83 resultados para INTRAMOLECULAR ENERGY-TRANSFER


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In this work, GdAlO3:Pr3+ was successfully prepared by the Pechini method at lower temperatures when compared to others methods such as solid-state synthesis and sol-gel process. In accordance to the XRD data, the fully crystalline single-phase GdAlO3 could be obtained at 900 degrees C. Luminescence measurements indicate Gd -> Pr3+ energy transfer. In the emission spectra, the P-3(0) ->(3) H-4 (blue emission) and D-1(2) ->(3) H-4 (red emission) transitions of Pr3+ ions can be observed and the ratio between their intensities depends on the Pr3+ content due to the cross-relaxation phenomenon.

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In this work, GdAlO3:RE3+ (RE = Eu or Tb) was successfully prepared by the Pechini method at lower temperatures when compared to others methods as solid-state synthesis and sol-gel process. In accordance to the XRD data, the fully crystalline single-phase GdAlO3 could be obtained at 900 degrees C. The differential thermal analysis (DTA) shows a crystallization peak at 850 degrees C. The samples are composed by monocrystalline particles (50-120 nm) exhibiting the formation of aggregates among them, which indicates the beginning of the sinterization process. This feature indicates a strong tendency to the formation of aggregates, which is a suitable ability for the close-packing of particles, and hence a potential application in X-ray intensifying screens. Luminescence measurements indicate Gd3+ -> RE3+ energy transfer. The Eu3+ emission spectra exhibit all the characteristics D-5(0) -> F-7(j) transitions and the observed profile suggests that RE3+ ions occupy at least one site without center of symmetry. For terbium-doped samples, the D-5(3) -> F-7(j) (blue emission) and D-5(4) -> F-7(j) (green emission) transitions were observed and the ratio between them may depend on the Tb3+ content due to cross-relaxation processes. (C) 2009 Elsevier B.V. All rights reserved.

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The synthesis and characterization of a new organic ligand monooctyldiphenylphosphinate (L) is described, as well as a new Eu(3+) diketonate complex [Eu(tta)(3)(L)(2)] (tta = thenoyltrifluoracetone). The ligand (L) was formed by substitution reaction (80% yield) and characterized by uni- and bidimensional (1)H, (13)C and (31)P NMR experiments, to confirm its molecular structure. The coordination of (L) to Eu(3+) in the complex [Eu(tta)(3)(L)(2)] was confirmed by FT-IR spectra. The emission spectra present the same profile when excited in Eu(3+) or in the ligands, suggesting an energy transfer from ligands to Eu(3+) ions. The emission spectra of the precursor [Eu(tta)(3)(H(2)O)(2)], and [Eu(tta)(3)(L(2))] present bands arising from f-f intra-configurational transitions. The only (5)D(0)-(7)F(0) transition shows the presence of at least one site without symmetry center. The FWHM of such transition is 7 cm(-1) and 57 cm(-1) for [Eu(tta)(3)(H(2)O)(2)] and [Eu(tta)(3)(L)(2)] complexes, respectively. This widening is provided by the presence of large groups around Eu(3+) ion. The calculated intensity parameters Omega(2) and Omega(4) show that the interaction features between center-ion and ligand are different; the small value of Omega(4) is related to long range effects of alkyl chain. The Langmuir isotherms of this ligand and complex have been investigated although their hydrolysis in water subphase does not allow stable monolayers. (C) 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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

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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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Er3+ emission in the wide bandgap matrix SnO2 is observed either through a direct Er ion excitation process as well as by an indirect process, through energy transfer in samples codoped with Yb3+ ions. Electron-hole generation in the tin dioxide matrix is also used to promote rare-earth ion excitation. Photoluminescence spectra as function of temperature indicate a slight decrease in the emission intensity with temperature increase, yielding low activation energy, about 3.8meV, since the emission even at room temperature is rather considerable.

