Low-energy three-body charge transfer reactions with Coulomb interaction in the final state

Three-body charge transfer reactions with Coulomb interaction in the final state are considered within the framework of coordinate-space integro-differential Faddeev-Hahn-type equations within two- and six-state close-coupling approximations. The method is employed to study direct muon transfer in low-energy collisions of the muonic hydrogen H-mu by helium (He2+) and lithium (Li3+) nuclei. The experimentally observed isotopic dependence is reproduced.

Spectrophotometric Determination of Captopril Through Charge Transfer Complex Formation Using Fractional Factorial and Central Composite Design

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Coordinate-space Faddeev-Hahn-type approach to three-body charge-transfer reactions involving exotic particles

Low-energy muon-transfer cross sections and rates in collisions of muonic atoms with hydrogen isotopes are calculated using a six-state close-coupling approximation to coordinate-space Faddeev-Hahn-type equations. In the muonic case satisfactory results are obtained for all hydrogen isotopes and the experimentaly observed strong isotopic dependence of transfer rates is also reproduced. A comparison with results of other theoretical and available experimental works is presented. The present model also leads to good transfer cross sections in the well-understood problem of antihydrogen formation in antiproton-positronium collision.

Multiferroicity in an organic charge-transfer salt that is suggestive of electric-dipole-driven magnetism

Multiferroics, showing simultaneous ordering of electrical and magnetic degrees of freedom, are remarkable materials as seen from both the academic and technological points of view. A prominent mechanism of multiferroicity is the spin-driven ferroelectricity, often found in frustrated antiferromagnets with helical spin order. There, as for conventional ferroelectrics, the electrical dipoles arise from an off-centre displacement of ions. However, recently a different mechanism, namely purely electronic ferroelectricity, where charge order breaks inversion symmetry, has attracted considerable interest. Here we provide evidence for ferroelectricity, accompanied by antiferromagnetic spin order, in a two-dimensional organic charge-transfer salt, thus representing a new class of multiferroics. We propose a charge-order-driven mechanism leading to electronic ferroelectricity in this material. Quite unexpectedly for electronic ferroelectrics, dipolar and spin order arise nearly simultaneously. This can be ascribed to the loss of spin frustration induced by the ferroelectric ordering. Hence, here the spin order is driven by the ferroelectricity, in marked contrast to the spin-driven ferroelectricity in helical magnets. © 2012 Macmillan Publishers Limited. All rights reserved.

A comparison of charge-transfer mechanisms at rotated disk electrode for biomimetic binuclear and tetranuclear oxo-manganese complex in aqueous solution

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Energy-transfer mechanisms and emission quantum yields in Eu3+-based siloxane-poly(oxyethylene) nanohybrids

We report the energy-transfer mechanisms and emission quantum yield measurements of sol-gel-derived Eu3+-based nanohybrids. The matrix of these materials, classified as diureasils and termed U(2000) and U(600), includes urea cross-links between a siliceous backbone and polyether-based segments of two molecular weights, 2000 and 600, respectively. These materials are full-color emitters in which the Eu3+ (5)Do --> F-7(0-4) lines merge with the broad green-blue emission of the nanoscopic matrix's backbone. The excitation spectra show the presence of a large broad band (similar to 27000-29000 cm(-1)) undoubtedly assigned to a ligand-to-metal charge-transfer state. Emission quantum yields range from 2% to 13.0% depending on the polymer molecular weight and Eu3+ concentration. Energy transfer between the hybrid hosts and the cations arises from two different and independent processes: the charge-transfer band and energy transfer from the hybrid's emitting centers. The activation of the latter mechanisms induces a decrease in the emission quantum yields (relative to undoped nanohybrids) and permits a fine-tuning of the emission chromaticity across the Comission Internacionalle d'Eclairage diagram, e.g., (x, y) color coordinates from (0.21, 0.24) to (0.39, 0.36). Moreover, that activation depends noticeably on the ion local coordination. For the diureasils with longer polymer chains, energy transfer occurs as the Eu3+ coordination involves the carbonyl-type oxygen atoms of the urea bridges, which are located near the hybrid's host emitting centers. on the contrary, in the U(600)-based diureasils, the Eu3+ ions are coordinated to the polymer chains, and therefore, the distance between the hybrid's emitting centers and the metal ions is large enough to allow efficient energy-transfer mechanisms.

