938 resultados para 4F-4F TRANSITIONS


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The use of AC/DC magnetic susceptibility and impedance measurements to detect oxygen depletion effects in La0.7Ca0.3MnO3 +/-delta and NiMn2O4+delta spinel-type compounds is reported. For the NiMn2O4, for which no Mn4+ was found, three superposed Debye relaxations were observed in the range 260-180 K. Otherwise, in La0.7Ca0.3MnO3, the argon annealed has contributed to a decrease in T-C, but the amount of Mn4+ is still too high to allow the observation of a relaxation in this frequency window. (c) 2006 Elsevier B.V. All rights reserved.

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We present the results of an intracavity Stark spectroscopy experiment on the fundamental state of (CD3OH)-C-13. We use an optically pumped hybrid waveguide FIR laser, CH2F2 as active molecule, and (CD3OH)-C-13 as absorbent molecule. No Brewster window is needed to separate the lasing gas from the absorbing deuterated methanol. An absorption line is assigned as E(l) symmetry (n, K, J): (1,4,18) --> (1,5,18) and its frequency is measured as 63.08631 cm(-1) with a precision of a few parts in 10(7); two more absorptions are reported and a tentative assignment for one of them.

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An investigation by optical spectroscopy of the Eu3 + and Er3 + active ions in the crystallized fluorozirconate matrix LaZr2F11 is presented. The D-5(1) --> F-7(0-5) emission lines of Eu3 + are used to extract the F-7(0-5) energy scheme and the observed extinctions permit the deduction of irreducible representations (IRREPS) associated with corresponding sub-levels in the D-2 symmetry. The crystal field analysis was carried out on a 387 x 387 basis set, comprising the F-7, D-5(1,2,3) F-5(1,2), (5)G(1,2,3) and P-3(1,2,3,4,5,6) terms of the Eu-3 (+) 4f(6) configuration. The deviation and rms are 6.8 and 7.9 cm (-1), respectively for 38 levels and ten parameters. The experimental crystal field parameters are in good agreement with the ab-initio ones. Moreover, the relative intensities of the D-5(0) --> F-7(2,3,4) emissions are well reproduced by an 'ab-initio' calculation, except for three lines. The Er3 + ions introduced in LaZr2F11, microcrystals also lie in an unique crystallographic site. A total of 31 energy levels were recorded and the crystal field analysis led to 6.6 and 7.8 cm (-1) for the deviation and rms, respectively, for nine variable parameters taken into account. The experimental CF parameters for Er3 + and Eu3 + are very similar, which seems to show that the host lattice contracts around the smaller Er3 + ion. The informations given by both Eu3 + and Eu3 + optical probes in LaZr2F11 are very consistent with the structure previously determined for the isotypic PrZr2F11 fluoride. (C) 2000 Elsevier B.V. B.V. All rights reserved.

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Glass transition temperatures of freeze-dried tomato conditioned at various water activities at 25 C were determined by differential scanning calorimetry (DSC). Air-dried tomato with and without osmotic pre-treatment in sucrose/NaCl solutions was also analyzed. Thermograms corresponding to the low water activity domain (0.11 less than or equal to a(w) less than or equal to 0.75) revealed the existence of two glass transitions, which were attributed to separated phases formed by sugars and water and other natural macromolecules present in the vegetable. Both transitions were plasticized by water and experimental data could be well correlated by the Gordon-Taylor equation in the low-temperature domain, and by the Kwei model in the high-temperature domain. For higher water activities, the low-temperature glass transition curve exhibited a discontinuity, with suddenly increased glass transition temperatures approaching a constant value that corresponds to the T-g of the maximally freeze-concentrated amorphous matrix. The unfreezable water content was determined through the melting enthalpy dependence on the moisture content. (C) 2002 Elsevier B.V. Ltd. All rights reserved.

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The complex dynamic Young's modulus of ceramic Nd2-xCexCuO4 with x = 0, 0.05 and 0.20 has been measured from 1.5 to 100 K at frequencies of 1 - 10 kHz. In the undoped sample the modulus starts decreasing below similar to 20 K, instead of approaching a constant value as in a normal solid. The modulus minimum has been interpreted in terms of paraelastic contribution from the relaxation of the Nd3+ 4f electrons between the levels of the ground state doublet, which is split by the interaction with the antiferromagnetically ordered Cu sublattice. The value of the splitting is found to be 0.34 meV, in excellent agreement with inelastic neutron scattering, infrared and specific heat experiments. With doping, the anomaly shifts to lower temperature and decreases in amplitude, consistently with a reduction of the local field from the Cu sublattice. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

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Anelastic spectroscopy measurements (internal friction) are sensitive tools for the study of defects in solids, in particular the mobility of interstitial oxygen. Samples of Bi2Sr2CaCu2Oy were analyzed after being submitted to two thermal treatments in vacuum, one at 973 K and another at 673 K. Anelastic spectroscopy measurements were performed using a torsion pendulum operating at around 38 Hz and at a temperature range of 88 and 700 K with heating rate of 1 K/min and vacuum better than 10(-5) Torr. Complex relaxation structures reversible with new thermal treatments were observed. These relaxation structures were attributed to O-M structural phase transitions. (c) 2005 Elsevier B.V. All rights reserved.

