976 resultados para ONE-ELECTRON OXIDATION
Resumo:
By using polarization-resolved photoluminescence spectra, we study the electron spin relaxation in single InAs quantum dots (QDs) with the configuration of positively charged excitons X+ (one electron, two holes). The spin relaxation rate of the hot electrons increases with the increasing energy of exciting photons. For electrons localized in QDs the spin relaxation is induced by hyperfine interaction with the nuclei. A rapid decrease of polarization degree with increasing temperature suggests that the spin relaxation mechanisms are mainly changed from the hyperfine interaction with nuclei into an electron-hole exchange interaction.
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A self-consistent solution of conduction band profile and subband energies for AlxGa1-xN-GaN quantum well is presented by solving the Schrodinger and Poisson equations. A new method is introduced to deal with the accumulation of the immobile charges at the AlxGa1-xN-GaN interface caused by spontaneous and piezoelectric polarization in the process of solving the Poisson equation. The effect of spontaneous and piezoelectric polarization is taken into account in the calculation. It also includes the effect of exchange-correlation to the one electron potential on the Coulomb interaction. Our analysis is based on the one electron effective-mass approximation and charge conservation condition. Based on this model, the electron wave functions and the conduction band structure are derived. We calculate the intersubband transition wavelength lambda(21) for different Al molar fraction of barrier and thickness of well. The calculated result can fit to the experimental data well. The dependence of the absorption coefficient a on the well width and the doping density is also investigated theoretically. (C) 2004 American Vacuum Society.
Resumo:
A single-electron turnstile and electrometer circuit was fabricated on a silicon-on-insulator substrate. The turnstile, which is operated by opening and closing two metal-oxide-semiconductor field-effect transistors (MOSFETs) alternately, allows current quantization at 20 K due to single-electron transfer. Another MOSFET is placed at the drain side of the turnstile to form an electron storage island. Therefore, one-by-one electron entrance into the storage island from the turnstile can be detected as an abrupt change in the current of the electrometer, which is placed near the storage island and electrically coupled to it. The correspondence between the quantized current and the single-electron counting was confirmed.
Resumo:
The energetics, lattice relaxation, and the defect-induced states of st single O vacancy in alpha-Al2O3 are studied by means of supercell total-energy calculations using a first-principles method based on density-functional theory. The supercell model with 120 atoms in a hexagonal lattice is sufficiently large to give realistic results for an isolated single vacancy (square). Self-consistent calculations are performed for each assumed configuration of lattice relaxation involving the nearest-neighbor Al atoms and the next-nearest-neighbor O atoms of the vacancy site. Total-energy data thus accumulated are used to construct an energy hypersurface. A theoretical zero-temperature vacancy formation energy of 5.83 eV is obtained. Our results show a large relaxation of Al (O) atoms away from the vacancy site by about 16% (8%) of the original Al-square (O-square) distances. The relaxation of the neighboring Al atoms has a much weaker energy dependence than the O atoms. The O vacancy introduces a deep and doubly occupied defect level, or an F center in the gap, and three unoccupied defect levels near the conduction band edge, the positions of the latter are sensitive to the degree of relaxation. The defect state wave functions are found to be not so localized, but extend up to the boundary of the supercell. Defect-induced levels are also found in the valence-band region below the O 2s and the O 2p bands. Also investigated is the case of a singly occupied defect level (an F+ center). This is done by reducing both the total number of electrons in the supercell and the background positive charge by one electron in the self-consistent electronic structure calculations. The optical transitions between the occupied and excited states of the: F and F+ centers are also investigated and found to be anisotropic in agreement with optical data.
Resumo:
he first order perturbations of the energy levels of a stationary hydrogen atom in a static external gravitational field, with Schwarzschild metric, are investigated. The energy shifts are calculated for the relativistic 1S, 2S, 2P, 3S, 3P, 3D, 4S, 4P, 4D, and 4F levels. The results show that the energy-level shifts of the states with total angular momentum quantum number 1/2 are all zero, and the ratio of absolute energy shifts with total angular momentum quantum number 5/2 is 145. This feature can be used to help us to distinguish the gravitational effect from other effects.
