization energy sequences from DFT are tabulated and used as model inputs. Absolute cross sections for the ionization of PAH molecules, and PAH ionization energies such as the ones presented here may be useful when considering the roles of PAHs and their ions in, e.g., interstellar chemistry, stellar atmospheres, and in related photoabsorption and photoemission spectroscopies.

  3. 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.

  4. Photoinduced electron transfer from aliphatic amines to coumarin dyes

    Science.gov (United States)

    Nad, Sanjukta; Pal, Haridas

    2002-01-01

    Electron transfer (ET) interactions of a series of 7-aminocoumarin dyes with aliphatic amine donors have been investigated using steady-state (SS) and time-resolved (TR) fluorescence quenching, picosecond laser flash photolysis (LFP) and pulse radiolysis (PR) techniques. For different coumarin-amine pairs, the estimated quenching constants (kq) from SS and TR fluorescence measurements are found to be similar within the experimental error. That ET from amine donors to excited (S1) coumarin dyes takes place has been established from the LFP and the PR results. For different coumarin-amine pairs, the kq values are seen to correlate well with the free energy changes (?G0) for the ET reactions following Marcus' outer-sphere ET theory. The total reorganization energy (?) estimated from this correlation is seen to be just similar to the solvent reorganization energy (?s). The leveled-off kq value under diffusion-controlled condition (kqDC) appears to be much lower (˜2.5 times) for the present systems compared to the corresponding value obtained for the ET reactions in coumarin-aromatic amine systems. The large difference in the kqDC values with aliphatic and aromatic amines as the electron donors has been rationalized on the basis of the shapes of the highest occupied molecular orbitals (HOMO) of the amine donors. For aliphatic amines, since their HOMOs are largely localized on the amino group, a large orientation factor is involved in the encounter complexes for the ET reaction to take place. With ? like HOMOs, such orientational restriction is just nominal with the aromatic amines as the electron donors. Present ET results under diffusive conditions have also been discussed with a comparison to the ET rates observed under nondiffusive conditions, where the amines are directly used as the solvent donors.

  5. Electron transfer in keV-energy 4He++ atomic collisions. I. Single and double electron transfer with He, Ar, H2, and N2

    International Nuclear Information System (INIS)

    Single- and double-electron-transfer cross sections have been measured for a 4He++ beam incident on thin He, Ar, H2, and N2 gas targets over the energy range 15--125 keV. Comparison with previous 3He++ experimental results is made at the same incident particle velocity. For He++ collisions with He, we find good agreement with the theory for double electron transfer, but conclude that the single-electron-transfer cross section is far from being understood. Interpretation of the data in terms of simple theoretical ideas indicates that capture into excited states of the He+ ion can be the dominant single-electron-transfer process in some keV-energy He++ atomic collisions

  6. Bimolecular processes on silica gel surfaces: energetic factors in determining electron-transfer rates.

    Science.gov (United States)

    Worrall, David R; Kirkpatrick, Iain; Williams, Sian L

    2004-01-01

    Triplet state and radical cation formation is observed following laser excitation of anthracene, phenanthrene and naphthalene (and their derivatives) adsorbed on silica gel. Energy- and electron-transfer reactions of these compounds with co-adsorbed azulene have been studied using a time-resolved diffuse reflectance laser flash photolysis technique. Triplet energy transfer from the arene derivative to azulene and electron transfer from azulene to the arene radical cation have been investigated in order to distinguish between diffusional and energetic control in these systems. Energy and electron transfer can be studied independently due to differing absorption properties and energy dependencies of production of the triplet states and radical cations. Transient decay kinetics for both electron and energy transfer have been modelled using two different rate constant distributions: a log Gaussian and a symmetrical Levy stable distribution. The latter model has also been demonstrated to be applicable to the decay of radical cations in the absence of an electron donor, which cannot be adequately described by the Gaussian model. Energy-transfer rates between the arene derivatives and azulene have been found to be close to the diffusion-controlled limit; however, in most cases, the rate of electron transfer is considerably lower. A correlation between the bimolecular rate constant and free energy of electron transfer has been found, indicating a Marcus inverted region. Compounds with bulky substituents show a further reduction in the rate of electron transfer, suggesting that an additional steric factor is involved in this process. PMID:14743281

  7. A new mechanism for electron transfer in fast ion-atomic collisions

    OpenAIRE

    Voitkiv, A. B.; Najjari, B.; Ullrich, J.

    2008-01-01

    We discuss a new mechanism for the electron capture in fast ion-atom collisions. Similarly like in the radiative capture, where the electron transfer occurs due to photon emission, within the mechanism under consideration the electron capture takes place due to the emission of an additional electron. This first order capture process leads to the so called transfer-ionization and has a number of interesting features, in particular, in the target frame it results in the electr...

  8. Coherent transfer of light polarization to electron spins in a semiconductor

    OpenAIRE

    Kosaka, Hideo; Shigyou, Hideki; Mitsumori, Yasuyoshi; Rikitake, Yoshiaki; Imamura, Hiroshi; Kutsuwa, Takeshi; Arai, Koichiro; Edamatsu, Keiichi

    2007-01-01

    We demonstrate that the superposition of light polarization states is coherently transferred to electron spins in a semiconductor quantum well. By using time-resolved Kerr rotation we observe the initial phase of Larmor precession of electron spins whose coherence is transferred from light. To break the electron-hole spin entanglement, we utilized the big discrepancy between the transverse g-factors of electrons and light holes. The result encourages us to make a quantum med...

  9. 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.

    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 on the electrode charge. The slope is smaller the more negative the charge density due to enhanced extension of the surface electronic density profile on the solution side, and thereby better electronic overlap with the reacting molecule. The effect is sensitive to the bulk electron density of the metal and the localization of the electronic state at the molecular reactant site. Effects similar to these have been observed experimentally and could be common for electronically light metals.

  10. Structural factors influencing the intramolecular charge transfer and photoinduced electron transfer in tetrapyrazinoporphyrazines.

    Science.gov (United States)

    Novakova, Veronika; Hladík, Petr; Filandrová, Tereza; Zajícová, Ivana; Krepsová, Veronika; Miletin, Miroslav; Len?o, Juraj; Zimcik, Petr

    2014-03-21

    A series of unsymmetrical tetrapyrazinoporphyrazines (TPyzPzs) from the group of azaphthalocyanines with one peripherally attached amino substituent (donor) were synthesized, and their photophysical properties (fluorescence quantum yield and singlet oxygen quantum yield) were determined. The synthesized TPyzPzs were expected to undergo intramolecular charge transfer (ICT) as the main pathway for deactivating their excited states. Several structural factors were found to play a critical role in ICT efficiency. The substituent in the ortho position to the donor center significantly influences the ICT, with tert-butylsulfanyl and butoxy substituents inducing the strongest ICTs, whereas chloro, methyl, phenyl, and hydrogen substituents in this position reduce the efficiency. The strength of the donor positively influences the ICT efficiency and correlates well with the oxidation potential of the amines used as the substituents on the TPyzPz as follows: n-butylamine < N,N-diethylamine < aniline < phenothiazine. The ICT (with conjugated donors and acceptors) in the TPyzPz also proved to be much stronger than a photoinduced electron transfer in which the donor and the acceptor are connected through an aliphatic linker. PMID:24509513

  11. Strong electronic correlations in superconducting organic charge transfer salts

    International Nuclear Information System (INIS)

    We review the role of strong electronic correlations in quasi-two-dimensional organic charge transfer salts such as (BEDT-TTF)2X (BETS)2Y, and ?'-(Pd(dmit)2)2Z. We begin by defining minimal models for these materials. It is necessary to identify two classes of material: the first class is strongly dimerized and is described by a half-filled Hubbard model; the second class is not strongly dimerized and is described by a quarter-filled extended Hubbard model. We argue that these models capture the essential physics of these materials. We explore the phase diagram of the half-filled quasi-two-dimensional organic charge transfer salts, focusing on the metallic and superconducting phases. We review work showing that the metallic phase, which has both Fermi liquid and 'bad metal' regimes, is described both quantitatively and qualitatively by dynamical mean field theory (DMFT). The phenomenology of the superconducting state is still a matter of contention. We critically review the experimental situation, focusing on the key experimental results that may distinguish between rival theories of superconductivity, particularly probes of the pairing symmetry and measurements of the superfluid stiffness. We then discuss some strongly correlated theories of superconductivity, in particular the resonating valence bond (RVB) theory of superconductivity. We conclude by discussing some of the major challenges currently facing the field. Thesellenges currently facing the field. These include parameterizing minimal models, the evidence for a pseudogap from nuclear magnetic resonance (NMR) experiments, superconductors with low critical temperatures and extremely small superfluid stiffnesses, the possible spin-liquid states in ?-(ET)2Cu2(CN)3 and ?'-[Pd(dmit)2]2Z, and the need for high quality large single crystals. (topical review)

  12. Strong electronic correlations in superconducting organic charge transfer salts

    Energy Technology Data Exchange (ETDEWEB)

    Powell, B J; McKenzie, Ross H [Department of Physics, University of Queensland, Brisbane, Queensland 4072 (Australia)

    2006-11-15

    We review the role of strong electronic correlations in quasi-two-dimensional organic charge transfer salts such as (BEDT-TTF){sub 2}X (BETS){sub 2}Y, and {beta}'-(Pd(dmit){sub 2}){sub 2}Z. We begin by defining minimal models for these materials. It is necessary to identify two classes of material: the first class is strongly dimerized and is described by a half-filled Hubbard model; the second class is not strongly dimerized and is described by a quarter-filled extended Hubbard model. We argue that these models capture the essential physics of these materials. We explore the phase diagram of the half-filled quasi-two-dimensional organic charge transfer salts, focusing on the metallic and superconducting phases. We review work showing that the metallic phase, which has both Fermi liquid and 'bad metal' regimes, is described both quantitatively and qualitatively by dynamical mean field theory (DMFT). The phenomenology of the superconducting state is still a matter of contention. We critically review the experimental situation, focusing on the key experimental results that may distinguish between rival theories of superconductivity, particularly probes of the pairing symmetry and measurements of the superfluid stiffness. We then discuss some strongly correlated theories of superconductivity, in particular the resonating valence bond (RVB) theory of superconductivity. We conclude by discussing some of the major challenges currently facing the field. These include parameterizing minimal models, the evidence for a pseudogap from nuclear magnetic resonance (NMR) experiments, superconductors with low critical temperatures and extremely small superfluid stiffnesses, the possible spin-liquid states in {kappa}-(ET){sub 2}Cu{sub 2}(CN){sub 3} and {beta}'-[Pd(dmit){sub 2}]{sub 2}Z, and the need for high quality large single crystals. (topical review)

  13. Desensitization and recovery of metastable intermolecular composites

    Science.gov (United States)

    Busse, James R. (South Fork, CO); Dye, Robert C. (Los Alamos, NM); Foley, Timothy J. (Los Alamos, NM); Higa, Kelvin T. (Ridgecrest, CA); Jorgensen, Betty S. (Jemez Springs, NM); Sanders, Victor E. (White Rock, NM); Son, Steven F. (Los Alamos, NM)

    2010-09-07

    A method to substantially desensitize a metastable intermolecular composite material to electrostatic discharge and friction comprising mixing the composite material with an organic diluent and removing enough organic diluent from the mixture to form a mixture with a substantially putty-like consistency, as well as a concomitant method of recovering the metastable intermolecular composite material.

  14. Theoretical study on the electronic structure of triphenyl sulfonium salts: Electronic excitation and electron transfer processes

    Science.gov (United States)

    Petsalakis, Ioannis D.; Theodorakopoulos, Giannoula; Lathiotakis, Nektarios N.; Georgiadou, Dimitra G.; Vasilopoulou, Maria; Argitis, Panagiotis

    2014-05-01

    Density functional theory (DFT) and Time Dependent DFT calculations on triphenyl sulfonium cation (TPS) and the salts of TPS with triflate, nonaflate, perfluoro-1-octanesulfonate and hexafluoro antimonate anions are presented. These systems are widely used as cationic photoinitiators and as electron ejection layer for polymer light-emitting diodes. While some differences exist in the electronic structure of the different salts, their lowest energy intense absorption maxima are calculated at nearly the same energy for all systems. The first excited state of TPS and of the TPS salts is dissociating. Electron addition to the TPS salts lowers their energy by 1.0-1.33 eV.

  15. Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles

    Science.gov (United States)

    Tvrdy, Kevin; Frantsuzov, Pavel A.; Kamat, Prashant V.

    2011-01-01

    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 (SnO2, TiO2, 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 (SnO2) were not the same as those which showed the highest photocurrent (TiO2). 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. PMID:21149685

  16. Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles.

    Science.gov (United States)

    Tvrdy, Kevin; Frantsuzov, Pavel A; Kamat, Prashant V

    2011-01-01

    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. PMID:21149685

  17. Electron and hole transfer in DNA: the role of tunneling and environment

    International Nuclear Information System (INIS)

    Owing to the biological significance of radiation induced DNA damage, electron and hole transfer processes in DNA have attracted considerable interest. Various mechanisms for these processes have been proposed including tunneling and hopping. In our efforts we have investigated electron transfer for DNA in glasses, ices and solids at low temperatures via electron spin resonance (ESR) spectroscopy. Electrons and holes generated by irradiation at 77 K are trapped on DNA and transfer to a randomly interspersed intercalator, mitoxantrone (MX). Monitoring the changes of ESR signals of MX radicals, one electron oxidized guanine (G·+), one-electron reduced cytosine [C(N3)H·], and thymine anion radicals (T·-) with time at 77 K allows for the direct observation of electron and hole transfer. For DNA in aqueous glasses at low temperatures we are able to isolate the tunneling of excess electrons and we report overall distances of travel and the tunneling decay constant, beta. Studies with the duplexes polydAdT·polydAdT and polydIdC·polydIdC randomly intercalated with mitoxantrone (MX) show the excess electron transfer distances to be longer for pdAdT·pdAdT, than for for pdIdC·pdIdC. The beta value for DNA (0.9Angstroms-1) lies intermediate between that for pdAdT·pdAdT (0.75 Angstroms-1) and that for pdIdC·pdIdC (1.4 Angstroms-1). These results suggest that proton transfer from I to C·- forming CH· significantly slows but does not stop cantly slows but does not stop electron transfer. Similarly in DNA proton transfer in GC anion radical is not found to prevent electron transfer. Electron and hole transfer processes in frozen solutions (D2O ices) show that electron/hole transfer in polyA·polyU is significantly further than in DNA and transfer distances in polyC·polyG are substantially less than in DNA. These findings confirm our results in aqueous glasses. Our investigations of the effect of hydration, space filling lipid amine cation complexes, and temperature will also be discussed. Our modeling of electron transfer rates and distances of electron transfer in DNA-complexes allow for estimates of the spacing between DNA double stranded helices in each complex. This research was supported by the NIH NCI Grant RO1 CA45424

  18. The electron transfer complex between nitrous oxide reductase and its electron donors.

    Science.gov (United States)

    Dell'acqua, Simone; Moura, Isabel; Moura, José J G; Pauleta, Sofia R

    2011-12-01

    Identifying redox partners and the interaction surfaces is crucial for fully understanding electron flow in a respiratory chain. In this study, we focused on the interaction of nitrous oxide reductase (N(2)OR), which catalyzes the final step in bacterial denitrification, with its physiological electron donor, either a c-type cytochrome or a type 1 copper protein. The comparison between the interaction of N(2)OR from three different microorganisms, Pseudomonas nautica, Paracoccus denitrificans, and Achromobacter cycloclastes, with their physiological electron donors was performed through the analysis of the primary sequence alignment, electrostatic surface, and molecular docking simulations, using the bimolecular complex generation with global evaluation and ranking algorithm. The docking results were analyzed taking into account the experimental data, since the interaction is suggested to have either a hydrophobic nature, in the case of P. nautica N(2)OR, or an electrostatic nature, in the case of P. denitrificans N(2)OR and A. cycloclastes N(2)OR. A set of well-conserved residues on the N(2)OR surface were identified as being part of the electron transfer pathway from the redox partner to N(2)OR (Ala495, Asp519, Val524, His566 and Leu568 numbered according to the P. nautica N(2)OR sequence). Moreover, we built a model for Wolinella succinogenes N(2)OR, an enzyme that has an additional c-type-heme-containing domain. The structures of the N(2)OR domain and the c-type-heme-containing domain were modeled and the full-length structure was obtained by molecular docking simulation of these two domains. The orientation of the c-type-heme-containing domain relative to the N(2)OR domain is similar to that found in the other electron transfer complexes. PMID:21739254

  19. 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.

  20. Theoretical study of ultrafast heterogeneous electron transfer reactions at dye-semiconductor interfaces

    International Nuclear Information System (INIS)

    A detailed study of photoinduced electron transfer reactions from an electronically excited state of a dye molecule to the conduction band of a semiconductor substrate is presented. Adopting a generic model for electronic-vibrational coupling in heterogeneous electron transfer reactions, the quantum dynamics of the electron injection process is simulated employing the recently proposed self-consistent hybrid method. The results reveal the influence of coherent and dissipative vibrational motion on the electron transfer dynamics. Furthermore, the dependence of the injection dynamics on various electron transfer parameters, such as the energetic position of the donor state, the coupling strength between the dye molecule and the semiconductor substrate, the characteristic timescale of the nuclear degrees of freedom and the temperature, is discussed in some detail

  1. 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, the average electron temperature is expected to be between 10,000 and 20,000 K. Thus only data for low energy electrons are relevant to the model.

