LIII absorption edge studies of mixed valent cerium intermetallics and related systems

LIII absorption edge measurements clearly delineate 3+ and 4+ states of Ce. Absorption edges of 3+ compounds show a single peak, while those of 4+ compounds show two peaks, both appearing at higher energies than the characteristic peaks of 3+ compounds. In systems where there is interconfigurational fluctuation, features due to both 3+ and 4+ states are distinctly seen.

Valence fluctuation in some Yb intermetallics by X-ray photoemission and X-ray absorption

The valence state of Yb in some of its intermetallics, YbNi2Ge2, YbCu2Si2 and YbPd2Si2 has been investigated by LIII(Yb) absorption edges and X-ray pnotoelectron spectra in the 4f and 4d regions. These studies establish the presence of mixed valence in all three systems and illustrate the utility of 4f and 4d spectra in the study of mixed valence in Yb compounds.

Application of molecular orbital theory to the interpretation of x-ray absorption spectra of platinum complexes

X-ray LIII-absorption edges of platinum in nine octahedral complexes have been recorded using a bent crystal spectrograph. The edge features of the discontinuities have been interpreted with the help of qualitative molecular orbital diagrams. A correlation between the energy separation of the first two absorption maxima and the spectrochemical series of the ligands has been arrived at.

Preparation of I-2 clusters and their absorption spectra

Samples have been prepared at different temperatures by loading It molecules into the cages of zeolite 5A, and the measurements of the absorption spectra have been carried out for the prepared samples. It is shown that 12 molecular clusters are formed in the cages of zeolite 5A, and it is also found that molecular clusters which are bonded with intermolecular forces have an important feature, namely, the intermolecular distance in molecular clusters can be changed on different preparing conditions and the blue shift of absorption edges can not be as the criterion of forming molecular clusters.

Absorption spectra of Se-8-ring clusters in zeolite 5A

Samples with different weight ratio of Se to zeolite 5A (Se concentration) have been prepared by loading Se into the pores of zeolite 5A, and the measuerments of the absorption and Raman spectra have been carried out for the prepared samples. The measured absorption edges of the samples are close to the value for monoclinic Se containing Se-8-ring, suggesting the formation of Se-8-ring clusters(1) in the pores. The continuous and broadening features of the absorption spectra are interpreted by the strong electron-nucleus coupling in the Se-8-ring cluster. The absorption edges are red shifted with the increase of the Se concentration. It is tentatively attributed to two reasons. One is the existence of the double Se-8-ring cluster in the high Se concentration samples, and the other is that for the strong electron-nucleus coupling cluster, the absorption edge of the clusters system will be red shifted with the increase of the cluster concentration in the clusters system. A single broad band at about 262 cm(-1) is observed in the Raman spectra, which further supports the formation of Se-8-ring clusters. (C) 1997 Published by Elsevier Science S.A.

Absorption and Raman spectra of Se-8-ring clusters in zeolite 5A

Samples with different weight ratio of Se to zeolite 5A (Se composition) have been prepared by loading Se into the cages of zeolite 5A and the measurements of the absorption and Raman spectra have been carried out for the prepared samples. The measured absorption edges of the samples close and blue shifted to the value for monoclinic Se containing Se-8-ring, suggesting the formation of Se-8-ring clusters dagger in the cages. The continuous and broadening features of the absorption spectra are interpreted by the strong electron-phonon coupling in Se-8-ring clusters. The sample with high Se composition has a red shift of the absorption band edge relative to the samples with less Se composition. It is tentatively attributed to the reason that with different Se composition, single Se-8-ring clusters and double Se-8-ring clusters are formed in the cages of zeolite 5A. A single broad band at about 262 cm(-1) is observed in the Raman spectra, that gives the further support of the formation of Se-8-ring clusters. Copyright (C) 1996 Elsevier Science Ltd

Disorder effects produced by the Mn and H incorporations on the optical absorption edge of Ga1-xMnxAs:H nanocrystalline films