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We present a simple model for the doped compound Nd2-yCevCuO4, in order to explain some recent experimental results on the latter. Within a Hartree-Fock context, we start from an impurity Anderson-like model and consider the magnetic splitting of the Nd-4f ground state Kramers doublet due to exchange interactions with the ordered Cu moments. Our results are in very good agreement with the experimental data, yielding a Schottky anomaly peak for the specific heat that reduces its amplitude, broadens and shifts to lower temperatures, upon Ce doping. For overdoped compounds at low temperatures, the specific heat behaves linearly and the magnetic susceptibility is constant. A smooth transition from this Fermi liquid-like behavior occurs as temperature is increased and, at high temperatures, the susceptibility exhibits a Curie-like behavior. Finally, we discuss some improvements our model is amenable to incorporate, (C) 1998 Elsevier B.V. B.V. All rights reserved.

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Electron spin resonance of Eu(2+) (4f(7), S=7/2) in a La hexaboride (LaB(6)) single crystal shows a single anisotropic Dysonian resonance. From the observed negative g shift of the resonance, it is inferred that the Eu(2+) ions are covalent exchange coupled to the B 2p-like host conduction electrons. From the anisotropy of the spectra (linewidth and field for resonance), we found that the S ground state of Eu(2+) ions experience a cubic crystal field of a negative fourth order crystal field parameter (CFP), b(4)=-11.5(2.0) Oe, in agreement with the negative fourth order CFP, A(4), found for the non-S ground state R hexaborides. These results support covalency as the dominant contribution to the fourth order CFP for the whole R hexaboride family.

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We used a Stark-Optoacoustic cell and hybrid waveguide resonators to perform an Infrared and Far Infrared Stark Spectroscopy study on some transitions of (CD3OH)-C-13. Different behaviours of the transitions in the presence of a d.c. electric field were observed. The Stark splittings of six FIR laser lines ranging from 34 to 136 MHz/kVcm(-1) were determined. The analysis of the behaviour of the IR and FIR transitions in the presence of the external electric fields gives important and exclusive information on the levels involved in the transitions.

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The electron spin resonance (ESR) spectra of Eu2+ (4f(7), S = 7/2) in LaB6 single crystal show a single Dysonian resonance for the localized Eu2+ magnetic moments. It is shown that the Eu2+ ions are covalent exchange coupled to the (B) 2p-like host conduction electrons. (c) 2007 Elsevier B.V. All rights reserved.

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The optical properties of cubic GaN epitaxial layers were investigated by modulated photoreflectance (PR) and photoluminescence in the temperature interval from 5 to 300 K. The epilayers were grown on GaAs(001) substrates by molecular beam epitaxy using a nitrogen RIF-activated plasma source. The PR spectra show a transition which is well fitted using the third-derivative functional form of the unperturbed dielectric function, which we interpret as band-to-band transition. Our results allow determination of the temperature dependence of the main gap of c-GaN and give insights into the residual strain in the film, as well as allow us to estimate the binding energy of the complex formed by an exciton bound to a neutral acceptor. (C) 2003 Elsevier B.V. B.V. All rights reserved.

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Pt-modified SnO2 electrodes were prepared onto titanium substrates in the form of thin films of similar to2 mum at different temperatures in the range from 200 to 400degreesC. Surface morphology was examined by scanning electron microscopy (SEM). It was found that Pt-SnO2 sol-gel layers are significantly rough and have a low porosity. X-ray diffraction (XRD) studies showed that the films consist of Pt nanoparticles with average size varying from about 5 to 10 nm, depending on the preparation temperature, and amorphous tin oxide. X-ray photoelectron spectroscopy (XPS) was employed to determine the superficial composition of the electrodes and demonstrated the presence of Sn4+ in all the samples. XPS spectra of the Pt 4f electrons showed the presence of Pt in the zero-valence state as well as in ionic forms. The general electrochemical behavior was characterized by cyclic voltammetry in 1 mol l(-1) HClO4 and the electrocatalytic activity towards the oxidation of formaldehyde was investigated by potential sweeps and chronoamperometry. The results obtained show that the Pt-SnO2/Ti system exhibits a significant catalytic activity for the oxidation of formaldehyde, with an onset potential below 0.1 V. (C) 2004 Elsevier Ltd. All rights reserved.

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The method of the fourth-order cumulant of Challa, Landau, and Binder is used together with the Monte Carlo histogram technique of Ferrenberg and Swendsen to study the order of the phase transitions of two-dimensional Ising systems with multispin interactions in the horizontal direction and two-body interactions in the vertical direction.