  2. Rydberg electron transfer to hydrogen iodide: Dissociative and nondissociative electron capture

    International Nuclear Information System (INIS)

    Rydberg electron transfer (RET) to jet-cooled hydrogen iodide (HI) molecules has been studied for alkali atoms excited to ns and nd Rydberg levels (9- ions produced by dissociative electron capture are observed for all Rydberg levels studied, even though dissociative RET becomes endothermic for n23, rate constants for I- formation are in good agreement with previous results for low energy free electron attachment. For lower values of n, the RET results deviate from the free electron results due to electrostatic interactions between the nascent positive (Rydberg core) and negative ions. A simple calculation based upon the ''free electron model'' agrees quantitatively with the rate constant data for n>13. For Rydberg levels with n- (and DI-) ions are observed which appear to be stable with respect to both dissociation and autodetachment. These observations indicate that a bound and stable anion state exists, correlating with the lowest H(D)+I- limit, with a potential well which supports at least one vibrational level for both HI- and DI-

  3. Non-Gaussian statistics of binding/unbinding events and the energetics of electron transfer reactions

    International Nuclear Information System (INIS)

    We describe a model of electron transfer reactions affected by local binding to the donor or acceptor sites of a particle in equilibrium with the solution. The statistics of fluctuations of the donor-acceptor energy gap caused by binding/unbinding events are non-Gaussian, and the resulting free energy surfaces of electron transfer are non-parabolic. The band-width of the charge-transfer optical transition is predicted to pass through a maximum as a function of the concentration of binding particles in the solution. The breakdown of the link between the Stokes shift and the reorganization energy of electron transfer is also predicted by the model

  4. Concerted proton-coupled electron transfer from a metal-hydride complex

    Science.gov (United States)

    Bourrez, Marc; Steinmetz, Romain; Ott, Sascha; Gloaguen, Frederic; Hammarström, Leif

    2015-02-01

    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 proton-coupled 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.

  5. Vibrational coherence probes the mechanism of ultrafast electron transfer in polymer–fullerene blends

    Science.gov (United States)

    Song, Yin; Clafton, Scott N.; Pensack, Ryan D.; Kee, Tak W.; Scholes, Gregory D.

    2014-09-01

    The conversion of photoexcitations into charge carriers in organic solar cells is facilitated by the dissociation of excitons at the donor/acceptor interface. The ultrafast timescale of charge separation demands sophisticated theoretical models and raises questions about the role of coherence in the charge-transfer mechanism. Here, we apply two-dimensional electronic spectroscopy to study the electron transfer process in poly(3-hexylthiophene)/PCBM (P3HT/PCBM) blends. We report dynamics maps showing the pathways of charge transfer that clearly expose the significance of hot electron transfer. During this ultrafast electron transfer, vibrational coherence is directly transferred from the P3HT exciton to the P3HT hole polaron in the crystalline domain. This result reveals that the exciton converts to a hole with a similar spatial extent on a timescale far exceeding other photophysical dynamics including vibrational relaxation.

  6. Vibrational coherence probes the mechanism of ultrafast electron transfer in polymer-fullerene blends.

    Science.gov (United States)

    Song, Yin; Clafton, Scott N; Pensack, Ryan D; Kee, Tak W; Scholes, Gregory D

    2014-01-01

    The conversion of photoexcitations into charge carriers in organic solar cells is facilitated by the dissociation of excitons at the donor/acceptor interface. The ultrafast timescale of charge separation demands sophisticated theoretical models and raises questions about the role of coherence in the charge-transfer mechanism. Here, we apply two-dimensional electronic spectroscopy to study the electron transfer process in poly(3-hexylthiophene)/PCBM (P3HT/PCBM) blends. We report dynamics maps showing the pathways of charge transfer that clearly expose the significance of hot electron transfer. During this ultrafast electron transfer, vibrational coherence is directly transferred from the P3HT exciton to the P3HT hole polaron in the crystalline domain. This result reveals that the exciton converts to a hole with a similar spatial extent on a timescale far exceeding other photophysical dynamics including vibrational relaxation. PMID:25215959

  7. The microwave-look into the photo electrode: What can we learn about interfacial electron transfer?

    International Nuclear Information System (INIS)

    By combining photo-electrochemical and photo-induced microwave conductivity measurements, information on potential dependent minority charge carrier accumulation, on interfacial minority carrier concentration and on interfacial charge transfer rates can be obtained. It suggests a correlation between electron transfer processes and accumulated charge carriers dominated by non-equilibrium conditions. This is inconsistent with the general assumptions leading to the classical Marcus-Gerischer electron transfer at electrodes, conceived for weak interaction, quasi-equilibrium and absence of polarisability effects. It is considered only to be applicable in special situations. A non-linear interfacial electron transfer theory, the properties of which are outlined, will on the other hand open the potential for new phenomena. They include faster (stimulated), and cooperative electron transfer. The latter, which is excluded by the classical theory, requires non linear dynamic feedback polarisability, which will have to be developed on the basis of structural-electronic considerations for semiconductor interfaces to become highly catalytic

  8. Selective electron transfer between the quantum dots under the resonant pulse

    OpenAIRE

    Tsukanov, A. V.; Openov, L. A.

    2004-01-01

    The coherent quantum dynamics of an electron in the quantum-dot ring structure under the resonant electromagnetic pulse is studied theoretically. A possibility of the selective electron transfer between any two dots is demonstrated. The transfer probability as a function of the pulse and dot parameters is calculated. It is shown that this probability can be close to unity. The factors lowering the transfer probability in real systems are discussed. The results obtained may b...

  9. 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.

  10. Electron transfer of peroxidase assemblies at tailored nanocarbon electrodes

    International Nuclear Information System (INIS)

    In bioelectrochemistry, the catalytic function of redox enzymes depends largely upon the nature of the working electrode material. One major example of this phenomenon is the improvement of biogenic analyte detection at graphitic carbon with increased edge plane character in the graphene lattice. In our laboratories, we have found that the edge plane character of carbon nanotubes (CNTs) prepared using chemical vapor deposition (CVD) can be tuned via selective doping with nitrogen, termed N-CNTs. In this report, we extend these studies to investigate the influence of N-doping of nanocarbons on the electron transfer of horseradish peroxidase (HRP) using spectrophotometric enzyme activity assays and electrochemical measurements. Our findings demonstrate that HRP adsorption at N-CNTs increases by a factor of two relative to that of nondoped CNTs, with surface coverages, ?m, of 75 ± 4 and 33 ± 5 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) U/mg, respectively. Surprisingly, however, only ?40% of the HRP adsorbed at N-CNTs is electroactive, as assessed by voltammetry of the HRP Fe2+/3+ redox response. By contrast, HRP adsorbed at nondoped CNTs is nearly 100% electroactive, suggesting that the nature of the HRP adsorption (e.g., electrostatic, van der Waals) and geometric factors of heme orientation affect the biocatalytic performance. We also describe studies that utilize the properties of both nondoped CNTs and N-CNTs with adsorbenondoped CNTs and N-CNTs with adsorbed HRP for unmediated, quantitative H2O2 sensing

  11. 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

    2013-10-01

    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 Fe(ox)(ADP)2 protein and the reduced MoFe protein. PMID:24062462

  12. Spectral and Kinetic Properties of Radical Cations Derived from Oxoisoaporphines: Relevance to Electron-Transfer Processes Involving Phytoalexins.

    Science.gov (United States)

    De la Fuente, Julio R; Kciuk, Gabriel; Aliaga, Christian; Bobrowski, Krzysztof

    2014-05-16

    The thermally induced intermolecular electron transfer reaction in acetonitrile between the tetracyanoethylene (TCNE), a ?-electron acceptor with a large electron affinity, and six oxoisoaporphines (2,3-dihydro-7H-dibenzo[de,h]quinolin-7-one, 5-methoxy-2,3-dihydro-7H-dibenzo[de,h]quinolin-7-one, 1-azabenzo[de]anthracen-7-one, 5-methoxy-1-azabenzo[de]anthracen-7-one, 7H-benzo[e]perimidin-7-one, and 2-methyl-7h-benzo[e]perimidin-7-one) is reported. Spectral and kinetic characteristics are presented for radical cations derived from these six oxoisoaporphines either generated by a thermal reaction or generated radiolytically in argon-saturated 1,2-dichloroethane, oxygen-saturated acetone, and acetonitrile. The radical cations of oxoisoaporphines are insensitive to oxygen and are mostly characterized by absorption maxima of their most intense bands located at ?max = 400-410 nm, except of the radical cations derived from 2,3-dihydrooxoisoaporphines. For the latter compounds, the absorption maxima of the most intense absorption bands are located at ?max = 290-295 nm. Their locations are independent of the presence of functional groups and the solvents used. They are formed in bimolecular processes with pseudo-first-order rate constants ranging from 2.1 × 10(5) to 1.5 × 10(6) s(-1) (in solutions containing 10(-4) M of the substrate), depending on the derivative and the solvent used. They are stable either when formed via the electron-transfer reaction with TCNE or when generated in isolation in pulse radiolysis of Ar-saturated 1,2-dichloroethane. In acetone and acetonitrile they decay predominantly by first-order kinetics with the first-order rate constants ranging from 2.3 × 10(4) to 5.1 × 10(4) s(-1). Formation of dimeric radical cations for all of the oxoisoaporphines studied was observed in acetonitrile solutions, and for azaoxoisoaporphines also in acetone solutions. The experimental spectra show a reasonably good agreement with the ZINDO/S semiempirical quantum mechanical calculations of radical cation absorptions. PMID:24802509

  13. Intermolecular interaction studies using small volumes.

    Science.gov (United States)

    Bourry, David; Sinnaeve, Davy; Gheysen, Katelijne; Fritzinger, Bernd; Vandenborre, Gianni; Van Damme, Els J M; Wieruszeski, Jean-Michel; Lippens, Guy; Ampe, Christophe; Martins, José C

    2011-01-01

    We present the use of 1-mm room-temperature probe technology to perform intermolecular interaction studies using chemical shift perturbation methods and saturation transfer difference (STD) spectroscopy using small sample volumes. The use of a small sample volume (5-10 µl) allows for an alternative titration protocol where individual samples are prepared for each titration point, rather than the usual protocol used for a 5-mm probe setup where the ligand is added consecutively to the solution containing the protein or host of interest. This allows for considerable economy in the consumption and cost of the protein and ligand amounts required for interaction studies. For titration experiments, the use of the 1-mm setup consumes less than 10% of the ligand amount required using a 5-mm setup. This is especially significant when complex ligands that are only available in limited quantities, typically because they are obtained from natural sources or through elaborate synthesis efforts, need to be investigated. While the use of smaller volumes does increase the measuring time, we demonstrate that the use of commercial small volume probes allows the study of interactions that would otherwise be impossible to address by NMR. PMID:21162136

  14. Enhanced electron transfer kinetics through hybrid graphene-carbon nanotube films.

    Science.gov (United States)

    Henry, Philémon A; Raut, Akshay S; Ubnoske, Stephen M; Parker, Charles B; Glass, Jeffrey T

    2014-11-01

    We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k(0), approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film. PMID:25309121

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

    Science.gov (United States)

    Vl?ek, 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 discussed process, back-ET in a porphyrin-Re(I)(CO)3(N,N) dyad, demonstrates that formation of a hot product accelerates highly exergonic ET in the Marcus inverted region. Overall, it follows that ET can be accelerated by enhancing the electronic interaction and by vibrational excitation of the reacting system and its medium, stressing the importance of quantum nuclear dynamics in ET reactivity. These effects are experimentally accessible by time-resolved vibrational spectroscopies (IR, Raman) in combination with quantum chemical calculations. It is suggested that structural dynamics play different mechanistic roles in light-triggered ET involving electronically excited donors or acceptors than in ground-state processes. While TRIR spectroscopy is well suitable to elucidate ET processes on a molecular-level, transient 2D-IR techniques combining optical and two IR (or terahertz) laser pulses present future opportunities for investigating, driving, and controlling ET. PMID:25699661

  16. Investigating the mechanism of thylakoid direct electron transfer for photocurrent generation

    International Nuclear Information System (INIS)

    Bioanodes incorporating thylakoids from spinach were studied to determine the mechanism of direct electron transfer to carbon electrodes. These electrodes generated a photocurrent of 0.43 ± 0.02 ?A/cm2. The change in this photocurrent was measured when individual components of thylakoids were removed, inhibited, or activated in order to determine which components contributed to the photocurrent. The results indicate that photosystems I and II, plastoquinone, cytochrome b6f, and plastocyanin are involved in the direct electron transfer mechanism and both electron transport pathways in photosynthesis (cyclic and noncyclic) contribute to the photocurrent. One of the benefits to using an organelle as a biocatalyst is the possibility for multiple electron transfer pathways at the electrode surface. The reported thylakoid electrodes show a contribution of electrons from the first five electron transfer steps in photosynthesis with only the last two steps not participating

  17. Heterogeneous electron transfer at nanoscopic electrodes: importance of electronic structures and electric double layers.

    Science.gov (United States)

    Chen, Shengli; Liu, Yuwen; Chen, Junxiang

    2014-08-01

    Heterogeneous electron-transfer (ET) processes at solid electrodes play key roles in molecular electronics and electrochemical energy conversion and sensing. Electrode nanosization and/or nanostructurization are among the major current strategies for performance promotion in these fields. Besides, nano-sized/structured electrodes offer great opportunities to characterize electrochemical structures and processes with high spatial and temporal resolution. This review presents recent insights into the nanoscopic size and structure effects of electrodes and electrode materials on heterogeneous ET kinetics, by emphasizing the importance of the electric double-layer (EDL) at the electrode/electrolyte interface and the electronic structure of electrode materials. It is shown, by general conceptual analysis and recent example demonstrations of representative electrode systems including electrodes of nanometer sizes and gaps and of nanomaterials such as sp(2) hybridized nanocarbons and semiconductor quantum dots, how the heterogeneous ET kinetics, the electronic structures of electrodes, the EDL structures at the electrode/electrolyte interface and the nanoscopic electrode sizes and structures may be related. PMID:24871071

  18. Ab initio quantum mechanical/molecular mechanical simulation of electron transfer process: Fractional electron approach

    International Nuclear Information System (INIS)

    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(H2O)62+/3+ and Ru(H2O)62+/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

  19. Photoinduced electron transfer in fullerene triads bearing pyrene and fluorene

    International Nuclear Information System (INIS)

    Photochemical properties of pyrene and fluorene appended fulleropyrrolidine triads (AH1-C60-AH2; AH1=pyrene and fluorene; AH2=naphthalene and phenyl) are reported. Electrochemical studies using cyclic voltammetry technique and DFT calculations at B3LYP/3-21G(*) method revealed that the charge-separated states in pyrene and fluorene appended triads are pyrenedot+-C60dot-AH2 and fluorenedot+-C60dot-AH2, respectively; however, no such charge-separated states could be established for naphthalene and phenyl appended triads. As demonstrated from the time resolved fluorescence, upon excitation of AH moiety in nonpolar solvents, energy transfer predominantly occurred from the singlet excited fluorophore to the C60 moiety, whereas in polar DMF charge-separation also contributed to the fluorescence quenching. Additionally, charge separation also occurred from the singlet excited C60 to the pyrene or fluorene entities of the triads in DMF. The rates and quantum yields of charge separation obtained by time-resolved emission studies were around 109s-1 and 0.9-0.6 for pyrene-C60-AH2 and fluorene-C60-AH2 triads. Nanosecond transient absorption spectral studies performed by using 355nm laser light on the triads, exhibited transient bands corresponding to thibited transient bands corresponding to the C60dot- and pyrenedot+ or fluorenedot+, thus establishing the occurrence of electron transfer in these triads in DMF. The rates of charge recombination obtained by monitoring the decay of the C60dot- were found to be around 106s-1 in DMF which resulted in the lifetimes of the radical ion pairs up to 1000ns indicating charge stabilization in pyrene-C60-AH2 and fluorene-C60-AH2 triads. The formations of long-lived charge-separated states, pyrenedot+-C60d'ot-AH2 and fluorenedot+-C60dot-AH2 in DMF, were rationalized by evaluating the Marcus parameters from the temperature dependence of the charge-recombination rate constants

  20. Fold versus Sequence Effects on the Driving Force for Protein Mediated Electron Transfer

    OpenAIRE

    Perrin, Bradley Scott; Ichiye, Toshiko

    2010-01-01

    Electron transport chains composed of electron transfer reactions mainly between proteins provide fast, efficient flow of energy in a variety of metabolic pathways. Reduction potentials are essential characteristics of the proteins because they determine the driving forces for the electron transfers. Since both polar and charged groups from the backbone and side chains define the electrostatic environment, both the fold and the sequence will contribute. However, while the role of a specific s...

  1. Intermolecular interactions in solid benzene

    Science.gov (United States)

    Kearley, G. J.; Johnson, M. R.; Tomkinson, J.

    2006-01-01

    The lattice dynamics and molecular vibrations of benzene and deuterated benzene crystals are calculated from force constants derived from density-functional theory (DFT) calculations and compared with measured inelastic neutron-scattering spectra. A very small change (0.5%) in lattice parameter is required to obtain real lattice-mode frequencies across the Brillouin zone. There is a strong coupling between wagging and breathing modes away from the zone center. This coupling and sensitivity to cell size arises from two basic interactions. Firstly, comparatively strong interactions that hold the benzene molecules together in layers. These include an intermolecular interaction in which H atoms of one molecule link to the center of the aromatic ring of a neighboring molecule. The layers are held to each other by weaker interactions, which also have components that hold molecules together within a layer. Small changes in the lattice parameters change this second type of interaction and account for the changes to the lattice dynamics. The calculations also reveal a small auxetic effect in that elongation of the crystal along the b axis leads to an increase in internal pressure in the ac plane, that is, elongation in the b direction induces expansion in the a and c directions.

  2. Role of ligand substitution on long-range electron transfer in azurins

    DEFF Research Database (Denmark)

    Farver, O; Jeuken, L J

    2000-01-01

    Azurin contains two potential redox sites, a copper centre and, at the opposite end of the molecule, a cystine disulfide (RSSR). Intramolecular electron transfer between a pulse radiolytically produced RSSR- radical anion and the blue Cu(II) ion was studied in a series of azurins in which single-site mutations were introduced into the copper ligand sphere. In the Met121His mutant, the rate constant for intramolecular electron transfer is half that of the corresponding wild-type azurin. In the His46Gly and His117Gly mutants, a water molecule is co-ordinated to the copper ion when no external ligands are added. Both these mutants also exhibit slower intramolecular electron transfer than the corresponding wild-type azurin. However, for the His117Gly mutant in the presence of excess imidazole, an azurin-imidazole complex is formed and the intramolecular electron-transfer rate increases considerably, becoming threefold faster than that observed in the native protein. Activation parameters for all these electron-transfer processes were determined and combined with data from earlier studies on intramolecular electron transfer in wild-type and single-site-mutated azurins. A linear relationship between activation enthalpy and activation entropy was observed. These results are discussed in terms of reorganization energies, driving force and possible electron-transfer pathways.