Resumo:
5,10,15,20-Tetra-[(p-alkoxy-m-ethyloxy)phenyl]porphyrin and [5-(p-alkoxy)phenyl-10,15,20-tri-phenyl]porphyrin and their holmium(III) complexes are reported. They display a hexagonal columnar discotic columnar Col(h)) liquid crystal phase and were studied by cyclic voltammetry, surface photovoltage spectroscopy (SPS), electric-field-induced surface photovoltage spectroscopy (EFISPS) and luminescence spectroscopy. Within the accessible potential window, all these compounds exhibit two one-electron reversible redox reactions. Quantum yields of Q band are in the region 0.0045-0.21 at room temperature. The SPS and EFISPS reveal that all the compounds are p-type semiconductors and exhibit photovoltaic response due to pi-pi* electron transitions.
Resumo:
For the first time horseradish peroxidase (HRP) immobilized on the surface of active carbon powder modified at the surface of a glassy carbon electrode has been shown to undergo a direct quasi-reversible electrochemical reaction. Its formal potential, E-o/, is -0.363 V in phosphate buffer solution (pH 6.8) at a scan rate of 100 mV/s and is almost independent of the scan rate in the range of 50-700 mV/s. The dependence of E-o/ on the pH of the buffer solution indicated that the conversion of HRP-Fe(III)/HRP-Fe(II) is a one-electron-transfer reaction process coupled with one-proton-transfer. The experimental results also demonstrated that the immobilized HRP retained its bioelectrocatalytic activity to the reduction of H2O2. Furthermore, the HRP adsorbed oil the surface of the active carbon powder can be stored at 4 degreesC for several months without any loss of the enzyme activity. The method presented for immobilizing HRP can be easily extended to immobilize and obtain the direct electrochemistry of other enzymes.
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A novel sandwich-type compound, Na-12[Fe-4(H2O)(2)(As2W15O56)2].41H(2)O, has been synthesized. The compound was well-characterized by means of IR, UV-vis, W-183 NMR and elemental analyses. The compound crystallizes in the triclinic, P (1) over bar symmetry group. The structure of the compound is similar to that of Na-16[M-4(H2O)(2)(As2W15O56)(2)].nH(2)O (M = Cu, Zn, Co, Ni, Mn, Cd), and consists of an oxo-aqua tetranuclear iron core, [(Fe4O14)-O-III(H2O)(2)], sandwiched by two trivacant alpha-Wells-Dawson structural moieties, alpha-[As2W15O56]. Redoxelectrochemistry of the compound has been studied in buffer solutions at pH = 4.7 using polarography and cyclic voltammetry ( CV). The compound exhibited four one-electron couples associated with the Fe(III) center followed by three four-electron redox processes attributed to the tungsten-oxo framework. The compound-containing monolayer and multilayer films have been fabricated on a 4-aminobenzoic acid modified glassy carbon electrode surface by alternating deposition with a quaternized poly(4-vinylpyridine) partially complexed with [Os(bpy)(2)Cl](2+/-). CV, X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy and atomic force microscopy (AFM) have been used to characterize the multilayer films.
Resumo:
The rational synthesis and the structural and magnetic characterization of a nickel cluster are presented. The compound comprises a rhomblike Ni4O16 group encapsulated between two-heptadentate tungstoarsenate ligands [AsW9O34](9-). The crystal structure of K-10[Ni-4(H2O)(2)(AsW9O34)(2)](.)4H(2)O was solved in monoclinic, P2(1)/n symmetry, with a = 12.258(3) Angstrom, b = 21.232(4) Angstrom, c = 15.837(3) Angstrom, beta = 92.05(3)degrees, V = 4119.1(14) Angstrom(3), Z = 2, and R = 0.0862. The crystal structure of the Ni(II) derivative was compared with that of the Cu(II), Zn(II), Co(II) and Mn(II) derivatives. The Ni4O14(H2O)(2) unit in the compound shows no Jahn-Teller distortion. On the other hand, the Ni(II) derivative shows ferromagnetic exchange interactions within the Ni4O16 group (J = 7.8 cm(-1), J' = 13.7 cm(-1)) and an S = 4 ground state, the highest spin state reported in a heteropoly complex. Its redox electrochemistry has been studied in acid buffer solutions using cyclic voltammetry. It exhibited two steps of one-electron redox waves attributed to redox processes of the tungsten-oxo framework. The new catalyst showed an electrocatalytic effect on the reduction of NO2-.