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The sensitized photolysis of [Ru(NH3)(6)](2+) by the organic dye rhodamine B and biacetyl was studied under conditions in which only the sensitizer absorbs. The reaction products resulting from ammonia aquation and Ru(II) to Ru(III) oxidation are the same for direct and sensitized photolysis. The energy transfer rate constant, calculated from the fluorescence quenching of rhodamine B, is similar to that estimated from the limiting quantum yield of the photosensitized photoaquation of the complex. Both reactions originate from a common reactive low-lying ligand-field (LF) state, which is also responsible for the direct photolysis reactions. This state, which leads directly to photoaquation, seems to have a certain charge transfer to solvent (CTTS) character, which is responsible for the photo-oxidation products. Sensitization is effective with rhodamine B (17 450 cm(-1)) and biacetyl (19 000 cm(-1)), whereas no reaction is observed with neutral red (16 900 cm(-1)). These results show that the excited state responsible for the photochemical reactions lies in the energy range between 16 900 cm(-1) and 17 700 cm(-1) and possesses spin-orbit character.

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Bright blue upconversion emission by thulium ions in PbGeO3-PbF2-CdF2 glass triply doped with Nd3+-Tm3+-Yb3+ under diode laser excitation around 800 nm is reported. The results revealed that the Nd3+/Tm3+/Yb3+-codoped sample generated ten times more 475 nm blue upconversion fluorescence than the Yb3+-sensitized Tm3+-doped one, under the same excitation power. The upconversion process also showed a strong dependence upon the Yb3+ concentration. The results also indicated that the neodymium ions played a major role in the upconversion process by transfering the 800 nm excitation to thulium ions. The population of the Tm3+ ions (1)G(4) emitting level was accomplished through a multiion interaction involving ground-state absorption of pump photons around 800 nm by the Nd3+(I-4(9/2)-->H-2(9/2), F-4(5/2)) and Tm3+(H-3(6)-->F-3(4)) ions followed by energy-transfer processes involving the Nd3+-Yb3+(F-4(3/2), F-2(7/2)-->I-4(11/2), F-2(5/2)) and Yb3+-Tm3+(F-2(5/2), F-3(4)-->F-2(7/2), (1)G(4)) pairs. (C) 2003 American Institute of Physics.

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The flat-panel-display's (FPD) market and demand for highly efficient and colored luminescent films have been growing quickly. In this work, thin films were obtained from Pechini's solution by dip-coating. The green films were thermally treated at 873 K in order to get ZnO:Eu 1 at% thin film. A Schott(R) glass plate hydrothermally treated was used as substrate. The films have a mosaic shaped feature that was observed by optical microscopy. That feature is a result of substrate thermal treatment. The film deposition decreases the substrate transmittance in the visible range. When the F-7(0) -->L-5(6) (392nm) Eu3+ transition is excited, it is possible to detect emission from D-5(0) --> F-7(J) (J = 1, 2, 3 and 4) transitions. The D-5(0) --> F-7(2) transition is also observed by using ZnO excitation wavelengths indicating energy transfer from ZnO to Eu3+ ion. (C) 2003 Elsevier B.V. (USA). All rights reserved.

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We present measurements of the non-linear oscillations of a portal frame foundation for a non-ideal motor. We consider a three-time redundant structure with two columns, clamped in their bases and a horizontal beam. An electrical unbalanced motor is mounted at mid span of the beam. Two non-linear phenomena are studied: a) mode saturation and energy transfer between modes; b) interaction between high amplitude motions of the structure and the rotation regime of a real limited power motor. The dynamic characteristics of the structure were chosen to have one-to-two internal resonance between the anti-symmetrical mode (sway motions) and the first symmetrical mode natural frequencies. As the excitation frequency reaches near resonance conditions with the 2nd natural frequency, the amplitude of this mode grows up to a certain level and then it saturates. The surplus energy pumped into the system is transferred to the sway mode, which experiences a sudden increase in its amplitude. Energy is transformed from low amplitude high frequency motion into high amplitude low frequency motion. Such a transformation is potentially dangerous.We consider the fact that real motors, such as the one used in this study, have limited power output. In this case, this energy source is said to be non-ideal, in contrast to the ideal source whose amplitude and frequency are independent of the motion of the structure. Our experimental research detected the Sommerfeld Effect: as the motor accelerates to reach near resonant conditions, a considerable part of its output energy is consumed to generate large amplitude motions of the structure and not to increase its own angular speed. For certain parameters of the system, the motor can get stuck at resonance not having enough power to reach higher rotation regimes. If some more power is available, jump phenomena may occur from near resonance to considerably higher motor speed regimes, no stable motions being possible between these two.