  3. A new mechanism for electron transfer in fast ion-atomic collisions

    CERN Document Server

    Voitkiv, A B; Ullrich, J

    2008-01-01

    We discuss a new mechanism for the electron capture in fast ion-atom collisions. Similarly like in the radiative capture, where the electron transfer occurs due to photon emission, within the mechanism under consideration the electron capture takes place due to the emission of an additional electron. This first order capture process leads to the so called transfer-ionization and has a number of interesting features, in particular, in the target frame it results in the electron emission mainly into the backward semi-sphere.

  4. Coherent transfer of light polarization to electron spins in a semiconductor.

    Science.gov (United States)

    Kosaka, Hideo; Shigyou, Hideki; Mitsumori, Yasuyoshi; Rikitake, Yoshiaki; Imamura, Hiroshi; Kutsuwa, Takeshi; Arai, Koichiro; Edamatsu, Keiichi

    2008-03-01

    We demonstrate that the superposition of light polarization states is coherently transferred to electron spins in a semiconductor quantum well. By using time-resolved Kerr rotation, we observe the initial phase of Larmor precession of electron spins whose coherence is transferred from light. To break the electron-hole spin entanglement, we utilized the big discrepancy between the transverse g factors of electrons and light-holes. The result encourages us to make a quantum media converter between flying photon qubits and stationary electron-spin qubits in semiconductors. PMID:18352739

  5. Coherent transfer of light polarization to electron spins in a semiconductor

    CERN Document Server

    Kosaka, Hideo; Mitsumori, Yasuyoshi; Rikitake, Yoshiaki; Imamura, Hiroshi; Kutsuwa, Takeshi; Arai, Koichiro; Edamatsu, Keiichi

    2007-01-01

    We demonstrate that the superposition of light polarization states is coherently transferred to electron spins in a semiconductor quantum well. By using time-resolved Kerr rotation we observe the initial phase of Larmor precession of electron spins whose coherence is transferred from light. To break the electron-hole spin entanglement, we utilized the big discrepancy between the transverse g-factors of electrons and light holes. The result encourages us to make a quantum media converter between flying photon qubits and stationary electron spin qubits in semiconductors.

  6. Differential cross sections and electron transfer mechanisms in multiply charged ion-atom collisions

    International Nuclear Information System (INIS)

    Differential cross sections or single- and double electron capture in collisions of fully stripped, H-like and He-like projectiles on H2 and rare gas targets are reported. Theoretical analysis is derived in the framework of the impact parameter approximation. The importance, for simultaneous two-electron transfer, of second-order one-electron interaction terms, is emphasised. (author)

  7. Study of intermediates from transition metal excited-state electron-transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Hoffman, M.Z.

    1992-07-31

    Conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used to study the intermediates involved in transition metal excited-state electron-transfer reactions. These intermediates were excited state of Ru(II) and Cr(III) photosensitizers, their reduced forms, and species formed in reactions of redox quenchers and electron-transfer agents. Of particular concern was the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes. (DLC)

  8. A theory for adiabatic bond breaking electron transfer reactions at metal electrodes

    Science.gov (United States)

    Koper, Marc T. M.; Voth, Gregory A.

    1998-01-01

    A theory is formulated for bond breaking and electron transfer at metal electrodes, based on an adaptation of the Anderson-Newns Hamiltonian. The model provides an extension of Savéant's model for concerted bond breaking and electron transfer and yields Savéant's predictions in the limit of vanishing electronic coupling. Solvent dynamical effects are investigated by assuming an overdamped solvent motion and a ballistic bond breaking motion. It is found that in a sufficiently slow solvent the transfer coefficient and the activation enthalpy may become temperature dependent, although the effect is probably small for most combinations of redox couples and solvents at room temperature.

  9. A reversible photoredox reaction: Electron-transfer photoreduction of. beta. -lapachone by triethylamine

    Energy Technology Data Exchange (ETDEWEB)

    Ci, Xiaohong; Goodman, J.L.; Whitten, D.G. (Univ. of Rochester, NY (USA)); da Silva, R.S.; Nicodem, D.E. (Univ. of Rio de Janeiro (Brazil))

    1988-12-07

    Light-induced electron-transfer reactions are being studied as possible energy conversion or storage processes. One such reaction of a light-induced electron-transfer reaction and subsequent electron- and atom-transfer processes, which are at least partially reversible, is reported herein. The specific reaction studied was the photooxidation of triethylamine by excited state o-quinones. The energy stored in the overall process is modest, and the degree of reversibility is limited by the reactivity of the amine oxidation products. 33 refs.

  10. Single-molecule interfacial electron transfer dynamics manipulated by external electric current

    CERN Document Server

    Zhang, Guofeng; Chen, Ruiyun; Gao, Yan; Wang, Xiaobo; Jia, Suotang

    2011-01-01

    Interfacial electron transfer (IET) dynamics in 1,1'-dioctadecyl-3, 3, 3', 3'-tetramethylindodicarbocyanine (DiD) dye molecules / indium tin oxide (ITO) film system have been probed at the ensemble and single-molecule level by recording the change of fluorescence emission intensity. By comparing the difference of the external electric current (EEC) dependence of lifetime and intensity for enambles and single molecules, it is shown that the single-molecule probe can effcienly demonstrate the IET dynamics. The backward electron transfer and electron transfer of ground state induce the single molecules fluorescence quenching when an EEC is applied to ITO film.

  11. Electron-transfer reactions between viologen radical cations and quinones in AOT reverse micelles studied by electron pulse radiolysis

    International Nuclear Information System (INIS)

    Electron-transfer reactions between viologen radical cations (CnVsm-bullet+, n = 1-18) and various quinones have been studied in aqueous and reverse micellar (AOT/isooctane/H2O) solution by use of the electron pulse radiolysis technique. By use of dynamic light scattering measurements, the concentration of water pools was determined and the number of electron-transfer reactants per water pool could be calculated. Rate constants measured for the reaction between CnVsm-bullet+ radicals and anthraquinonesulfonate ions (AQS-) decreased with increasing length of the aliphatic chain of the viologens, caused by association of the viologen with the surfactant interface

  12. On the involvement of electron transfer reactions in the fluorescence decay kinetics heterogeneity of proteins.

    Science.gov (United States)

    Ababou, A; Bombarda, E

    2001-10-01

    Time-resolved fluorescence study of single tryptophan-containing proteins, nuclease, ribonuclease T1, protein G, glucagon, and mastoparan, has been carried out. Three different methods were used for the analysis of fluorescence decays: the iterative reconvolution method, as reviewed and developed in our laboratory, the maximum entropy method, and the recent method that we called "energy transfer" method. All the proteins show heterogeneous fluorescence kinetics (multiexponential decay). The origin of this heterogeneity is interpreted in terms of current theories of electron transfer process, which treat the electron transfer process as a radiationless transition. The theoretical electron transfer rate was calculated assuming the peptide bond carbonyl as the acceptor site. The good agreement between experimental and theoretical electron-transfer rates leads us to suggest that the electron-transfer process is the principal quenching mechanism of Trp fluorescence in proteins, resulting in heterogeneous fluorescence kinetics. Furthermore, the origin of apparent homogeneous fluorescence kinetics (monoexponential decay) in some proteins also can be explained on the basis of electron-transfer mechanism. PMID:11567101

  13. Electron Transfer Processes to Continuum in Near-Relativistic Ion-Atom Collisions

    International Nuclear Information System (INIS)

    Theories for electron transfer to the continuum have encountered considerable difficulties to take into account the intrinsic many-electron processes in the capture channel. This may partially be attributed to large momentum transfers involved and thus collision systems are mostly not in the realm of first order perturbation theories. For this reason we have studied collision systems where simultaneously distinct competing electron transfer processes are found to be active, like radiative (RECC) and non-radiative electron capture to continuum (ECC) in the relativistic domain where one or two even active electrons are involved; here another, though distinct, transfer process, the projectile electron loss to continuum (ELC), permits additionally to study the dynamics of ionization very close to threshold. We have studied these electron transfer processes simultaneously in forward electron emission in two systems of different projectile Compton profile, U88++N2 and Sn47++N2 collisions using the forward electron spectrometer at the supersonic jet-target of the ESR storage ring. We report first results and compare with theory.

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

    DEFF Research Database (Denmark)

    Shrestha, Pravin Malla; Rotaru, Amelia-Elena

    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 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.

  15. 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. PMID:24249299

  16. Effects of anharmonicity on diffusive-controlled symmetric electron transfer rates: From the weak to the strong electronic coupling regions

    International Nuclear Information System (INIS)

    The approach for the diffusive-controlled electron transfer rates [W. Zhu and Y. Zhao, J. Chem. Phys. 126, 184105 (2007)], which is modeled after the Sumi-Marcus theory, is applied to symmetric electron-transfer reactions in a solvent environment with anharmonic potential functions. The electron-transfer rates are evaluated using the quantum R-matrix theory for dealing with the intramolecular vibrational motions and imaginary-time split operator technique for solving the diffusive equations, thereby taking explicit account of the weak-to-strong electronic couplings. The effect of anharmonicity for both the solvent and intramolecular vibrational degrees of freedom are investigated. It is found that the anharmonicity of the intramolecular modes always enhances the rate while the solvent anharmonicity decreases the rate, compared with the harmonic modes. The possible mechanisms have been clarified.

  17. The Role of Protein Fluctuation Correlations in Electron Transfer in Photosynthetic Complexes

    CERN Document Server

    Nesterov, Alexander I

    2014-01-01

    We consider the dependence of the electron transfer in photosynthetic complexes on correlation properties of random fluctuations of the protein environment. The electron subsystem is modeled by a finite network of connected electron (exciton) sites. The fluctuations of the protein environment are modeled by random telegraph processes, which act either collectively (correlated) or independently (uncorrelated) on the electron sites. We derived an exact closed system of first-order linear differential equations with constant coefficients, for the average density matrix elements and for their first moments. Under some conditions, we obtain analytic expressions for the electron transfer rates. We compare the correlated and uncorrelated regimes, and demonstrated numerically that the uncorrelated fluctuations of the protein environment can, under some conditions, either increase or decrease the electron transfer rates.

  18. Transferable pseudoclassical electrons for aufbau of atomic ions.

    Science.gov (United States)

    Ekesan, Solen; Kale, Seyit; Herzfeld, Judith

    2014-06-01

    Generalizing the LEWIS reactive force field from electron pairs to single electrons, we present LEWIS• in which explicit valence electrons interact with each other and with nuclear cores via pairwise interactions. The valence electrons are independently mobile particles, following classical equations of motion according to potentials modified from Coulombic as required to capture quantum characteristics. As proof of principle, the aufbau of atomic ions is described for diverse main group elements from the first three rows of the periodic table, using a single potential for interactions between electrons of like spin and another for electrons of unlike spin. The electrons of each spin are found to distribute themselves in a fashion akin to the major lobes of the hybrid atomic orbitals, suggesting a pointillist description of the electron density. The broader validity of the LEWIS• force field is illustrated by predicting the vibrational frequencies of diatomic and triatomic hydrogen species. PMID:24752384

  19. Pulse radiolytic studies of electron transfer processes and applications to solar photochemistry. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    Neta, P.

    1995-02-01

    The pulse radiolysis technique is applied to the study of electron transfer processes in a variety of chemical systems. Reactive intermediates are produced in solution by electron pulse irradiation and the kinetics of their reactions are followed by time resolved absorption spectrophotometry. Complementary experiments are carried out with excimer laser flash photolysis. These studies are concerned with mechanisms, kinetics, and thermodynamics of reactions of organic and inorganic radicals and unstable oxidation states of metal ions. Reactions are studied in both aqueous and non-aqueous solutions. The studies focus on the unique ability of pulse radiolysis to provide absolute rate constants for reactions of many inorganic radicals and organic peroxyl radicals, species that are key intermediates in many chemical processes. A special concern of this work is the study of electron transfer reactions of metalloporphyrins, which permits evaluation of these molecules as intermediates in solar energy conversion. Metalloporphyrins react with free radicals via electron transfer, involving the ligand or the metal center, or via bonding to the metal, leading to a variety of chemical species whose behavior is also investigated. The highlights of the results during the past three years are summarized below under the following sections: (a) electron transfer reactions of peroxyl radicals, concentrating on the characterization of new peroxyl radicals derived from vinyl, phenyl, other aryl, and pyridyl; (b) solvent effects on electron transfer reactions of inorganic and organic peroxyl radicals, including reactions with porphyrins, and (c) electron transfer and alkylation reactions of metalloporphyrins and other complexes.

  20. Ultrafast tryptophan-to-heme electron transfer in myoglobins revealed by UV 2D spectroscopy.

    Science.gov (United States)

    Consani, Cristina; Auböck, Gerald; van Mourik, Frank; Chergui, Majed

    2013-03-29

    Tryptophan is commonly used to study protein structure and dynamics, such as protein folding, as a donor in fluorescence resonant energy transfer (FRET) studies. By using ultra-broadband ultrafast two-dimensional (2D) spectroscopy in the ultraviolet (UV) and transient absorption in the visible range, we have disentangled the excited state decay pathways of the tryptophan amino acid residues in ferric myoglobins (MbCN and metMb). Whereas the more distant tryptophan (Trp(7)) relaxes by energy transfer to the heme, Trp(14) excitation predominantly decays by electron transfer to the heme. The excited Trp(14)?heme electron transfer occurs in <40 picoseconds with a quantum yield of more than 60%, over an edge-to-edge distance below ~10 angstroms, outcompeting the FRET process. Our results raise the question of whether such electron transfer pathways occur in a larger class of proteins. PMID:23393092

  1. Dynamic modulation of electron correlation by intramolecular modes in charge transfer compounds

    CERN Document Server

    Meneghetti, M

    1999-01-01

    Electron-phonon and electron-electron interactions are in competition in determining the properties of molecular charge transfer conductors and superconductors. The direct influence of phonons on the electron-electron interaction was not before considered and in the present work the coupling of intramolecular modes to electron-electron interaction (U-vib interaction) is investigated.The effect of this coupling on the frequency of the normal modes of a dimer model is obtained and it is shown that frequency shifts of the Raman active modes are directly related to this coupling. The results are used to obtain the values of the U-vib coupling constants of intramolecular modes of a representative molecule of charge transfer conductors, like tetramethyltetratiafulvalene. Consequences of this coupling on the electron pairing are also suggested.

  2. Model-free Investigation of Ultrafast Bimolecular Chemical Reactions: Bimolecular Photo Induced Electron Transfer

    OpenAIRE

    Rosspeintner Arnulf; Lang Bernhard; Vauthey Eric

    2013-01-01

    Using photoinduced bimolecular electron transfer reactions as example we demonstrate how diffusion controlled bimolecular chemical reactions can be studied in a model-free manner by quantitatively combining different ultrafast spectroscopical tools.

  3. Density functional reactivity theory characterizes charge separation propensity in proton-coupled electron transfer reactions.

    Science.gov (United States)

    Liu, Shubin; Ess, Daniel H; Schauer, Cynthia K

    2011-05-12

    Proton-coupled electron transfer (PCET) reactions occur in many biological and artificial solar energy conversion processes. In these reactions the electron is often transferred to a site distant to the proton acceptor site. In this work, we employ the dual descriptor and the electrophilic Fukui function from density functional reactivity theory (DFRT) to characterize the propensity for an electron to be transferred to a site other than the proton acceptor site. The electrophilic regions of hydrogen bond or van der Waal reactant complexes were examined using these DFRT descriptors to determine the region of space to which the electron is most likely to be transferred. This analysis shows that in PCET reactions the electrophilic region of the reactant complex does not include the proton acceptor site. PMID:21506583

  4. Design of a Molecular Memory Device: The Electron Transfer Shift Register Memory

    Science.gov (United States)

    Beratan, D.

    1993-01-01

    A molecular shift register memory at the molecular level is described. The memory elements consist of molecules can exit in either an oxidized or reduced state and the bits are shifted between the cells with photoinduced electron transfer reactions.

  5. THEORETICAL STUDY OF 100 GHz GaAs TRANSFERRED-ELECTRON DEVICES

    OpenAIRE

    Rolland, P.; Friscourt, M.; Salmer, G.; Constant, E.

    1981-01-01

    Computer simulations of GaAs Transferred Electron Devices have been performed using a model which includes relaxation effects as well as spatial dependence. Some results are presented and discussed for 100 GHz GaAs short Gunn diodes.

  6. Energy transfer mechanism of electron excitation from UO22+ to Eu3+ in phosphate glasses

    International Nuclear Information System (INIS)

    The concentration dependence of luminescent-kinetic properties of the Eu3+-activated cesium uranyl-phosphate glasses is investigated. It is concluded that the energy transfer mechanism of electron excitation may be explained from the viewpoint of exchange interactions

  7. Electrode assemblies composed of redox cascades from microbial respiratory electron transfer chains

    Energy Technology Data Exchange (ETDEWEB)

    Gates, Andrew J.; Marritt, Sophie; Bradley, Justin; Shi, Liang; McMillan, Duncan G.; Jeuken, Lars J.; Richardson, David; Butt, Julea N.

    2013-10-01

    Respiratory and photosynthetic electron transfer chains are dependent on vectorial electron transfer through a series of redox proteins. Examples include electron transfer from NapC to NapAB nitrate reductase in Paracoccus denitrificans and from CymA to Fcc3 (flavocytochrome c3) fumarate reductase in Shewanella oneidensis MR-1. In the present article, we demonstrate that graphite electrodes can serve as surfaces for the stepwise adsorption of NapC and NapAB, and the stepwise adsorption of CymA and Fcc3. Aspects of the catalytic properties of these assemblies are different from those of NapAB and Fcc3 adsorbed in isolation. We propose that this is due to the formation of NapC-NapAB and of CymA-Fcc3 complexes that are capable of supporting vectorial electron transfer.

