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.

Luminescence and non-radiative processes in lanthanide squarate hydrates

The luminescence properties of solid hydrated lanthanide squarates (Ln2(C4O4)3(H2O) x; x = 8 or 13;Ln3+ = Gd, La, Eu, Tb, Pr) are reported for temperatures down to 4.2K. The luminescence of the squarate group is observed for the Gd3+ and La3+ compounds at low temperatures (below 150K). The Pr3+ compound does not show any emission at all, not even at 4.2K. This is ascribed to the quenching of the Pr3+ emission by multiphonon relaxation and/or concentration quenching. The quantum efficiencies of the 5D0 emission of Eu3+ and of the 5D4 emission of Tb3+ in these squarate complexes are strikingly different. Whereas the Tb3+ emission shows a temperature independent quantum efficiency of 50% upon ligand excitation, the Eu3+ emission is strongly quenched, showing a temperature dependent quantum efficiency of 0.8% at 4.2K upon ligand excitation. This quenching is ascribed to the low energy position of the charge-transfer state of Eu3+ in these compounds.

Estudo das propriedades estruturais e ópticas do sistema vítreo 80TeO2-20WO3 dopado com Yb2O3

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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.

Low-energy direct muon transfer from H to Ne10+, S16+ and Ar18+ using the two-state close-coupling approximation to the Faddeev-Hahn-type equation

We perform a three-body calculation of direct muon-transfer rates from thermalized muonic hydrogen isotopes to bare nuclei Ne10+, S16+ and Ar18+ employing integro-differential Faddeev-Hahn-type equations in configuration space with a two-state close-coupling approximation scheme. All Coulomb potentials including the strong final-state Coulomb repulsion are treated exactly. A long-range polarization potential is included in the elastic channel to take into account the high polarizability of the muonic hydrogen. The transfer rates so-calculated are in good agreement with recent experiments. We find that the muon is captured predominantly in the n = 6, 9 and 10 states of muonic Ne10+, S16+ and Ar18+, respectively.

Electron transfer by singlet excited state of porphyn and electron acceptor affinity in rigid medium: photoacoustic phase angle analysis

A espectroscopia fotoacústica obtém informações sobre amplitude e fase, da resposta de um sistema submetido a excitação por luz. Este artigo apresenta estudos do ângulo de fase no processo de transfereência de elétrons entre octaetilporfirina (OEP) e derivados de quinona ambos dispersos em uma matriz polimérica. Observou-se uma tendência no comportamento da fase para valores menores na região espectral próximo de 620 nm. Enquanto que para comprimentos de onda menores este efeito não foi apresentado. Estas medidas sugerem que a transferência de elétrons para o aceitador ocorreu com a participação do estado singleto excitado da octaetilporfirina.

Distribution of Ra-226, Th-232 and K-40 in soils and sugar cane crops at Corumbatai river basin, São Paulo State, Brazil

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

H-infinity control design for time-delay linear systems: a rational transfer function based approach

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

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.

Statistics and kinetics of single-molecule electron transfer dynamics in complex environments: A simulation model study

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

Metal fluxes at the sediment-water interface in rivers in the Turvo/Grande drainage basin, So Paulo State, Brazil

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

Low-energy muon-transfer reaction from hydrogen isotopes to helium isotopes

Direct muon transfer in low-energy collisions of the muonic hydrogen H-mu and helium (He++) is considered in a three-body quantum-mechanical framework of coordinate-space integro-differential Faddeev-Hahn-type equations within two- and six-state close coupling approximations. The final-state Coulomb interaction is treated without any approximation employing appropriate Coulomb waves in the final state. This procedure of treating Coulomb interaction leads to much improved results for low-energy transfer rates. The present results agree reasonably well with previous semiclassical calculations. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Ultracold collisions between two light indistinguishable diatomic molecules: Elastic and rotational energy transfer in HD plus HD

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

On an Non-Ideal Global and Local Energy Transfer, Using an Electro-Magneto and Magneto-Rheological Dampers

In this paper, we investigated the nonlinear vibrations of a Non-ideal (NIS) electromechanical absorber (NEVA), taking into account a modified mathematical model of (MR) Damper. We observed the presence of the Sornmerfeld effect (it is the steady state frequencies of the DC motor, which it will usually increasing as more power (Voltage) is given to it, in a step-by-step fashion. When a resonance condition it is reached, the better part of this energy it is consumed to generate large amplitude vibrations of the foundation, without sensible change of the motor frequency). The obtained results, by using numerical and analytical simulations, were discussed, in details.

On energy transfer phenomena, in a nonlinear ideal and nonideal essential vibrating systems, coupled to a (MR) magneto-rheological damper

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