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V(IV) and V(V) containing mixed-valence heteropolytungstogermanates have been prepared by controlled potential reduction of corresponding GeW9V3O407-, their electronic spectra have been recorded. The ESR spectra of one-electron-reduced anions in solution at 340K consist of more than 40 equally spaced lines, showing that the three VO6 octahedra in both alpha- and beta-forms are corner-shaped and one of the bridging oxygen atoms is protonated at pH 4.7.
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Electrochemical reactions of cyanocobalamin, CN-Cbl[Co(III)], were studied at glassy carbon electrodes in acidic media by means of cyclic voltammetry and differential pulse polarography. It was found that in pH 0 solution, CN-Cbl[Co(III)] exists mainly in the base-off form, {CN-Cbl[Co(III)]}(base-off). It can undergo a one-electron reduction and a follow-up chemical reaction to form {H2O-Cbl[Co(II)]}(base-off). The rate-constant k of the follow-up decyanation reaction is 0.022 s(-1). {H2O-Cbl[Co(II)]}(base-off) is further reduced to obtain H2O-Cbl[Co(I)]. (C) 1997 Elsevier Science S.A.
Resumo:
The electrochemical behavior of the electroactive self-assembled monolayers (SAMs) of thiol-functionalized viologen, CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is a viologen group, on the gold electrodes is examined by cyclic voltammetry and electrochemical a.c. impedance. A monolayer of viologen is immobilized on the gold electrode surface via the Au-S bond and the normal potentials corresponding to the two successive one-electron transfer processes of the viologen active centers are -310 mV and -652 mV (vs. Ag/AgCl) in 0.1 mol l(-1) phosphate buffer solution (pH 6.96) respectively. These results suggest that the viologen SAMs are stable and well-behaved monolayers. The experimental impedance data corresponding to different forms of viologen group have been fitted to equivalent electrical circuits, and the surface capacitances and resistances have been given. The heterogenous electron transfer rates of the first and the second redox processes are 7.57 s(-1) and 1.49 s(-1) respectively through a.c. impedance.
Resumo:
Eastman-AQ 55D was coated onto a carbon fiber microelectrode surface, and the resulting modified electrodes exhibited high stability. Substantial improvement in the stability was observed as a result of good adhesion and the strong binding of large hydrophobic cations of Eastman AQ 55D. The electrode reaction of meldola blue bound in the polymer film showed a reversible, one-electron transfer process. The effects of solution pH and influence of supporting electrolyte on the modified carbon fiber microelectrode are discussed. The diffusion coefficient of meldola blue in the AQ polymer film determined by chronoamperometry is 2.3 x 10(-18) cm(2) s(-1), and the heterogeneous rate constant of meldola blue at the AQ polymer film/electrode determined by normal pulse voltammetry is 3.97 x 10(-3) cms(-1).
Resumo:
Electroactive self-assembled monolayers (SAMs) containing viologen group are formed through the adsorption of thiol-functionalized viologen compound CH3(CH2)(9)V2+(CH2)(8)SH, where V2+ is N,N'-dialkylbipyridinium (i.e. a viologen group), onto gold electrodes from methanol/water solution and its electrochemical behavior is investigated ty Ac voltammetry and square wave voltammetry, which have the high sensitivity against background charging. The viologen SAM formed is a sub-monolayer and the normal potentials corresponding to the two successive one-electron transfer processes of the active centers (viologen) are -360 mV and -750 mV (vs. Ag/AgCl) in 0.1 mol/L phosphate buffer solutions (pH 6.96) respectively, and the standard electron transfer rate constant is 9.0 s(-1). The electrochemical behavior of this SAM in various solutions has been preliminarily discussed.