  8. ElectronTransfer Induced Ring Opening of α-Epoxyketones: Spirodioxolane Formation

    Directory of Open Access Journals (Sweden)

    Farzad Nikpour

    2002-01-01

    Full Text Available Stereospecific formation of spirodioxolanes has been observed on electron transfer induced ring opening of α-epoxyketones by 2,4,6-triphenylpyrylium tetrafluoroborate in the presence of cyclohexanone

  9. An efficient implementation of the localized operator partitioning method for electronic energy transfer

    OpenAIRE

    Nagesh, Jayashree; Izmaylov, Artur F.; Brumer, Paul

    2014-01-01

    The localized operator partitioning method [Y. Khan and P. Brumer, J. Chem. Phys. 137, 194112 (2012)] rigorously defines the electronic energy on any subsystem within a molecule and gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. However, an efficient implementation of this approach has been hindered by complicated one- and two-electron integrals arising in i...

  10. Topological and Conformational Effects on Electron Transfer Dynamics in Porphyrin-[60]Fullerene Interlocked Systems

    OpenAIRE

    Megiatto, Jackson D.; Schuster, David I.; Miguel, Gustavo; Wolfrum, Silke; Guldi, Dirk M.

    2012-01-01

    The effect of molecular topology, and conformation on the dynamics of photoinduced electron transfer (ET) processes has been studied in interlocked electron donor-acceptor systems, specifically rotaxanes with zinc(II)-tetraphenylporphyrin (ZnP) electron donor and [60]fullerene (C60) as the electron acceptor. Formation or cleavage of coordinative bonds was used to induce major topological and conformational changes in the interlocked architecture. In the first approach, the tweezers-like struc...

  11. Electron transfer dynamics and excited state branching in a charge-transfer platinum(II) donor-bridge-acceptor assembly.

    Science.gov (United States)

    Scattergood, Paul A; Delor, Milan; Sazanovich, Igor V; Bouganov, Oleg V; Tikhomirov, Sergei A; Stasheuski, Alexander S; Parker, Anthony W; Greetham, Gregory M; Towrie, Michael; Davies, E Stephen; Meijer, Anthony J H M; Weinstein, Julia A

    2014-12-21

    A linear asymmetric Pt(ii) trans-acetylide donor-bridge-acceptor triad designed for efficient charge separation, NAP[triple bond, length as m-dash]Pt(PBu3)2[triple bond, length as m-dash]Ph-CH2-PTZ (), containing strong electron acceptor and donor groups, 4-ethynyl-N-octyl-1,8-naphthalimide (NAP) and phenothiazine (PTZ) respectively, has been synthesised and its photoinduced charge transfer processes characterised in detail. Excitation with 400 nm, ?50 fs laser pulse initially populates a charge transfer manifold stemming from electron transfer from the Pt-acetylide centre to the NAP acceptor and triggers a cascade of charge and energy transfer events. A combination of ultrafast time-resolved infrared (TRIR) and transient absorption (TA) spectroscopies, supported by UV-Vis/IR spectroelectrochemistry, emission spectroscopy and DFT calculations reveals a self-consistent photophysical picture of the excited state evolution from femto- to milliseconds. The characteristic features of the NAP-anion and PTZ-cation are clearly observed in both the TRIR and TA spectra, confirming the occurrence of electron transfer and allowing the rate constants of individual ET-steps to be obtained. Intriguingly, has three separate ultrafast electron transfer pathways from a non-thermalised charge transfer manifold directly observed by TRIR on timescales ranging from 0.2 to 14 ps: charge recombination to form either the intraligand triplet (3)NAP with 57% yield, or the ground state, and forward electron transfer to form the full charge-separated state (3)CSS ((3)[PTZ(+)-NAP(-)]) with 10% yield as determined by target analysis. The (3)CSS decays by charge-recombination to the ground state with ?1 ns lifetime. The lowest excited state is (3)NAP, which possesses a long lifetime of 190 ?s and efficiently sensitises singlet oxygen. Overall, molecular donor-bridge-acceptor triad demonstrates excited state branching over 3 different pathways, including formation of a long-distant (18 Å) full charge-separated excited state from a directly observed vibrationally hot precursor state. PMID:25361227

  12. Bridge Mediated Electron Transfer in Conjugated and Cross-Conjugated Donor-Acceptor Compounds

    OpenAIRE

    Go?ransson, Erik

    2012-01-01

    Detailed understanding of electron transfer reactions is important in many aspects of chemistry, biology and solar energy conversion. The main aim of this thesis is to provide further insight into electron transfer through highly conjugated bridge structures. Towards this end, three series of donor-acceptor dyads have been studied, all using an oligo(1,4-phenylene-ethynylene) moiety as the bridge. A common theme in these series is that they explore the effects of having either an ethynylene o...

  13. Constraint-Based Modeling of Carbon Fixation and the Energetics of Electron Transfer in Geobacter metallireducens

    OpenAIRE

    Feist, Adam M.; Nagarajan, Harish; Rotaru, Amelia-elena; Tremblay, Pier-luc; Zhang, Tian; Nevin, Kelly P.; Lovley, Derek R.; Zengler, Karsten

    2014-01-01

    Geobacter species are of great interest for environmental and biotechnology applications as they can carry out direct electron transfer to insoluble metals or other microorganisms and have the ability to assimilate inorganic carbon. Here, we report on the capability and key enabling metabolic machinery of Geobacter metallireducens GS-15 to carry out CO2 fixation and direct electron transfer to iron. An updated metabolic reconstruction was generated, growth screens on targeted conditions of in...

  14. Electrostatic effects on electron-transfer kinetics in the cytochrome f-plastocyanin complex.

    OpenAIRE

    Soriano, G. M.; Cramer, W. A.; Krishtalik, L. I.

    1997-01-01

    In a complex of two electron-transfer proteins, their redox potentials can be shifted due to changes in the dielectric surroundings and the electrostatic potentials at each center caused by the charged residues of the partner. These effects are dependent on the geometry of the complex. Three different docking configurations (DCs) for intracomplex electron transfer between cytochrome f and plastocyanin were studied, defined by 1) close contact of the positively charged region of cytochrome f a...

  15. Rate of Interfacial Electron Transfer through the 1,2,3-Triazole Linkage

    OpenAIRE

    Devaraj, Neal K.; Decreau, Richard A.; Ebina, Wataru; Collman, James P.; Chidsey, Christopher E. D.

    2006-01-01

    The rate of electron transfer is measured to two ferrocene and one iron tetraphenylporphyrin redox species coupled through terminal acetylenes to azide-terminated thiol monolayers by the Cu(I)-catalyzed azide–alkyne cycloaddition (a Sharpless “click” reaction) to form the 1,2,3-triazole linkage. The high yield, chemoselectivity, convenience, and broad applicability of this triazole formation reaction make such a modular assembly strategy very attractive. Electron-transfer rate constants...

  16. Electronic transfer of prescription-related information: comparing views of patients, general practitioners, and pharmacists.

    OpenAIRE

    Porteous, Terry; Bond, Christine; Robertson, Roma; Hannaford, Philip; Reiter, Ehud

    2003-01-01

    BACKGROUND: The National Health Service (NHS) intends to introduce a system of electronic transfer of prescription-related information between general practitioners (GPs) and community pharmacies. The NHS Plan describes how this will be achieved. AIM: To gather opinions of patients, GPs, and community pharmacists on the development of a system of electronic transfer of prescription-related information between GPs and community pharmacies. DESIGN OF STUDY: Survey combining interviews, focus gr...

  17. Nanofibers of hydrogen-bonded two-component gel with closely connected p- and n-channels and photoinduced electron transfer.

    Science.gov (United States)

    Xue, Pengchong; Wang, Panpan; Yao, Boqi; Sun, Jiabao; Gong, Peng; Zhang, Zhenqi; Qian, Chong; Lu, Ran

    2014-12-10

    An D-A-D gelator (DTCQ) was designed and synthesized using 2,3-dimethyl-5,8-di(thiophen-2-yl)quinoxaline and N-alkyl 3-aminocarbazole units as acceptor and donor, respectively, which were linked by a single bond. The compound could gelate several solvents, such as benzyl alcohol, aniline, acetophenone, and o-dichlorobenzene, as well as self-assemble into one-dimensional (1D) nanofibers in gel phase. The absorption and infrared spectra of the gels indicated that ?-? interactions between aromatic moieties, intermolecular hydrogen bonds between amide units, and van der Waals forces were the driving forces for the formation of 1D self-assemblies and gel. DTCQ gel was red and emits red fluorescence because it has a strong absorption band at 487 nm and an emissive band at 620 nm. Moreover, DTCQ and a fullerene carboxylic acid formed two-component gel, in which the two compounds developed a hydrogen bond complex and self-assembled into 1D nanofibers with closely connected p- and n-channels. The nanofibrous xerogel film can rapidly generate a photocurrent under visible-light radiation through electron transfer from the gelator to fullerene, and then, the excellent exciton separation and charge transfer to two electrodes. PMID:25347786

  18. Toward transferable interatomic van der Waals potentials: The role of multipole electrostatics and many-body dispersion without electrons

    CERN Document Server

    Bereau, Tristan

    2014-01-01

    We estimate polarizabilities of atoms in molecules without electron density, using a Voronoi partitioning approach instead. The resulting atomic dispersion coefficients are calculated, as well as many-body dispersion effects on intermolecular potential energies. We also estimate contributions from multipole electrostatics and compare them to dispersion. We assess the performance of the resulting intermolecular potential from dispersion and electrostatics for more than 1,300 neutral and charged, small organic molecular dimers. Applications to water clusters, the benzene crystal, the anti-cancer drug ellipticine---intercalated between two Watson-Crick DNA base pairs, as well as six macro-molecular host-guest complexes highlight the potential of this method and help to identify points of future improvement. Overall, the method achieves an accuracy well within sophisticated empirical force fields, such as OPLS and Amber FF03, while exhibiting a simple parametrization protocol without the need for experimental inp...

  19. Microbial nanowires: a new paradigm for biological electron transfer and bioelectronics.

    Science.gov (United States)

    Malvankar, Nikhil S; Lovley, Derek R

    2012-06-01

    The discovery that Geobacter sulfurreducens can produce protein filaments with metallic-like conductivity, known as microbial nanowires, that facilitate long-range electron transport is a paradigm shift in biological electron transfer and has important implications for biogeochemistry, microbial ecology, and the emerging field of bioelectronics. Although filaments in a wide diversity of microorganisms have been called microbial nanowires, the type IV pili of G. sulfurreducens and G. metallireducens are the only filaments that have been shown to be required for extracellular electron transport to extracellular electron acceptors or for conduction of electrons through biofilms. Studies of G. sulfurreducens pili preparations and intact biofilms under physiologically relevant conditions have provided multiple lines of evidence for metallic-like conduction along the length of pili and for the possibility of pili networks to confer high conductivity within biofilms. This mechanism of electron conduction contrasts with the previously known mechanism for biological electron transfer via electron tunneling or hopping between closely associated molecules, a strategy unlikely to be well adapted for long-range electron transport outside the cell. In addition to promoting electron exchange with abiotic electron acceptors, microbial nanowires have recently been shown to be involved in direct interspecies electron transfer between syntrophic partners. An improved understanding of the mechanisms for metallic-like conductivity in microbial nanowires, as well as engineering microorganisms with desirable catalytic abilities with nanowires, could lead to new applications in microbial electrosynthesis and bioelectronics. PMID:22614997

  20. Experimental and Theoretical Demonstrations for the Mechanism behind Enhanced Microbial Electron Transfer by CNT Network

    Science.gov (United States)

    Liu, Xian-Wei; Chen, Jie-Jie; Huang, Yu-Xi; Sun, Xue-Fei; Sheng, Guo-Ping; Li, Dao-Bo; Xiong, Lu; Zhang, Yuan-Yuan; Zhao, Feng; Yu, Han-Qing

    2014-01-01

    Bioelectrochemical systems (BESs) share the principle of the microbially catalyzed anodic substrate oxidation. Creating an electrode interface to promote extracellular electron transfer from microbes to electrode and understanding such mechanisms are crucial for engineering BESs. In this study, significantly promoted electron transfer and a 10-times increase in current generation in a BES were achieved by the utilization of carbon nanotube (CNT) network, compared with carbon paper. The mechanisms for the enhanced current generation with the CNT network were elucidated with both experimental approach and molecular dynamic simulations. The fabricated CNT network was found to be able to substantially enhance the interaction between the c-type cytochromes and solid electron acceptor, indicating that the direct electron transfer from outer-membrane decaheme c-type cytochromes to electrode might occur. The results obtained in this study will benefit for the optimized design of new materials to target the outer membrane proteins for enhanced electron exchanges.

  1. Charge transfer dynamics from adsorbates to surfaces with single active electron and configuration interaction based approaches

    Science.gov (United States)

    Ramakrishnan, Raghunathan; Nest, Mathias

    2015-01-01

    We employ wavepacket simulations based on many-body time-dependent configuration interaction (TD-CI), and single active electron theories, to predict the ultrafast molecule/metal electron transfer time scales, in cyano alkanethiolates bonded to model gold clusters. The initial states represent two excited states where a valence electron is promoted to one of the two virtual ?? molecular orbitals localized on the cyanide fragment. The ratio of the two time scales indicate the efficiency of one charge transfer channel over the other. In both our one-and many-electron simulations, this ratio agree qualitatively with each other as well as with the previously reported experimental time scales (Blobner et al., 2012), measured for a macroscopic metal surface. We study the effect of cluster size and the description of electron correlation on the charge transfer process.

  2. Transfer of single electrons and single cooper pairs in nanojunction circuits

    International Nuclear Information System (INIS)

    Electrons can be made to pass through a circuit one by one, in nanoscale devices based on the combination of the Coulomb interaction between electrons and their passage by quantum tunnelling through an insulating barrier. Under appropriate conditions, when parts of the circuit are superconducting, it is possible to observe a direct manifestation of electron pairing: the transfer of electrons two by two. Single-electron devices provide a new way of measuring the charge quantum, and clarify how electronic signal processing at the molecular level might function. (authors). 59 refs., 10 figs

  3. Proton-Coupled Electron Transfer of Ruthenium(III)-Pterin Complexes: A Mechanistic Insight

    OpenAIRE

    Miyazaki, Soushi; Kojima, Takahiko; Mayer, James M.; Fukuzumi, Shunichi

    2009-01-01

    Ruthenium(II) complexes having pterins of redox-active heteroaromatic coenzymes as ligands were demonstrated to perform multistep proton transfer (PT), electron transfer (ET), and proton-coupled electron transfer (PCET) processes. Thermodynamic parameters including pKa, bond dissociation energy (BDE) of multistep PCET processes in acetonitrile (MeCN) were determined for ruthenium-pterin complexes, [RuII(Hdmp)(TPA)](ClO4)2 (1), [RuII(Hdmdmp)(TPA)](ClO4)2 (2), [RuII(dmp?)(TPA)]ClO4 (3) and [R...

  4. Use of electron-excitation energy transfer in dye laser active media

    Energy Technology Data Exchange (ETDEWEB)

    Rodchenkova, V.V.; Reva, M.G.; Akimov, A.I.; Uzhinov, B.M.

    1984-01-01

    A study was made of the spectral luminescence and lasing characteristics of two-component dye mixtures, and of the use of electron-excitation energy transfer to improve the laser emission parameters. A considerable increase in the lasing efficiencyu was found on exciting Trypaflavine by energy transfer from coumarin dyes. The use of electron-excitation energy transfer enabled the laser emission spectrum to be broadened. It was found that by varying the energy donor and acceptor concentrations one could produce laser emission of constant intensity in the spectral range between the donor and acceptor lasing regions.

  5. Intermolecular interactions during ultrafiltration of pegylated proteins.

    Science.gov (United States)

    Ruanjaikaen, Krisada; Zydney, Andrew L

    2013-01-01

    Recent studies have demonstrated the feasibility of using membrane ultrafiltration for the purification of pegylated proteins; however, the separations have all been performed at relatively low protein concentrations where intermolecular interactions are unimportant. The objective of this study was to examine the behavior at higher PEG concentrations and to develop an appropriate theoretical framework to describe the effects of intermolecular interactions. Ultrafiltration experiments were performed using pegylated ?-lactalbumin as a model protein with both neutral and charged composite regenerated cellulose membranes. The transmission of the pegylated ?-lactalbumin, PEG, and ?-lactalbumin all increase with increasing PEG concentration due to the increase in the solute partition coefficient arising from unfavorable intermolecular interactions in the bulk solution. The experimental results were in good agreement with a simple model that accounts for the change in Gibbs free energy associated with these intermolecular interactions, including the effects of concentration polarization on the local solute concentrations upstream of the membrane. These intermolecular interactions are shown to cause a greater than expected loss of pegylated product in a batch ultrafiltration system, and they alter the yield and purification factor that can be achieved during a diafiltration process to remove unreacted PEG. PMID:23436792

  6. Energy transfer processes in solar energy conversion

    Energy Technology Data Exchange (ETDEWEB)

    Fayer, M.D.

    1987-01-01

    This program involves the experimental and theoretical study of optically induced electron transfer and electronic excitation transport in systems with complex structures. The focus is to obtain an understanding of the intimate interplay among intermolecular interactions, structure, and dynamics. A combination of picosecond transient grating experiments, time resolved fluorescence depolarization experiments, conventional optical spectroscopy, and statistical mechanical theory is being employed to elucidated fundamental aspects of processes which are important in the conversion of solar energy to usable forms of energy. We are continuing to address the very important problem of electron back transfer following optically induced donor to acceptor electron transfer. In a system in which there are donors (low concentration) and acceptors (high concentration) randomly distributed in solution, optical excitation of a donor can be followed by transfer of an electron to an acceptor. One electron transfer has occurred. there exists a ground state radical cation (D{sup +}) near a ground state radical anion (A{sup {minus}}). Since the thermodynamically stable state is neutral ground state D and A, back transfer will occur. The electron will back transfer from A{sup {minus}} to D{sup +} to regenerate the neutral species. In liquid solution, back transfer competes with separation by diffusion. Separated ions are extremely reactive and can go on to do useful chemistry. 10 refs.