Smooth landscape solvent dynamics in electron transfer reactions

Solvent effects play a major role in controlling electron-transfer reactions. The solvent dynamics happens on a very high-dimensional surface, and this complex landscape is populated by a large number of minima. A critical problem is to understand the conditions under which the solvent dynamics can be represented by a single collective reaction coordinate. When this unidimensional representation is valid, one recovers the successful Marcus theory. In this study the approach used in a previous work [V. B. P. Leite and J. N. Onuchic; J. Phys. Chem. 100, 7680 (1996)] is extended to treat a more realistic solvent model, which includes energy correlation. The dynamics takes place in a smooth and well behaved landscape. The single shell of solvent molecules around a cavity is described by a two-dimensional system with periodic boundary conditions with nearest neighbor interaction. It is shown how the polarization-dependent effects can be inferred. The existence of phase transitions depends on a factor y proportional to the contribution from the two parameters of the model. For the present model, γ suggests the existence of weak kinetic phase transitions, which are used in the analysis of solvent effects in charge-transfer reactions. © 1999 American Institute of Physics.

Dynamical calculation of direct muon-transfer rates from thermalized muonic hydrogen to C6+ and O8+

Moun-transfer reactions from muonic hydrogen to carbon and oxygen nuclei employing a full quantum-mechanical few-body description of rearrangement scattering were studied by solving the Faddeev-Hahn-type equations using close-coupling approximation. The application of a close-coupling-type ansatz led to satisfactory results for direct muon-transfer reactions from muonic hydrogen to C6+ and O8+.

Charge-ordering transition in (TMTTF)2X explored via dilatometry

Charge-ordering phenomena have been highly topical over the past few years. A phase transition towards a charge-ordered state has been observed experimentally in several classes of materials. Among them, many studies have been devoted to the family of quasi-one-dimensional organic charge-transfer salts (TMTTF)2X, where (TMTTF) stands for tetramethyltetrathiafulvalene and X for a monovalent anion (X = PF6, AsF6 and SbF6). However, the relationship between the electron localization phenomena and the role of the lattice distortion in stabilizing the charge-ordering pattern is poorly documented in the literature. Here we present a brief overview of selected literature results, with emphasis placed on recent thermal expansion experiments probing the charge-ordering transition of these salts. © 2013 IOP Publishing Ltd.

The effect of Eu3+ concentration on the Y2O3 host lattice obtained from citrate precursors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Luminescent and morphological study of Sr2CeO4 blue phosphor prepared from oxalate precursors

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrochemical Redox Behavior of Omeprazole Using a Glassy Carbon Electrode

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Understanding the origin of photoluminescence in disordered Ca0.60Sr0.40WO4: An experimental and first-principles study

Visible photoluminescence (PL) was observed for the first time at room temperature in structurally disordered calcium strontium tungstate powder, Ca0.60Sr0.40WO4 (CSW), obtained by the polymeric precursor method. The PL behavior of CSW powders has been analyzed as a function of the disorder rate, based on experimental and theoretical studies. Quantum mechanical theory based on density functional theory at the B3LYP level has been employed to study the electronic structure of two periodic models representing both crystalline and disordered powders. Their electronic structures have been analyzed in terms of density of states, band dispersion and charge densities. The calculations indicate a break in symmetry when passing from crystalline to disordered models, creating localized electronic levels above the valence band. Moreover, a negative charge transfer process takes place from the [WO3] cluster to the [WO4] cluster. The polarization induced by the break in symmetry and the existence of localized levels favors the creation of trapped holes and electrons, originating the PL phenomenon. (c) 2007 Elsevier B.V. All rights reserved.

Surface Passivation of Nanoporous TiO2 via Atomic Layer Deposition of ZrO2 for Solid-State Dye-Sensitized Solar Cell Applications

We report here the utilization of atomid layer deposition to passivate surface map states in mosoporous TiO2 nanoparticles for solid state dye sensitized solar cells based on 9,9'-spirobifluorene (spiro-OMeTAD). By depositing ZrO2 films with angstrom-level precision, coating the mesoporous TiO2 produces over a two-fold enhancement in short-circuit current density, as compared to a control device. Impedance spectroscopy measurements provide evidence that the ZrO2 coating reduces recombination lossed at the TiO2/spiro-OMeTAD interface and passivates localized surface states. Low-frequency negative capacitances, frequently observed in nanocomposite solar cells, have been associated with the surface-state mediated charge transfer from TiO2 to the spiro-OMeTAD.