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Optical spectroscopic properties of Tm3+-doped 60TeO(2)-10GeO(2)-10K(2)O-10Li(2)O-10Nb(2)O(5) glass are reported. The absorption spectra were obtained and radiative parameters were determined using the Judd-Ofelt theory. Characteristics of excited states were studied in two sets of experiments. Excitation at 360 nm originates a relatively narrow band emission at 450 nm attributed to transition D-1(2)-->F-3(4) of the Tm3+ ion with photon energy larger than the band-gap energy of the glass matrix. Excitation at 655 nm originates a frequency upconverted emission at 450 nm (D-1(2)-->F-3(4)) and emission at 790 nm (H-3(4)-->H-3(6)). The radiative lifetimes of levels D-1(2) and H-3(4) were measured and the differences between their experimental values and the theoretical predictions are understood as due to the contribution of energy transfer among Tm3+ ions. (C) 2003 American Institute of Physics.

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Blue, green, red, and near-infrared upconversion luminescence in the wavelength region of 480-740 nm in Pr3+/Yb3+-codoped lead-cadmium-germanate glass under 980 nm diode laser excitation, is presented. Upconversion emission peaks around 485, 530, 610, 645, and 725 nm which were ascribed to the P-3(0)-H-3(J) (J = 4, 5, and 6), and P-3(0)-F-3(J) (J = 2, 3, and 4), transitions, respectively, were observed. The population of the praseodymium upper P-3(0) emitting level was accomplished through a combination of ground-state absorption of Yb3+ ions at the F-2(7/2), energy-transfer Yb3+(2F(5/2))-Pr3+(H-3(4)), and excited-state absorption of Pr3+ ions provoking the (1)G(4)-P-3(0) transition. The dependence of the upconversion luminescence upon the Yb3+-concentration and diode laser power, is also examined, in order to subsidize the proposed upconversion excitation mechanism. (C) 2004 Elsevier B,V. All rights reserved.

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Intense red upconversion emission around 650 nm in PbGeO3-PbF2-CdF2 transparent glass ceramic containing beta-PbF2:Ho3+ nanocrystals, is presented. The holmium-doped vitroceramic samples were excited by a 980 nm diode laser source. The 650 nm upconversion signal was assigned to the F-5(5) --> I-5(8) transition of holmium ions. Very low intensity signals around 490 and 540 nm corresponding to the F-5(2,3) --> I-5(8) and S-4(2), F-5(4) --> I-5(8) transitions, respectively, were also detected. The upconversion excitation mechanism was achieved through a combination of stepwise phonon-assisted multiphoton absorption, cross-relaxation processes involving pairs of holmium ions, and excited-state absorption. Using a diode laser pump source around 850 nm green upconversion emission around 540 nm was the observed predominant signal. (C) 2004 Elsevier B.V. All rights reserved.

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The deactivation of the two lowest excited states of Ho3+ was investigated in Ho3+ singly doped and Ho3+, Pr3+-codoped fluoride (ZBLAN) glasses. We establish that 0.1-0.3 mol % Pr3+ can efficiently deactivate the first excited (I-5(7)) state of Ho3+ while causing a small reduction of similar to 40% of the initial population of the second excited (I-5(6)) state. The net effect introduced by the Pr3+ ion deactivation of the Ho3+ ion is the fast recovery of the ground state of Ho3+. The Burshstein model parameters relevant to the Ho3+-> Pr3+ energy transfer processes were determined using a least squares fit to the measured luminescence decay. The energy transfer upconversion and cross relaxation parameters for 1948, 1151, and 532 nm excitations of singly Ho3+-doped ZBLAN were determined. Using the energy transfer rate parameters we determine from the measured luminescence, a rate equation model for 650 nm excitation of Ho3+-doped and Ho3+, Pr3+-doped ZBLAN glasses was developed. The rate equations were solved numerically and the population inversion between the I-5(6) and the I-5(7) excited states of Ho3+ was calculated to examine the beneficial effects on the gain associated with Pr3+ codoping. (c) 2007 American Institute of Physics.