  7. Concerted electron-proton transfer in the optical excitation of hydrogen-bonded dyes

    Science.gov (United States)

    Westlake, Brittany C.; Brennaman, M. Kyle; Concepcion, Javier J.; Paul, Jared J.; Bettis, Stephanie E.; Hampton, Shaun D.; Miller, Stephen A.; Lebedeva, Natalia V.; Forbes, Malcolm D. E.; Moran, Andrew M.; Meyer, Thomas J.; Papanikolas, John M.

    2011-01-01

    The simultaneous, concerted transfer of electrons and protons—electron-proton transfer (EPT)—is an important mechanism utilized in chemistry and biology to avoid high energy intermediates. There are many examples of thermally activated EPT in ground-state reactions and in excited states following photoexcitation and thermal relaxation. Here we report application of ultrafast excitation with absorption and Raman monitoring to detect a photochemically driven EPT process (photo-EPT). In this process, both electrons and protons are transferred during the absorption of a photon. Photo-EPT is induced by intramolecular charge-transfer (ICT) excitation of hydrogen-bonded-base adducts with either a coumarin dye or 4-nitro-4?-biphenylphenol. Femtosecond transient absorption spectral measurements following ICT excitation reveal the appearance of two spectroscopically distinct states having different dynamical signatures. One of these states corresponds to a conventional ICT excited state in which the transferring H+ is initially associated with the proton donor. Proton transfer to the base (B) then occurs on the picosecond time scale. The other state is an ICT-EPT photoproduct. Upon excitation it forms initially in the nuclear configuration of the ground state by application of the Franck–Condon principle. However, due to the change in electronic configuration induced by the transition, excitation is accompanied by proton transfer with the protonated base formed with a highly elongated +H?B bond. Coherent Raman spectroscopy confirms the presence of a vibrational mode corresponding to the protonated base in the optically prepared state. PMID:21555541

  8. 77 FR 30923 - Electronic Fund Transfers (Regulation E)

    Science.gov (United States)

    2012-05-24

    ...linked to a traditional checking account. The Bureau...information about a specific type of prepaid card known...linked to a traditional checking account, non-reloadable...account. Examples of types of transfers covered...a demand deposit (checking), savings, or...

  9. A comparison of electron transfer in ribonucleotide reductase and the bacterial photosynthetic reaction center

    Science.gov (United States)

    Siegbahn, Per E. M.; Blomberg, Margareta R. A.; Pavlov, Maria

    1998-08-01

    The energy requirements for electron transfer in two different proteins are compared, based on quantum chemical calculations. The methods used are the hybrid density functional B3LYP combined with dielectric cavity models to account for the effects of the polarizable protein. The experimental exothermicities for the electron transfer steps from the chlorophyll special pair both to the pheophytin and to the quinone are well reproduced. For ribonucleotide reductase (RNR), the same methods in contrast predict a large endothermicity for the electron transfer from the cysteine at the substrate site to the tyrosyl radical in the interior of the protein. This indicates that another type of process is active in RNR. Previous work has suggested that this process is hydrogen atom transfer.

  10. What are the benefits of bound (protonation) states for the electron-transfer kinetics?

    CERN Document Server

    Matyushov, Dmitry V

    2007-01-01

    We describe a model of electron transfer reactions affected by local binding to the donor or acceptor sites of a particle in equilibrium with the solution. The statistics of fluctuations of the donor-acceptor energy gap caused by binding/unbinding events are non-Gaussian, and the resulting free energy surfaces of electron transfer are non-parabolic. The band-width of the charge-transfer optical transition is predicted to pass through a maximum as a function of the concentration of binding particles in the solution. The model is used to rationalize recent observations of pH-dependence of electron transfer rates involving changes in the protonation state of the donor-acceptor complex.

  11. MAGNETIC PROPERTIES AND ELECTRON TRANSFER IN BINUCLEAR ORGANO-IRON SANDWICHES

    OpenAIRE

    Guillin, J.; Desbois, M.; Lacoste, M.; Astruc, D.; Varret, F.

    1988-01-01

    Bi-iron electron reservoirs complexes, of sandwich structure, have been studied in the 36, 37, 38 e- states, by Mössbauer spectroscopy in external magnetic fields. The nature of the various couplings between the 19 e- subunits has been elucidated, and correlated to the electron transfer to the bridge in the mixed valence state.

  12. ESR studies of radiation induced electron transfer between myosin and caffeic acid

    International Nuclear Information System (INIS)

    The mechanism of radiation induced electron transfer within a series of binary molecular aggregates, which were composed of myosin and caffeic acid with varied molar ratios (r) of amino acid residues in myosin to caffeic acid, has been studied by resolution of composite ESR spectra recorded at 77 K. A series of spin transfer ratios (RST) defined as the spin concentration ratios of caffeic acid anion radical arising from transfer of captured electron by peptide chain of myosin to that from directly trapping of secondary electrons by caffeic acid were obtained. A series of RST were plotted against r varied from 1:1 to 100:1. A linear relationship between RSt and r demonstrates that RSt increase linearly with decrease of caffeic acid content. The capture of radiation induced secondary electrons depend on the electron affinities of components including electron affinitive amino acid residues and peptide carbonyl of myosin and caffeic acid. The process of electron transfer along peptide chain and trapping on caffeic acid finally has been elucidated based on the comparison of the energies of lowest empty molecular orbital (ELUMO) of the electron affinitive components and reaction rate constants of eaq- with these components respectively using pulse radiolysis techniques

  13. Excitation of the ligand-to-metal charge transfer band induces electron tunnelling in azurin

    Energy Technology Data Exchange (ETDEWEB)

    Baldacchini, Chiara [Biophysics and Nanoscience Centre, DEB-CNISM, Università della Tuscia, I-01100 Viterbo (Italy); Institute of Agro-environmental and Forest Biology, National Research Council, I-05010 Porano (Italy); Bizzarri, Anna Rita; Cannistraro, Salvatore, E-mail: cannistr@unitus.it [Biophysics and Nanoscience Centre, DEB-CNISM, Università della Tuscia, I-01100 Viterbo (Italy)

    2014-03-03

    Optical excitation of azurin blue copper protein immobilized on indium-tin oxide, in resonance with its ligand-to-metal charge transfer absorption band, resulted in a light-induced current tunnelling within the protein milieu. The related electron transport rate is estimated to be about 10{sup 5}?s{sup ?1}. A model based on resonant tunnelling through an azurin excited molecular state is proposed. The capability of controlling electron transfer processes through light pulses opens interesting perspectives for implementation of azurin in bio-nano-opto-electronic devices.

  14. Au25 clusters as electron-transfer catalysts induced the intramolecular cascade reaction of 2-nitrobenzonitrile.

    Science.gov (United States)

    Chong, Hanbao; Li, Peng; Wang, Shuxin; Fu, Fangyu; Xiang, Ji; Zhu, Manzhou; Li, Yadong

    2013-01-01

    Design of atomically precise metal nanocluster catalysts is of great importance in understanding the essence of the catalytic reactions at the atomic level. Here, for the first time, Au25(z) nanoslusters were employed as electron transfer catalysts to induce an intramolecular cascade reaction at ambient conditions and gave rise to high conversion (87%) and selectivity (96%). Electron spin-resonance spectra indeed confirmed the consecutive electron transfer process and the formation of N radical. UV-vis absorption spectra also verified Au25(z) was intact after the catalytic circle. Our research may open up wide opportunities for extensive organic reactions catalyzed by Au25(z). PMID:24225495

  15. Excitation of the ligand-to-metal charge transfer band induces electron tunnelling in azurin

    International Nuclear Information System (INIS)

    Optical excitation of azurin blue copper protein immobilized on indium-tin oxide, in resonance with its ligand-to-metal charge transfer absorption band, resulted in a light-induced current tunnelling within the protein milieu. The related electron transport rate is estimated to be about 105?s?1. A model based on resonant tunnelling through an azurin excited molecular state is proposed. The capability of controlling electron transfer processes through light pulses opens interesting perspectives for implementation of azurin in bio-nano-opto-electronic devices

  16. Collective and Plasma Screening Effects on Electron Transfer Processes in Nonideal Plasmas

    International Nuclear Information System (INIS)

    Collective and plasma screening effects on the maximum principal quantum number and the maximum internuclear distance in electron transfers in nonideal plasmas are investigated. An effective pseudopotential model taking into account collective and plasma screening effects is applied to obtain the interaction potential and screened effective charge in nonideal plasmas. The screened over the barrier model is applied to obtain the electron capture radius and the maximum principal quantum number of the final state of the transferred electron. The results show that the electron capture radius is more sensitive to the collective effect rather than the plasma screening effect. The electron capture radius is found to increase with increasing nonideality plasmas parameter. It is also found that the maximum principal quantum number of the final state of the electron increases with increasing nonideality plasma parameter and reciprocal Debye length

  17. Search for resonant electron transfer and double excitation in Kr34+ + H2 collisions

    International Nuclear Information System (INIS)

    Resonant electron transfer and double excitation (RME) is a correlated electron process which is expected to occur in an ion-atom collision when electron capture is accompanied by the simultaneous excitation of two inner-shell electrons. RT2 is similar to resonant transfer excitation (RTE) in which only a single electron is excited. RT2E was investigated experimentally for 38--42 MeV/u Kr34 + H2 collisions by observing x-ray emission associated with single-electron capture. No events associated with Kr K x rays (near 13 keV were observed; however, events do occur at about twice (> 22 keV) the Kr K x-ray energy. Several possible sources of these latter x rays have been considered

  18. Proton-coupled electron transfer: Free radicals under control

    Science.gov (United States)

    Barry, Bridgette A.

    2014-05-01

    Biological solar energy conversion requires the coordinated and rapid movement of protons and electrons through complex proteins, called reaction centres. Now, an artificial and structurally simple reaction centre has been synthesized that mimics an important, photosynthetic charge relay.

  19. Electron transfer within xanthine oxidase: A solvent kinetic isotope effect study

    International Nuclear Information System (INIS)

    Solvent kinetic isotope effect studies of electron transfer within xanthine oxidase have been performed, using a stopped-flow pH-jump technique to perturb the distribution of reducing equivalents within partially reduced enzyme and follow the kinetics of reequilibration spectrophotometrically. It is found that the rate constant for electron transfer between the flavin and one of the iron-sulfur centers of the enzyme observed when the pH is jumped from 10 to 6 decreases from 173 to 25 s-1 on going from HJ2O to D2O, giving an observed solvent kinetic isotope effect of 6.9. An effect of comparable magnitude is observed for the pH jump in the opposite direction, the rate constant decreasing form 395 to 56 s-1. The solvent kinetic isotope effect on kobs is found to be directly proportional to the mole fraction of D2O in the reaction mix for the pH jump in each direction, consistent with the effect arising from a single exchangeable proton. Calculations of the microscopic rate constants for electron transfer between the flavin and the iron-sulfur center indicate that the intrinsic solvent kinetic isotope effect for electron transfer from the neutral flavin semiquinone to the iron-sulfur center designated Fe/S I is substantially greater than for electron transfer in the opposite direction and that the observed solvent kinetic isotope effect is a weighted average of the intrinsic isotope effects for the forward intrinsic isotope effects for the forward and reverse microscopic electron-transfer steps. The results emphasize the importance of prototropic equilibria in the kinetic as well as thermodynamic behavior of xanthine oxidase and indicate that protonation/deprotonation of the isoalloxazine ring is concomitant with electron transfer in the xanthine oxidase system

  20. Electron Transfer Between Colloidal ZnO Nanocrystals

    OpenAIRE

    Hayoun, Rebecca; Whitaker, Kelly M.; Gamelin, Daniel R.; Mayer, James M.

    2011-01-01

    Colloidal ZnO nanocrystals, capped with dodecylamine and dissolved in toluene, can be charged photochemically to give stable solutions in which electrons are present in the conduction bands of the nanocrystals. These conduction band electrons are readily monitored by EPR spectroscopy, with g* values that correlate with the nanocrystal sizes. Mixing a solution of charged small nanocrystals with a solution of uncharged large nanocrystals, e-CB:ZnO–S + ZnO–L, causes changes in the EPR spectr...

  1. Electron transfer from sulfate-reducing becteria biofilm promoted by reduced graphene sheets

    Science.gov (United States)

    Wan, Yi; Zhang, Dun; Wang, Yi; Wu, Jiajia

    2012-01-01

    Reduced graphene sheets (RGSs) mediate electron transfer between sulfate-reducing bacteria (SRB) and solid electrodes, and promote the development of microbial fuel cells (MFC). We have investigated RSG-promoted electron transfer between SRB and a glassy carbon (GC) electrode. The RGSs were produced at high yield by a chemical sequence involving graphite oxidation, ultrasonic exfoliation of nanosheets, and N2H4 reduction. Cyclic voltammetric testing showed that the characteristic anodic peaks (around 0.3 V) might arise from the combination of bacterial membrane surface cytochrome c3 and the metabolic products of SRB. After 6 d, another anodic wave gradually increased to a maximum current peak and a third anodic signal became visible at around 0 V. The enhancements of two characteristic anodic peaks suggest that RSGs mediate electron-transfer kinetics between bacteria and the solid electrode. Manipulation of these recently-discovered electron-transport mechanisms will lead to significant advances in MFC engineering.

  2. Charge transfer by a double-scattering mechanism involving target electrons

    International Nuclear Information System (INIS)

    A classical mechanism of charge transfer was suggested by Thomas (Proc. R. Soc.; 114 561 (1927)) whereby the attachment of a target electron to an incident ion is facilitated by the recoil of a second target electron. This second electron recoils with the speed of the incident ion in a direction perpendicular to the ion direction. A quantum-mechanical description of this process is given. The cross section for charge transfer, differential in the electron recoil momentum, is shown to peak when the classical Thomas scattering conditions are satisfied. At asymptotically high collision velocities v, the total cross section for charge transfer via this double-scattering mechanism exhibits the same v-11 decrease as the classical cross section of Thomas. (author)

  3. Influence of bridge topology and torsion on the intramolecular electron transfer.

    Science.gov (United States)

    Lloveras, Vega; Vidal-Gancedo, José; Ruiz-Molina, Daniel; Figueira-Duarte, Teresa M; Nierengarten, Jean-François; Veciana, Jaume; Rovira, Concepció

    2006-01-01

    To study molecules able to act as good "molecular wires", intramolecular electron transfer between two triphenylmethyl redox centers connected by bridges with different topologies and substituents have been studied in solution, both by UV-Vis-NIR and EPR spectroscopies. The synthetic methodology used allows a complete control of the geometry of polychlorotriphenylmethyl diradicals 1 and 2, which have para and meta topologies, respectively, as well as of their E/Z isomerism. This fact is used to show the influence of the different topologies in the ease of electron transfer, which is larger for the para than for the meta isomer where a small or negligible electronic coupling is observed. The related diradical 3 that have the same topology as the para isomer 1 but bearing two substituents on the central phenyl ring shows similar ease of electron transfer, that the para isomer 1. PMID:16512379

  4. Comparison of three methods for calculation of electron transfer probability in H+ + Ne

    International Nuclear Information System (INIS)

    We have developed a theoretical model of ion-atom collisions where we described electron dynamics by the time-dependent density-functional theory (TDDFT) and the ion dynamics by classical mechanics through the Ehrenfest method. We have compared three methods to calculate the probability of electron transfer during H+ + Ne collision. By discussing these issues we shall be able to understand how these methods work, what their limitations are and whether they admit of any improvements. -- Highlights: ? We have developed a theoretical model of ion-atom collisions based on TDDFT. ? We have compared three methods to calculate the probability of electron transfer in H+ + Ne. ? Electron transfer cross sections showed a good agreement with available experimental data.

  5. Effect of size quantization on interfacial electron transfer dynamics in TiO{sub 2} nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Hirendra N. [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai (India); Max-Born Institute for Nonlinear and Short Pulse Spectroscopy, Berlin (Germany)

    2008-07-01

    Interfacial electron transfer dynamics was carried out in alizarin sensitized TiO{sub 2} nanoparticles with quantum size using femtosecond transient absorption (TA) spectroscopy. The TiO{sub 2} nanoparticles have been synthesized by arrested precipitation method. Electron injection dynamics were found to be multi-exponential with time constants of 100 fs, 17 ps and 50 ps. This observation was explained on the basis discreteness of the conduction band levels due to finite size effect. The back electron transfer (BET) dynamics found to be very slow as compared to the bulk system. The result gives us direct proof of non-adiabatic electron transfer reaction in a strong binding dye like alizarin.

  6. Importance of the donor:fullerene intermolecular arrangement for high-efficiency organic photovoltaics.

    Science.gov (United States)

    Graham, Kenneth R; Cabanetos, Clement; Jahnke, Justin P; Idso, Matthew N; El Labban, Abdulrahman; Ngongang Ndjawa, Guy O; Heumueller, Thomas; Vandewal, Koen; Salleo, Alberto; Chmelka, Bradley F; Amassian, Aram; Beaujuge, Pierre M; McGehee, Michael D

    2014-07-01

    The performance of organic photovoltaic (OPV) material systems are hypothesized to depend strongly on the intermolecular arrangements at the donor:fullerene interfaces. A review of some of the most efficient polymers utilized in polymer:fullerene PV devices, combined with an analysis of reported polymer donor materials wherein the same conjugated backbone was used with varying alkyl substituents, supports this hypothesis. Specifically, the literature shows that higher-performing donor-acceptor type polymers generally have acceptor moieties that are sterically accessible for interactions with the fullerene derivative, whereas the corresponding donor moieties tend to have branched alkyl substituents that sterically hinder interactions with the fullerene. To further explore the idea that the most beneficial polymer:fullerene arrangement involves the fullerene docking with the acceptor moiety, a family of benzo[1,2-b:4,5-b']dithiophene-thieno[3,4-c]pyrrole-4,6-dione polymers (PBDTTPD derivatives) was synthesized and tested in a variety of PV device types with vastly different aggregation states of the polymer. In agreement with our hypothesis, the PBDTTPD derivative with a more sterically accessible acceptor moiety and a more sterically hindered donor moiety shows the highest performance in bulk-heterojunction, bilayer, and low-polymer concentration PV devices where fullerene derivatives serve as the electron-accepting materials. Furthermore, external quantum efficiency measurements of the charge-transfer state and solid-state two-dimensional (2D) (13)C{(1)H} heteronuclear correlation (HETCOR) NMR analyses support that a specific polymer:fullerene arrangement is present for the highest performing PBDTTPD derivative, in which the fullerene is in closer proximity to the acceptor moiety of the polymer. This work demonstrates that the polymer:fullerene arrangement and resulting intermolecular interactions may be key factors in determining the performance of OPV material systems. PMID:24932575

  7. Modulating the electronic structure of chromophores by chemical substituents for efficient energy transfer: application to fluorone.

    Science.gov (United States)

    Sand, Andrew M; Liu, Claire; Valentine, Andrew J S; Mazziotti, David A

    2014-08-01

    Strong electron correlation within a quasi-spin model of chromophores was recently shown to enhance exciton energy transfer significantly. Here we investigate how the modulation of the electronic structure of the chromophores by chemical substitution can enhance energy-transfer efficiency. Unlike previous work that does not consider the direct effect of the electronic structure on exciton dynamics, we add chemical substituents to the fluorone dimer to study the effect of electron-donating and electron-withdrawing substituents on exciton energy transfer. The exciton dynamics are studied from the solution of a quantum Liouville equation for an open system whose model Hamiltonian is derived from excited-state electronic structure calculations. Both van der Waals energies and coupling energies, arising from the Hellmann-Feynman force generated upon transferring the dimers from infinity to a finite separation, are built into the model Hamiltonian. Though these two effects are implicitly treated in dipole-based models, their explicit and separate treatment as discussed here is critical to forging the correct connection with the electronic structure calculations. We find that the addition of electron-donating substituents to the fluorone system results in an increase in exciton-transfer rates by factors ranging from 1.3-1.9. The computed oscillator strength is consistent with the recent experimental results on a larger heterodimer system containing fluorone. The oscillator strength increases with the addition of electron-donating substituents. Our results indicate that the study of chromophore networks via electronic structure will help in the future design of efficient synthetic light-harvesting systems. PMID:25062094

  8. Properties of the transfer matrices of deflecting magnet systems for free electron laser

    International Nuclear Information System (INIS)

    The oscillation of the free electron laser (FEL) requires the high current and low emittance electron beam. The beam transport system should be achromatic and isochronous to preserve the brightness and the emittance of the electron beam. In this paper we clarify the algebraic properties of the transfer matrices of the magnetic deflection system, which is a key component in the beam transport line. (author)

  9. Long-range intramolecular electron transfer in aromatic radical anions and binuclear transition metal complexes

    OpenAIRE

    Kuznetsov, A. M.; Ulstrup, Jens

    1981-01-01

    Intramolecular electron transfer (ET) over distances up to about 10 Å between states in which the electron is localized on donor and acceptor groups by interaction with molecular or external solvent nuclear motion occurs, in particular, in two classes of systems. The excess electron in anionic radicals containing two aromatic end groups connected by a flexible polymethylene chain or a rigid cyclohexane frame is thus trapped on either aromatic end group, and ET between these groups can be det...

  10. Electron transfer between protein and DNA in gamma-irradiated deoxyribonucleoprotein

    International Nuclear Information System (INIS)

    When deoxyribonucleoprotein-proflavine complexes were studied by electron spin resonance spectroscopy following gamma-irradiation, it was found that stable free radicals were not formed at random on the complex but were preferentially located on proflavine. Since proflavine intercalated to DNA bases serves as a final acceptor of electrons liberated by ionization, the result of our experiment was regarded as suggesting that the electron transfer from the protein moiety to the DNA moiety occurred in the irradiated deoxyribonucleoprotein

  11. Selection rules for electron transfer to the continuum in ion-atom collision

    International Nuclear Information System (INIS)

    We consider the process of electron transfer to the in first order Born approximation. We analyse the expansion of the double-differential cross section in series of electron velocity and ejection angle. We found that the coefficients obey precise selection rules. We discuss the relation of these rules, which predict an asymmetric shape for the electron loss to the continuum cusp, with the interpretation of recent experimental results

  12. DFT/B3LYP study of the substituent effect on the reaction enthalpies of the individual steps of single electron transfer-proton transfer and sequential proton loss electron transfer mechanisms of phenols antioxidant action.

    Science.gov (United States)

    Klein, Erik; Lukes, Vladimír

    2006-11-01

    The reaction enthalpies related to the individual steps of two phenolic antioxidants action mechanisms, single electron transfer-proton transfer (SET-PT) and sequential proton loss electron transfer (SPLET), for 30 meta and para-substituted phenols (ArOH) were calculated using DFT/B3LYP method. These mechanisms represent the alternative ways to the extensively studied hydrogen atom transfer (HAT) mechanism. Except the comparison of calculated reaction enthalpies with available experimental and/or theoretical values, obtained enthalpies were correlated with Hammett constants. We have found that electron-donating substituents induce the rise in the enthalpy of proton dissociation (PDE) from ArOH+* radical cation (second step in SET-PT) and in the proton affinities of phenoxide ions ArO- (reaction enthalpy of the first step in SPLET). Electron-withdrawing groups cause the increase in the reaction enthalpies of the processes where electron is abstracted, i.e., in the ionization potentials of ArOH (first step in SET-PT) and in the enthalpy of electron transfer from ArO- (second step in SPLET). Found results indicate that all dependences of reaction enthalpies on Hammett constants of the substituents are linear. The calculations of liquid-phase reaction enthalpies for several para-substituted phenols indicate that found trends hold also in water, although substituent effects are weaker. From the thermodynamic point of view, entering SPLET mechanism represents the most probable process in water. PMID:17078630

  13. The transfer between electron bulk kinetic energy and thermal energy in collisionless magnetic reconnection

    Science.gov (United States)

    Lu, San; Lu, Quanming; Huang, Can; Wang, Shui

    2013-06-01

    By performing two-dimensional particle-in-cell simulations, we investigate the transfer between electron bulk kinetic and electron thermal energy in collisionless magnetic reconnection. In the vicinity of the X line, the electron bulk kinetic energy density is much larger than the electron thermal energy density. The evolution of the electron bulk kinetic energy is mainly determined by the work done by the electric field force and electron pressure gradient force. The work done by the electron gradient pressure force in the vicinity of the X line is changed to the electron enthalpy flux. In the magnetic island, the electron enthalpy flux is transferred to the electron thermal energy due to the compressibility of the plasma in the magnetic island. The compression of the plasma in the magnetic island is the consequence of the electromagnetic force acting on the plasma as the magnetic field lines release their tension after being reconnected. Therefore, we can observe that in the magnetic island the electron thermal energy density is much larger than the electron bulk kinetic energy density.

  14. The transfer between electron bulk kinetic energy and thermal energy in collisionless magnetic reconnection

    International Nuclear Information System (INIS)

    By performing two-dimensional particle-in-cell simulations, we investigate the transfer between electron bulk kinetic and electron thermal energy in collisionless magnetic reconnection. In the vicinity of the X line, the electron bulk kinetic energy density is much larger than the electron thermal energy density. The evolution of the electron bulk kinetic energy is mainly determined by the work done by the electric field force and electron pressure gradient force. The work done by the electron gradient pressure force in the vicinity of the X line is changed to the electron enthalpy flux. In the magnetic island, the electron enthalpy flux is transferred to the electron thermal energy due to the compressibility of the plasma in the magnetic island. The compression of the plasma in the magnetic island is the consequence of the electromagnetic force acting on the plasma as the magnetic field lines release their tension after being reconnected. Therefore, we can observe that in the magnetic island the electron thermal energy density is much larger than the electron bulk kinetic energy density

  15. Electronic coupling effects on photoinduced electron transfer in carotene-porphyrin-fullerene triads detected by time-resolved EPR.

    Science.gov (United States)

    Di Valentin, Marilena; Bisol, Arianna; Agostini, Giancarlo; Carbonera, Donatella

    2005-01-01

    Photoinduced charge separation and recombination in a carotenoid-porphyrin-fullerene triad C-P-C60 (Bahr et al., 2000) have been followed by time-resolved electron paramagnetic resonance. The electron-transfer process has been characterized in a glass of 2-methyltetrahydrofuran and in the nematic phase of two uniaxial liquid crystals (E-7 and ZLI-1167). In all the different media, the molecular triad undergoes two-step photoinduced electron transfer, with the generation of a long-lived charge-separated state (C*+-P-C60*-), and charge recombination to the triplet state, localized in the carotene moiety, mimicking different aspects of the photosynthetic electron-transfer process. The magnetic interaction parameters have been evaluated by simulation of the spin-polarized radical pair spectrum. The weak exchange interaction parameter (J = +1.7 +/- 0.1 G) provides a direct measure of the dominant electronic coupling matrix element V between the C*+-P-C60*- radical pair state and the recombination triplet state 3C-P-C60. Comparison of the estimated values of V for this triad and a structurally related triad differing only in the porphyrin bridge (octaalkylporphyrin vs tetraarylporphyrin) explains in terms of an electronic coupling effect the approximately 6-fold variation of the recombination rate induced by the modification of the porphyrin bridge as derived by kinetic experiments (Bahr et al., 2000). PMID:16309257

  16. Energy transfer between electronically excited zinc and calcium atoms

    International Nuclear Information System (INIS)

    A series of experiments have been performed in which zinc atoms carried in a flowing stream of helium are excited to the 4(3P1) state by optical pumping with a XeCl excimer laser. Addition of calcium atoms to the flow results in quenching of the excited zinc atoms. The cross section for this energy transfer process is sigma> or =3 x 10-16 cm2, corresponding to Zn(4 3P/sub J/) quenching in fewer than 10 collisons with calcium atoms. Subsequent to optical excitation of the zinc atoms, emission was observed from both the 4 1P1 and 5 3S1 excited states of calcium. Integration of the intensities of the calcium emissions indicated that excitation of the singlet and triplet manifolds in calcium occurs with comparable probability, suggesting that spin conservation is not a strong constraint in the energy transfer process. Summation of the intensities indicate that the E--E transfer process accounts for most of the quenching of the excited zinc atoms

  17. Designed Surface Residue Substitutions in [NiFe] Hydrogenase that Improve Electron Transfer Characteristics

    Science.gov (United States)

    Yonemoto, Isaac T.; Smith, Hamilton O.; Weyman, Philip D.

    2015-01-01

    Photobiological hydrogen production is an attractive, carbon-neutral means to convert solar energy to hydrogen. We build on previous research improving the Alteromonas macleodii “Deep Ecotype” [NiFe] hydrogenase, and report progress towards creating an artificial electron transfer pathway to supply the hydrogenase with electrons necessary for hydrogen production. Ferredoxin is the first soluble electron transfer mediator to receive high-energy electrons from photosystem I, and bears an electron with sufficient potential to efficiently reduce protons. Thus, we engineered a hydrogenase-ferredoxin fusion that also contained several other modifications. In addition to the C-terminal ferredoxin fusion, we truncated the C-terminus of the hydrogenase small subunit, identified as the available terminus closer to the electron transfer region. We also neutralized an anionic patch surrounding the interface Fe-S cluster to improve transfer kinetics with the negatively charged ferredoxin. Initial screening showed the enzyme tolerated both truncation and charge neutralization on the small subunit ferredoxin-binding face. While the enzyme activity was relatively unchanged using the substrate methyl viologen, we observed a marked improvement from both the ferredoxin fusion and surface modification using only dithionite as an electron donor. Combining ferredoxin fusion and surface charge modification showed progressively improved activity in an in vitro assay with purified enzyme. PMID:25603181

  18. Intermolecular adhesion in conducting polymers

    CERN Document Server

    Schmit, J D; Schmit, Jeremy D.; Levine, Alex J.

    2004-01-01

    We analyze the interaction of two conducting, charged polymer chains in solution using a minimal model for their electronic degrees of freedom. We show that a crossing of the two chains in which the polymers pass within Angstroms of each other leads to a decrease of the electronic energy of the combined system that is significantly larger than the thermal energy and thus promotes interchain aggregation. We consider the competition of this attractive interaction with the screened electrostatic repulsion and thereby propose a phase diagram for such polymers in solution; depending on the charge density and persistence length of the chains, the polymers may be unbound, bound in loose, braid-like structures, or tightly bound in a parallel configuration.

  19. Single-molecule transistors: Electron transfer in the solid state

    International Nuclear Information System (INIS)

    Single-molecule transistors (SMTs) incorporating individual small molecules are unique tools for examining the fundamental physics and chemistry of electronic transport in molecular systems at the single nanometer scale. We describe the fabrication and characterization of such devices, and the synthesis and surface attachment chemistry of novel transition metal complexes that have been incorporated into such SMTs. We present gate-modulated inelastic electron tunneling vibrational spectroscopy of single molecules, strong Kondo physics (T K ? 75 K) as evidence of excellent molecule/electrode electronic coupling, and a demonstration that covalent attachment chemistry can produce SMTs that survive repeated thermal cycling to room temperature. We conclude with a look ahead at the prospects for these nanoscale systems

  20. Interatomic and intermolecular Coulombic decay: the coming of age story

    Science.gov (United States)

    Jahnke, T.

    2015-04-01

    In pioneering work by Cederbaum et al an excitation mechanism was proposed that occurs only in loosely bound matter (Cederbaum et al 1997 Phys. Rev. Lett. 79 4778): it turned out, that (in particular) in cases where a local Auger decay is energetically forbidden, an excited atom or molecule is able to decay in a scheme which was termed ‘interatomic Coulombic decay’ (or ‘intermolecular Coulombic decay’) (ICD). As ICD occurs, the excitation energy is released by transferring it to an atomic or molecular neighbor of the initially excited particle. As a consequence the neighboring atom or molecule is ionized as it receives the energy. A few years later the existence of ICD was confirmed experimentally (Marburger et al 2003 Phys. Rev. Lett. 90 203401; Jahnke et al 2004 Phys. Rev. Lett. 93 163401; Öhrwall et al 2004 Phys. Rev. Lett. 93 173401) by different techniques. Since this time it has been found that ICD is not (as initially suspected) an exotic feature of van der Waals or hydrogen bonded systems, but that ICD is a very general and common feature occurring after a manifold of excitation schemes and in numerous weakly bound systems, as revealed by more than 200 publications. It was even demonstrated, that ICD can become more efficient than a local Auger decay in some system. This review will concentrate on recent experimental investigations on ICD. It will briefly introduce the phenomenon and give a short summary of the ‘early years’ of ICD (a detailed view on this episode of investigations can be found in the review article by U Hergenhahn with the same title (Hergenhahn 2011 J. Electron Spectrosc. Relat. Phenom. 184 78)). More recent articles will be presented that investigate the relevance of ICD in biological systems and possible radiation damage of such systems due to ICD. The occurrence of ICD and ICD-like processes after different excitation schemes and in different systems is covered in the middle section: in that context the helium dimer (He2) is a particularly interesting (and exotic) system in which ICD was detected. It was employed in several publications to elucidate the strong impact of nuclear motion on ICD and its longrange-character. The review will present these findings and their initial theoretical predictions and give insight into most recent time-resolved measurements of ICD.

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

    Science.gov (United States)

    Della Pia, Eduardo Antonio; Chi, Qijin; Macdonald, J Emyr; Ulstrup, Jens; Jones, D Dafydd; Elliott, Martin

    2012-11-21

    The electron transfer properties of proteins are normally measured as molecularly averaged ensembles. Through these and related measurements, proteins are widely regarded as macroscopically insulating materials. Using scanning tunnelling microscopy (STM), we present new measurements of the conductance through single-molecules of the electron transfer protein cytochrome b(562) in its native conformation, under pseudo-physiological conditions. This is achieved by thiol (SH) linker pairs at opposite ends of the molecule through protein engineering, resulting in defined covalent contact between 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 b(562) molecules near zero electrochemical overpotential. This strongly points to the important role of the heme co-factor bound to the natively structured protein. We suggest that the two-step model of protein electron transfer in the STM geometry requires a multi-electron transfer to explain such a high conductance. The model also yields a low value for the reorganisation energy, implying that solvent reorganisation is largely absent. PMID:23069929

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

    DEFF Research Database (Denmark)

    Della Pia, Eduardo Antonio; Chi, Qijin

    2012-01-01

    The electron transfer properties of proteins are normally measured as molecularly averaged ensembles. Through these and related measurements, proteins are widely regarded as macroscopically insulating materials. Using scanning tunnelling microscopy (STM), we present new measurements of the conductance through single-molecules of the electron transfer protein cytochrome b562 in its native conformation, under pseudo-physiological conditions. This is achieved by thiol (SH) linker pairs at opposite ends of the molecule through protein engineering, resulting in defined covalent contact between 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 of the heme co-factor bound to the natively structured protein. We suggest that the two-step model of protein electron transfer in the STM geometry requires a multi-electron transfer to explain such a high conductance. The model also yields a low value for the reorganisation energy, implying that solvent reorganisation is largely absent.

  3. Correlation between biological activity and electron transferring of bovine liver catalase: Osmolytes effects

    International Nuclear Information System (INIS)

    Highlights: • Proline increases ET in Bovine Liver Catalase (BLC) whereas histidine decreases it. • Proline also increased the biological activity, whereas histidine decreased it. • Electron transferring and biological activity for BLC are directly correlated. • Proline causes favorable ET for BLC shown by positive E1/2 (E°?) and negative ?G. • Histidine makes ET unfavorable for BLC, manifested by E1/2 (E°?) 0. -- Abstract: Catalase is a crucial antioxidant enzyme that protects life against detrimental effects of H2O2 by disproportionating it into water and molecular oxygen. Effect of proline as a compatible and histidine as a non compatible osmolyte on the electron transferring and midpoint potential of catalase has been investigated. Proline increases the midpoint potential (?Em > 0), therefore causing the ?GET to be less positive and making the electron transfer reaction more facile whereas histidine decreases the Em (?Em ET, thereby rendering the electron transfer reaction less efficient. These results indicate the inhibitory effect of histidine evident by a ?37% decrease in the cathodic peak current compared to 16% increase in the case of proline indicative of activation. The insight paves the tedious way towards our ultimate goal of elucidating a correlation between biological activity and electron transferring

  4. A new intermolecular mechanism to selectively drive photoinduced damages

    CERN Document Server

    Gokhberg, Kirill; Kuleff, Alexander I; Cederbaum, Lorenz S

    2014-01-01

    Low-energy electrons (LEEs) are known to be effective in causing strand breaks in DNA. Recent experiments show that an important direct source of LEEs is the intermolecular Coulombic decay (ICD) process. Here we propose a new cascade mechanism initiated by core excitation and terminated by ICD and demonstrate its properties. Explicit calculations show that the energies of the emitted ICD-electrons can be controlled by selecting the initial atomic excitation. The properties of the cascade may have interesting applications in the fields of electron spectroscopy and radiation damage. Initiating such a cascade by resonant X-ray absorption from a high-Z element embedded in a cancerous cell nucleus, ICD will deliver genotoxic particles \\textit{locally} at the absorption site, increasing in that way the controllability of the induced damage.

  5. Exclusive electron scattering from deuterium at high momentum transfer

    International Nuclear Information System (INIS)

    Cross sections are presented for the reaction 2H(e,e'p)n for momentum transfers in the range 1.2?Q2?6.8(GeV/c)2 and for missing momenta from 0 to 250 MeV/c. The longitudinal-transverse interference structure function has been separated at Q2=1.2(GeV/c)2. The observables are compared to calculations performed in nonrelativistic and relativistic frameworks. The data are best described by a fully relativistic calculation

  6. Shedding light on the photostability of two intermolecular charge-transfer complexes between highly fluorescent bis-1,8-naphthalimide dyes and some ?-acceptors: A spectroscopic study in solution and solid states

    Science.gov (United States)

    Refat, Moamen S.; Ismail, Lamia A.; Adam, Abdel Majid A.

    2015-01-01

    Given the great importance of the various uses of 1,8-naphthalimides in the trends of biology, medicine and industry, the current study focused on extending the scope of these dyes by introducing some of their charge-transfer (CT) complexes. For this purpose, two highly fluorescent bis-1,8-naphthalimide dyes and their complexes with some ?-acceptors have been synthesized and characterized spectroscopically. The ?-acceptors include picric acid (PA), chloranilic acid (CLA), tetracyanoquinodimethane (TCNQ) and dichlorodicyanobenzoquinone (DDQ). The molecular structure, spectroscopic and fluorescence properties as well as the binding modes were deduced from IR, UV-vis and 1H NMR spectral studies. The binding ratio of complexation was determined to be 1:1 according to the elemental analyses and photometric titrations. It has been found that the order of acceptance ability for the different acceptors is TCNQ > DDQ > CLA > PA. The photostability of 1,8-naphthalimide dye as a donor and its charge-transfer complex doped in polymethyl methacrylate/PMMA were exposed to UV-Vis radiation and the change in the absorption spectra was achieved at different times during irradiation period.

  7. Cellular electron transfer and radical mechanisms for drug metabolism

    International Nuclear Information System (INIS)

    Aerobic and anaerobic reductions of various nitroaromatic compounds by mammalian cells result in the production of reactive intermediates. Drug reduction is dependent upon glucose, nonprotein thiols, endogenous enzyme levels, and drug electron affinity. Drugs with electron affinities approaching that of oxygen are reduced, in the presence of oxygen, beyond a one-electron radical anion. Nitroaromatic radical anion inactivation occurs by reaction with cellular ferricytochrome c, endogenous thiols, and with oxygen. In the latter case the reaction results in the production of peroxide. Drugs that are substrates for the enzyme glutathione-S-transferase remove endogeneous thiols and demonstrate peroxide production without prior thiol removal. Less electron affinic drugs such as misonidazole require thiol removal as well as the presence of cyanide or azide for maximal peroxide production. Under anaerobic conditions radical anion and nitroso intermediates are reactive with glutathione. Removal of endogenous thiols by hypoxic preincubation with misonidazole may be related to the enhanced radiation response and cytotoxicity of this drug. Reduction of nitro compounds in the presence of DNA and chemicals such as dithionite, zinc dust, or polarographic techniques causes binding to macromolecules and DNA breaks. Chemical-reduction of nitro compounds by ascorbate in the presence of cells enhances drug cytotoxic effects

  8. An improved intermolecular potential for sulfur hexafluoride

    International Nuclear Information System (INIS)

    Second virial coefficient data and viscosity were used to evaluate effective isotropic intermolecular potential functions proposed in the literature for sulfur hexafluoride. It was found that none of the potentials could predict the properties simultaneously. We have constructed a Morse--Morse--Spline--van der Waals (MMSV) potential which satisfactorily correlates second virial coefficient and viscosity data at the same time

  9. Extracellular electron transfer through microbial reduction of solid-phase humic substances

    Science.gov (United States)

    Roden, Eric E.; Kappler, Andreas; Bauer, Iris; Jiang, Jie; Paul, Andrea; Stoesser, Reinhard; Konishi, Hiromi; Xu, Huifang

    2010-06-01

    The decay of soil and sedimentary organic matter yieldsorganic compounds with a high molecular weight, termed humic substances. Microorganisms can transfer electrons to dissolved humic substances, and reduced humic substances can rapidly reduce iron(III) oxides. Thus, dissolved humic substances can serve as electron shuttles that promote iron(III) oxide reduction in sediments. However, most humic substances in soils and sediments are in particulate, rather than dissolved, form; the ability of microorganisms to reduce solid-phase humics and their capacity to shuttle electrons is thus far unknown. Here we show through incubation experiments and electron spin resonance measurements that iron(III)-oxide-reducing bacteria can transfer electrons to solid-phase humic substances in sediments sampled from wetlands. Although the electron-accepting capacity of the solid-phase humics was modest, solid-phase humics significantly accelerated iron(III) oxide reduction, by shuttling electrons from bacteria to oxide surfaces. Microbial solid-phase humics reduction represents a new mechanism for extracellular electron transfer that can facilitate reduction of iron(III) oxide and other redox reactions in sediments and soils.

  10. Current Theoretical Challenges in Proton-Coupled Electron Transfer: Electron-Proton Nonadiabaticity, Proton Relays, and Ultrafast Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Hammes-Schiffer, Sharon

    2011-06-16

    Proton-coupled electron transfer (PCET) reactions play an important role in a wide range of biological and chemical processes. The motions of the electrons, transferring protons, solute nuclei, and solvent nuclei occur on a wide range of timescales and are often strongly coupled. As a result, the theoretical description of these processes requires a combination of quantum and classical methods. This perspective discusses three of the current theoretical challenges in the field of PCET. The first challenge is the calculation of electron-proton nonadiabatic effects, which are significant for these reactions because the hydrogen tunneling is often faster than the electronic transition. The second challenge is the modeling of electron transfer coupled to proton transport along hydrogen-bonded networks. The third challenge is the simulation of the ultrafast dynamics of nonequilibrium photoinduced PCET reactions in solution. Insights provided by theoretical studies may assist in the design of more effective catalysts for energy conversion processes. The proton relay portion of this review is based upon work 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.

  11. Current Theoretical Challenges in Proton-Coupled Electron Transfer: Electron Proton Nonadiabaticity, Proton Relays, and Ultrafast Dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Hammes-Schiffer, Sharon

    2011-06-16

    Proton-coupled electron transfer (PCET) reactions play an important role in a wide range of biological and chemical processes. The motions of the electrons, transferring protons, solute nuclei, and solvent nuclei occur on a wide range of time scales and are often strongly coupled. As a result, the theoretical description of these processes requires a combination of quantum and classical methods. This Perspective discusses three of the current theoretical challenges in the field of PCET. The first challenge is the calculation of electron proton nonadiabatic effects, which are significant for these reactions because the hydrogen tunneling is often faster than the electronic transition. The second challenge is the modeling of electron transfer coupled to proton transport along hydrogen-bonded networks. The third challenge is the simulation of the ultrafast dynamics of nonequilibrium photoinduced PCET reactions in solution. Insights provided by theoretical studies may assist in the design of more effective catalysts for energy conversion processes. The proton relay portion of this review is based upon work 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.

  12. Electron transfer reactions in ternary systems on silica gel surfaces: evidence for radical cation diffusion.

    Science.gov (United States)

    Williams, Sian L; Kirkpatrick, Iain; Worrall, David R

    2010-07-30

    Electron transfer reactions have been studied between 9-anthracenecarboxylic acid co-adsorbed with perylene on silica gel surfaces employing azulene as a molecular shuttle in order to facilitate hole transfer. In this paper we present for the first time a ternary system that unambiguously demonstrates an appreciable mobility of radical cations on the silica gel surface. Rates of hole transfer from the 9-anthracenecarboxylic acid radical cation to perylene via azulene have been studied using diffuse reflectance laser flash photolysis spectroscopy. Azulene has been shown to enhance the rate of electron transfer in the ternary system, proving significant mobility of the azulene and its radical cation species on silica gel surfaces. The data shows that the azulene radical cation can diffuse at an appreciable rate on the silica gel surface. PMID:20464021

  13. Proton transfer between phenol and ammonia in ground and excited electronic states

    Science.gov (United States)

    Yi, Manyin; Scheiner, Steve

    1996-11-01

    Ab initio calculations consider the H-bonded complex between phenol and ammonia. The transfer of a proton in the ground electronic state, which would form PhO - … +HNH 3, is highly disfavored. However, the situation changes dramatically in the first excited singlet state where the proton transfer potential develops a second minimum, competitive in energy with the neutral pair PhOH … NH 3. Following electron ejection, the radical cation complex, PhOH + … NH 3, contains a very flat proton transfer potential connecting PhOH ·+ … NH 3 with PhO · … H +NH 3. Addition of more ammonia molecules further stabilizes the proton-transfered PhO · … H +NH 3 configuration.

  14. Local intermolecular interactions for selective CO2 capture by zeolitic imidazole frameworks: energy decomposition analysis

    International Nuclear Information System (INIS)

    Intermolecular energy decomposition analysis (EDA) is reported for the binding of CO2 with zeolitic imidazole frameworks (ZIF) to provide a molecular level interpretation of the recent capacity and selectivity measurements of several ZIFs and to suggest a theoretical guideline to improve their performance further, using 1 nm size of organic linker fragment of the ZIFs as a target molecule. The EDA suggests that the local electronic interaction of CO2 and the substituent groups, mainly frozen density and polarization interactions with little charge transfer, is the primary binding interaction, but the electron correlation effects can be equally or more important depending on the binding geometry and functional groups. The present correlated calculations identify the preferred ZIF binding sites for various gases including CO2 to be mostly near the benzene substituent groups rather than the plane of imidazole rings. We predict that the NH2-substituted ZIF would have an enhanced capacity of CO2 as compared to the NO2-substituted ZIF that was recently synthesized and reported to be one of the materials with the best capacity results along with high gas selectivity. The present calculations may imply that the local functionality of the linking organics, rather than detailed framework structures, may be of primary importance in designing certain high capacity MOF or ZIF materials.F materials.

  15. Surface-induced intramolecular electron transfer in multi-centre redox metalloproteins: the di-haem protein cytochrome c4 in homogeneous solution and at electrochemical surfaces

    International Nuclear Information System (INIS)

    Intramolecular electron transfer (ET) between transition metal centres is a core feature of biological ET and redox enzyme function. The number of microscopic redox potentials and ET rate constants is, however, mostly prohibitive for experimental mapping, but two-centre proteins offer simple enough communication networks for complete mapping to be within reach. At the same time, multi-centre redox proteins operate in a membrane environment where conformational dynamics and ET patterns are quite different from the conditions in a homogeneous solution. The bacterial respiratory di-haem protein Pseudomonas stutzeri cytochrome c4 offers a prototype target for environmental gating of intra-haem ET. ET between P. stutzeri cyt c4 and small molecular reaction partners in solution appears completely dominated by intermolecular ET of each haem group/protein domain, with no competing intra-haem ET, for which accompanying propionate-mediated proton transfer is a further barrier. The protein can, however, be immobilized on single-crystal, modified Au(111) electrode surfaces with either the low-potential N terminal or the high-potential C terminal domain facing the surface, clearly with fast intramolecular ET as a key feature in the electrochemical two-ET process. This dual behaviour suggests a pattern for multi-centre redox metalloprotein function. In a homogeneous solution, which is not the natural environment of cyt c4, the two haem group domains c4, the two haem group domains operate largely independently with conformations prohibitive for intramolecular ET. Binding to a membrane or electrochemical surface, however, triggers conformational opening of intramolecular ET channels. The haem group orientation in P. stutzeri cyt c4 is finally noted to offer a case for orientation dependent electronic rectification between a substrate and a tip in electrochemical in situ scanning tunnelling microscopy or nanoscale electrode configurations

  16. Quenching of the excited state of hydrated Europium(III) ions by electron transfer

    Energy Technology Data Exchange (ETDEWEB)

    Christensen, K.

    1993-08-01

    This thesis explores the oxidation-reduction chemistry of the excited state of Eu(III) ions, *Eu{sub aq}{sup 3+}, in aqueous solutions. Evidence is presented for the quenching of *Eu{sup 3+} by reductive electron transfer. It is concluded that *Eu{sup 3+} is not a strong energy transfer reagent. The reactivity of *Eu{sub aq}{sup 3+} is compared with that of *UO{sub 2}{sup 2+}.

  17. Electronic system for the automatic transfer of data from multichannel analyzer memory to computer

    International Nuclear Information System (INIS)

    An electronic system has been build for the automatic transfer of data from Intertechnique Multichannel analyzer Memory to HP 2116 C computer. By using a balanced twisted-pair transmission line, transfer can be made from devices separated up to 300 meters. A logic interface is associated to each apparatus. Computer manages the transmission process and indicates the errors that could happen. 4096 channels are transmitted into 17 sec

  18. Femtosecond laser field induced modifications of electron-transfer processes in Ne+-He collisions

    International Nuclear Information System (INIS)

    We demonstrate the presence of femtosecond laser induced charge transfer in Ne+-He collisions. Electron transfer in ion-atom collisions is considerably modified when the collision is embedded in a strong laser field with the laser intensity of ?1015 W/cm2. The observed anisotropy of the He+ angular distribution confirms the prediction of early work that the capture probability varies significantly with the laser polarization angle.

  19. Nobel Prize 1992: Rudolph A. Marcus: theory of electron transfer reactions in chemical systems

    International Nuclear Information System (INIS)

    A review of the theory developed by Rudolph A. Marcus is presented, who for his rating to the theory of electron transfer in chemical systems was awarded the Nobel Prize in Chemistry in 1992. Marcus theory has constituted not only a good extension of the use of a spectroscopic principle, but also has provided an energy balance and the application of energy conservation for electron transfer reactions. A better understanding of the reaction coordinate is exposed in terms energetic and establishing the principles that govern the transfer of electrons, protons and some labile small molecular groups as studied at present. Also, the postulates and equations described have established predictive models of reaction time, very useful for industrial environments, biological, metabolic, and others that involve redox processes. Marcus theory itself has also constituted a large contribution to the theory of complex transition

  20. Study of intermediates from transition metal excited-state electron-transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Hoffman, M.Z.

    1991-12-31

    During this period, conventional and fast-kinetics techniques of photochemistry, photophysics, radiation chemistry, and electrochemistry were used for the characterization of the intermediates that are involved in transition metal excited-state electron-transfer reactions. The intermediates of interest were the excited states of Ru(II) and Cr(III) photosensitizers, their reduced forms, and the species formed in the reactions of redox quenchers and electron-transfer agents. Of particular concern has been the back electron-transfer reaction between the geminate pair formed in the redox quenching of the photosensitizers, and the dependence of its rate on solution medium and temperature in competition with transformation and cage escape processes.

  1. Characterization of Electron Transfer Dissociation in the Orbitrap Velos HCD Cell

    Science.gov (United States)

    Frese, Christian K.; Nolting, Dirk; Altelaar, A. F. Maarten; Griep-Raming, Jens; Mohammed, Shabaz; Heck, Albert J. R.

    2013-11-01

    Electron transfer dissociation (ETD) is commonly employed in ion traps utilizing rf fields that facilitate efficient electron transfer reactions. Here, we explore performing ETD in the HCD collision cell on an Orbitrap Velos instrument by applying a static DC gradient axially to the rods. This gradient enables simultaneous three dimensional, charge sign independent, trapping of cations and anions, initiating electron transfer reactions in the center of the HCD cell where oppositely charged ions clouds overlap. Here, we evaluate this mode of operation for a number of tryptic peptide populations and the top-down sequence analysis of ubiquitin. Our preliminary data show that performing ETD in the HCD cell provides similar fragmentation as ion trap-ETD but requires further optimization to match performance of ion trap-ETD.

  2. Electron-transfer kinetics in cyanobacterial cells: Methyl viologen is a poor inhibitor of linear electron flow.

    Science.gov (United States)

    Sétif, Pierre

    2015-02-01

    The inhibitor methyl viologen (MV) has been widely used in photosynthesis to study oxidative stress. Its effects on electron transfer kinetics in Synechocystis sp. PCC6803 cells were studied to characterize its electron-accepting properties. For the first hundreds of flashes following MV addition at submillimolar concentrations, the kinetics of NADPH formation were hardly modified (less than 15% decrease in signal amplitude) with a significant signal decrease only observed after more flashes or continuous illumination. The dependence of the P700 photooxidation kinetics on the MV concentration exhibited a saturation effect at 0.3mM MV, a concentration which inhibits the recombination reactions in photosystem I. The kinetics of NADPH formation and decay under continuous light with MV at 0.3mM showed that MV induces the oxidation of the NADP pool in darkness and that the yield of linear electron transfer decreased by only 50% after 1.5-2 photosystem-I turnovers. The unexpectedly poor efficiency of MV in inhibiting NADPH formation was corroborated by in vitro flash-induced absorption experiments with purified photosystem-I, ferredoxin and ferredoxin-NADP(+)-oxidoreductase. These experiments showed that the second-order rate constants of MV reduction are 20 to 40-fold smaller than the competing rate constants involved in reduction of ferredoxin and ferredoxin-NADP(+)-oxidoreductase. The present study shows that MV, which accepts electrons in vivo both at the level of photosystem-I and ferredoxin, can be used at submillimolar concentrations to inhibit recombination reactions in photosystem-I with only a moderate decrease in the efficiency of fast reactions involved in linear electron transfer and possibly cyclic electron transfer. PMID:25448535

  3. The transfer of energy between electrons and ions in solids

    International Nuclear Information System (INIS)

    In this review we consider those processes in condensed matter that involve the irreversible flow of energy between electrons and nuclei that follows from a system being taken out of equilibrium. We survey some of the more important experimental phenomena associated with these processes, followed by a number of theoretical techniques for studying them. The techniques considered are those that can be applied to systems containing many non-equivalent atoms. They include both perturbative approaches (Fermi's Golden Rule and non-equilibrium Green's functions) and molecular dynamics based (the Ehrenfest approximation, surface hopping, semi-classical Gaussian wavefunction methods and correlated electron-ion dynamics). These methods are described and characterized, with indications of their relative merits

  4. Challenges in reduction of dinitrogen by proton and electron transfer.

    Science.gov (United States)

    van der Ham, Cornelis J M; Koper, Marc T M; Hetterscheid, Dennis G H

    2014-08-01

    Ammonia is an important nutrient for the growth of plants. In industry, ammonia is produced by the energy expensive Haber-Bosch process where dihydrogen and dinitrogen form ammonia at a very high pressure and temperature. In principle one could also reduce dinitrogen upon addition of protons and electrons similar to the mechanism of ammonia production by nitrogenases. Recently, major breakthroughs have taken place in our understanding of biological fixation of dinitrogen, of molecular model systems that can reduce dinitrogen, and in the electrochemical reduction of dinitrogen at heterogeneous surfaces. Yet for efficient reduction of dinitrogen with protons and electrons major hurdles still have to be overcome. In this tutorial review we give an overview of the different catalytic systems, highlight the recent breakthroughs, pinpoint common grounds and discuss the bottlenecks and challenges in catalytic reduction of dinitrogen. PMID:24802308

  5. Adiabatic Transfer of Electrons in Coupled Quantum Dots

    CERN Document Server

    Brandes, T

    2002-01-01

    We investigate the influence of dissipation on one- and two-qubit rotations in coupled semiconductor quantum dots, using a (pseudo) spin-boson model with adiabatically varying parameters. For weak dissipation, we solve a master equation, compare with direct perturbation theory, and derive an expression for the `fidelity loss' during a simple operation that adiabatically moves an electron between two coupled dots. We discuss the possibility of visualizing coherent quantum oscillations in electron `pump' currents, combining quantum adiabaticity and Coulomb blockade. In two-qubit spin-swap operations where the role of intermediate charge states has been discussed recently, we apply our formalism to calculate the fidelity loss due to charge tunneling between two dots.

  6. Full counting statistics of electron transfer between superconductors

    OpenAIRE

    Belzig, W.; Nazarov, Yu V.

    2000-01-01

    We present an extension of the Keldysh-Green s function method, which allows one to calculate the full distribution of transmitted particles through a mesoscopic superconductor. The method is applied to the statistics of supercurrent in short contacts. If the current is carried by Andreev bound states the distribution corresponds to switching between long trains of electrons going in opposite directions. For weak (gapless) superconductors or tunnel junctions we find that at low temperatures t...

  7. Solvation-induced one-dimensional polarons and electron transfer

    OpenAIRE

    Ussery, G. L.; Gartstein, Yu N.

    2009-01-01

    When a one-dimensional (1D) semiconductor nanostructure is immersed in a sluggish polar solvent, fluctuations of the medium may result in the appearance of localized electronic levels inside the band gap. An excess charge carrier can occupy such a level and undergo self-localization into a large-radius adiabatic polaron surrounded by a self-consistent medium polarization pattern. Within an appropriately adapted framework of the Marcus theory, we explore the description and q...

  8. Recent Advances in Photoinduced Electron Transfer Processes of Fullerene-Based Molecular Assemblies and Nanocomposites

    Directory of Open Access Journals (Sweden)

    Osamu Ito

    2012-05-01

    Full Text Available Photosensitized electron-transfer processes of fullerenes hybridized with electron donating or other electron accepting molecules have been surveyed in this review on the basis of the recent results reported mainly from our laboratories. Fullerenes act as photo-sensitizing electron acceptors with respect to a wide variety of electron donors; in addition, fullerenes in the ground state also act as good electron acceptors in the presence of light-absorbing electron donors such as porphyrins. With single-wall carbon nanotubes (SWCNTs, the photoexcited fullerenes act as electron acceptor. In the case of triple fullerene/porphyrin/SWCNT architectures, the photoexcited porphyrins act as electron donors toward the fullerene and SWCNT. These mechanisms are rationalized with the molecular orbital considerations performed for these huge supramolecules. For the confirmation of the electron transfer processes, transient absorption methods have been used, in addition to time-resolved fluorescence spectral measurements. The kinetic data obtained in solution are found to be quite useful to predict the efficiencies of photovoltaic cells.

  9. A systematic study of electron or hole transfer along DNA dimers, trimers and polymers

    CERN Document Server

    Simserides, Constantinos

    2014-01-01

    A systematic study of electron or hole transfer along DNA dimers, trimers and polymers is presented with a tight-binding approach at the base-pair level, using the relevant on-site energies of the base-pairs and the hopping parameters between successive base-pairs. A system of $N$ coupled differential equations is solved numerically with the eigenvalue method, allowing the temporal and spatial evolution of electrons or holes along a $N$ base-pair DNA segment to be determined. Useful physical quantities are defined and calculated including the maximum transfer percentage $p$ and the pure maximum transfer rate $\\frac{p}{T}$ for cases where a period $T$ can be defined, as well as the pure mean carrier transfer rate $k$ and the speed of charge transfer $u=kd$, where $d = N \\times$ 3.4 {\\AA} is the charge transfer distance. The inverse decay length $\\beta$ used for the exponential fit $k = k_0 \\exp(-\\beta d)$ and the exponent $\\eta$ used for the power law fit $k = k_0' N^{-\\eta}$ are computed. The electron and hol...

  10. Fe electron transfer and atom exchange in goethite: influence of Al-substitution and anion sorption.

    Science.gov (United States)

    Latta, Drew E; Bachman, Jonathan E; Scherer, Michelle M

    2012-10-01

    The reaction of Fe(II) with Fe(III) oxides and hydroxides is complex and includes sorption of Fe(II) to the oxide, electron transfer between sorbed Fe(II) and structural Fe(III), reductive dissolution coupled to Fe atom exchange, and, in some cases mineral phase transformation. Much of the work investigating electron transfer and atom exchange between aqueous Fe(II) and Fe(III) oxides has been done under relatively simple aqueous conditions in organic buffers to control pH and background electrolytes to control ionic strength. Here, we investigate whether electron transfer is influenced by cation substitution of Al(III) in goethite and the presence of anions such as phosphate, carbonate, silicate, and natural organic matter. Results from (57)Fe Mössbauer spectroscopy indicate that both Al-substitution (up to 9%) and the presence of common anions (PO(4)(3-), CO(3)(2-), SiO(4)(4-), and humic acid) does not inhibit electron transfer between aqueous Fe(II) and Fe(III) in goethite under the conditions we studied. In contrast, sorption of a long-chain phospholipid completely shuts down electron transfer. Using an enriched isotope tracer method, we found that Al-substitution in goethite (10%), does, however, significantly decrease the extent of atom exchange between Fe(II) and goethite (from 43 to 12%) over a month's time. Phosphate, somewhat surprisingly, appears to have little effect on the rate and extent of atom exchange between aqueous Fe(II) and goethite. Our results show that electron transfer between aqueous Fe(II) and solid Fe(III) in goethite can occur under wide range of geochemical conditions, but that the extent of redox-driven Fe atom exchange may be dependent on the presence of substituting cations such as Al. PMID:22963051

  11. Verification of the electron/proton coupled mechanism for phenolic H-atom transfer using a triplet ?,? ? carbonyl

    Science.gov (United States)

    Yamaji, Minoru; Oshima, Juro; Hidaka, Motohiko

    2009-06-01

    Evidence for the coupled electron/proton transfer mechanism of the phenolic H-atom transfer between triplet ?,? ? 3,3'-carbonylbis(7-diethylaminocoumarin) and phenol derivatives is obtained by using laser photolysis techniques. It was confirmed that the quenching rate constants of triplet CBC by phenols having positive Hammett constants do not follow the Rehm-Weller equation for electron transfer while those by phenols with negative Hammett constants do it. From the viewpoint of thermodynamic parameters for electron transfer, the crucial factors for phenolic H-atom transfer to ?,? ? triplet are discussed.

  12. Mimicking the electron transfer chain in photosystem II with a molecular triad thermodynamically capable of water oxidation

    OpenAIRE

    Megiatto, Jackson D.; Antoniuk-pablant, Antaeres; Sherman, Benjamin D.; Kodis, Gerdenis; Gervaldo, Miguel; Moore, Thomas A.; Moore, Ana L.; Gust, Devens

    2012-01-01

    In the photosynthetic photosystem II, electrons are transferred from the manganese-containing oxygen evolving complex (OEC) to the oxidized primary electron-donor chlorophyll P680•+ by a proton-coupled electron transfer process involving a tyrosine-histidine pair. Proton transfer from the tyrosine phenolic group to a histidine nitrogen positions the redox potential of the tyrosine between those of P680•+ and the OEC. We report the synthesis and time-resolved spectroscopic study of a molec...

  13. Controlling factors in electron and energy transfer reactions on silica gel surfaces.

    Science.gov (United States)

    Worrall, David R; Kirkpatrick, Iain; Williams, Sian L

    2002-11-01

    Energy and electron transfer reactions between co-adsorbed molecules on silica gel have been studied using nanosecond time-resolved diffuse reflectance laser flash photolysis. The systems under investigation are anthracene and 9-carboxylic acid anthracene co-adsorbed with azulene, which undergo both triplet-triplet energy transfer and electron transfer from azulene to the anthracene radical cation following laser excitation. The decay traces have been analysed using a model which assumes a log gaussian distribution of rate constants and the methodology behind the optimisation of the fitting parameters is described. Bimolecular rate constants for energy and electron transfer between anthracene (and its derivative) and azulene have been obtained. Ground state association between anthracene and azulene has been observed, and an equilibrium constant for the process determined. The kinetic data is corrected for these ground state association effects which reduce the free azulene concentration. For both systems and for both the energy and electron transfer processes, analysis of the quenching data yields the same quenching constant. This indicates that the rate of reaction of anthracene (and the 9-carboxylic acid anthracene) on silica gel is predominantly governed by the rate of diffusion of the quencher. PMID:12659530

  14. Multiple electron transfer processes in collisions of N6+ and O7+ with methane

    International Nuclear Information System (INIS)

    Recent experiments on collision processes of O7+ and N6+ ions colliding with methane at the same velocity show unexpected differences in the fragmentation cross sections of the methane. Despite the expected similarity of these two processes, as both projectiles are hydrogenic, the mechanisms of electron transfer are different and lead to different fragmentation cross sections. In the present work, the collisions between N6+ and O7+ ions and methane are investigated theoretically at equal velocities corresponding to projectile energies of 30 and 35 keV, respectively. Electron-nuclear dynamics is used to study multiple electron transfer processes occurring in these collisions. Several multiple charge transfer probabilities are calculated and results, averaged over various orientations of the methane molecule, are reported. The collisions proceed in two stages: a fast stage of electron transfer from methane to the ion, and a much slower stage of breakup of the methane. We find and explain the intuitively unexpected result that the total charge transfer cross section for N6+ is slightly larger, but that the O7+ leaves the methane in a higher charged state with higher probability, leading to more fragmentation in the collisions with O7+.

  15. Excitational energy and photoinduced electron transfer reactions in Ge(IV) corrole–porphyrin hetero dimers

    Energy Technology Data Exchange (ETDEWEB)

    Giribabu, Lingamallu, E-mail: giribabu@iict.res.in; Kandhadi, Jaipal; Kanaparthi, Ravi Kumar; Reeta, P. Silviya

    2014-01-15

    We have constructed hetero dimers by utilizing the axial bonding capabilities as well as known oxophilicity of Germanium(IV) ion of Germanium(IV) corroles as basal scaffolding unit and either free-base or Zn{sup II} porphyrin at axial position for the first time. Both the hetero dimers have been completely characterized by elemental analysis, UV–visible, proton nuclear magnetic resonance (1D and {sup 1}H–{sup 1}H COSY) and fluorescence spectroscopies as well as electrochemical methods. The ground state properties indicate that there exists a minimum ?–? interactions between the macrocyclic units of these dyads. Excited state properties showed that there is an electronic energy transfer competing photoinduced electron transfer from singlet state of basal metalloid corrole to the axial porphyrin and a photoinduced electron transfer from excited state of axial porphyrin to the ground state of central metalloid corrole are possible. -- Highlights: ? • We have constructed hetero dimers based on corrole–porphyrin by utilizing axial position of Ge(IV) corrole. • There exists mimum ?–? interactions between the macrocyclic units. • The excited state properties indicate that both excitation energy transfer and photoinduced electron transfer reactions are possible in these hetero dimers.

  16. Intramolecular aspects of the electron transfer in the biferrocenium mixed-valence cation, using PKS theory

    Science.gov (United States)

    Boukheddaden, Kamel; Linares, Jorge; Bousseksou, Azzedine; Nasser, Jamil; Rabah, Hamid; Varret, François

    1993-02-01

    The electron transfer properties of the mixed-valence biferrocenium cation are investigated using the Piepho-Krausz-Schatz (PKS) vibronic theory. Parameters of the model are deduced from both vibrational spectroscopy (stiffness constant) and MO calculations (transfer integral and vibronic coupling parameter); the computed asymmetric distortion agrees with structural data; a specific heat Schottky anomaly, recently reported, is also explained in the frame of that model. The low-temperature transfer rate is also computed. it ranges from 1.5 × 10 10 to 8.7 x 10 12 s -1, according to the nature of the HOMO, and definitely lies higher than the Mössbauer timescale (? 10 8 s -1).

  17. An efficient implementation of the localized operator partitioning method for electronic energy transfer

    Science.gov (United States)

    Nagesh, Jayashree; Izmaylov, Artur F.; Brumer, Paul

    2015-02-01

    The localized operator partitioning method [Y. Khan and P. Brumer, J. Chem. Phys. 137, 194112 (2012)] rigorously defines the electronic energy on any subsystem within a molecule and gives a precise meaning to the subsystem ground and excited electronic energies, which is crucial for investigating electronic energy transfer from first principles. However, an efficient implementation of this approach has been hindered by complicated one- and two-electron integrals arising in its formulation. Using a resolution of the identity in the definition of partitioning, we reformulate the method in a computationally efficient manner that involves standard one- and two-electron integrals. We apply the developed algorithm to the 9 - ((1 - naphthyl) - methyl) - anthracene (A1N) molecule by partitioning A1N into anthracenyl and CH2 - 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 the excited electronic states.

  18. Electron transfer and solvation in 3-methylpentane-1-propanol mixtures ?-irradiated at 77 and 4 K

    International Nuclear Information System (INIS)

    The trapped electron in 3-methylpentane-1-propanol mixtures ?-irradiated at 77 and 4 K was investigated by observing the evolution of the trapped electron spectra at 77 K by conventional spectrophotometric method. An isosbestic point observed during the spectral evolution indicated that almost all the electrons in 3-methylpentane traps transformed efficiently to those in 1-propanol traps at high concentration of 1-propanol (> 0.6 mol dm-3). Results were interpreted in terms of diffusional transfer of the electron or combined diffusion and tunneling mechanism. The electron spectra observed from the mixture irradiated at 4 K were different from the spectra for irradiation at 77 K: the former spectra were due to both shallowly-trapped alcoholated electrons and unrelaxed hydrocarbonated electrons. (author)

  19. Linear free-enthalpy relation for radical yield in fluorescence quenching by electron transfer

    OpenAIRE

    Iwa, Peter; Steiner, Ulrich; Vogelmann, Ekehardt; Kramer, Horst E. A.

    1982-01-01

    The rate constant (kq) and net electron-transfer yield (?r) in the quenching of an excited oxonine singlet by 24 aromatic amines and methoxy compounds were determined in methanol from stationary fluorescence measurements and flash spectroscopy. The systems investigated correspond to a variation of ?Get°, the standard free reaction enthalpy of the electron transfer from the quencher to excited singlet oxonine, between -0.12 and -1.56 eV. Whereas the kq values observed are all close to the d...

  20. Tensor polarization measurement in elastic electron-deuteron scattering at large momentum transfer

    International Nuclear Information System (INIS)

    The three tensor polarization components (t20, t21 and t22) of the recoil deuteron in elastic electron-deuteron scattering have been measured in the range of 4-momentum transfer Q = 4.1-6.8 fm-1. The experiment was performed with the multi-GeV, high intensity electron beam available at the Jefferson Laboratory and using the tensor deuteron polarimeter POLDER. These new data are used to separate the charge GC and quadrupole GQ form factors at large momentum transfer and provide additional constraints on theoretical models. (author)