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

The optical absorption edge of nanocrystalline Ga(1-x)Mn(x)N films deposited by reactive sputtering

We have focused on the optical absorption edge of nanocrystalline Ga(1-x)Mn(x)N (0.00 <= x <= 0.18) films deposited by reactive RF magnetron sputtering. The films obtained are nanocrystalline with grain sizes of about 25 nm, having wurtzite structure and strong orientation texture in the c-axis direction. The optical characterizations of the absorption edges were obtained in the 190-2600 nm spectral range. The increase of the Mn content causes an increase of the absorption coefficient which can be clearly noticed at low energies, and a quasi-linear decrease of the optical gap. Broad absorption bands observed around similar to 1.3 and similar to 2.2 eV were associated with transitions between the Mn acceptor level and the valence and conduction bands, respectively. The observed changes in the optical properties due to the Mn incorporation observed in these nanocrystalline films are similar to those reported for ferromagnetic GaMnN single-crystal films.

Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (&GE; 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

EPR, optical absorption and luminescence studies of Cr3+-doped antimony phosphate glasses

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Thiophene-benzothiadiazole-thiophene (D-A-D) based polymers : Effect of donor/acceptor moieties adjacent to D-A-D segment on photophysical and photovoltaic properties

New push-pull copolymers based on thiophene (donor) and benzothiadiazole (acceptor) units, poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co- thiophene] (PT3B1) and poly[4,7-bis(3-dodecylthiophene-2-yl) benzothiadiazole-co-benzothiadiazole] (PT2B2), are designed and synthesized via Stille and Suzuki coupling routes respectively. Gel permeation chromatography shows the number average molecular weights are 31100 and 8400 g mol-1 for the two polymers, respectively. Both polymers have shown absorption throughout a wide range of the UV-vis region, from 300 to 650 nm. A significant red shift of the absorption edge is observed in thin films compared to solution of the copolymers; the optical band gap is in the range of 1.7 to 1.8 eV. Cyclic voltammetry indicates reversible oxidation and reduction processes with HOMO energy levels calculated to be in the range of 5.2 to 5.4 eV. Upon testing both materials for organic field-effect transistors (OFETs), PT3B1 showed a hole mobility of 6.1 × 10-4 cm2 V-1 s -1, while PT2B2 did not show any field effect transport. Both copolymers displayed a photovoltaic response when combined with a methanofullerene as an electron acceptor. The best performance was achieved when the copolymer PT3B1 was blended with [70]PCBM in a 1:4 ratio, exhibiting a short-circuit current of 7.27 mA cm-2, an open circuit voltage of 0.85 V, and a fill factor of 41% yielding a power conversion efficiency of 2.54% under simulated air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm-2). Similar devices utilizing PT2B2 in place of PT3B1 demonstrated reduced performance with a short-circuit current of 4.8 mA cm -2, an open circuit voltage of 0.73 V, and a fill factor of 30% resulting in a power conversion efficiency of roughly 1.06%.

X-ray spectroscopic study of chromium, nickel, and molybdenum compounds

Chemical shifts in the K-absorption edges, AE, of a series of chromium, nickel, and molybdenum compounds have been investigated. The AE values in a given series vary in the same direction as the metal-core-level binding energies obtained from X-ray photoelectron spectroscopy. The AI3 values are related to the effective atomic charge of the metal by a parabolic relation. In the case of molybdenum compounds, the chemical shifts of the K, emission lines vary in the same manner as M.

Anomalous X-ray scattering study of local structures in the superionic conducting class (CuI)(0.3)(Cu2O)(0.35)(MoO3)(0.35)

The anomalous X-ray scattering (AXS) method using Cu and Mo K absorption edges has been employed for obtaining the local structural information of superionic conducting glass having the composition (CuI)(0.3)(Cu2O)(0.35)(MoO3)(0.35). The possible atomic arrangements in near-neighbor region of this glass were estimated by coupling the results with the least-squares analysis so as to reproduce two differential intensity profiles for Cu and Mo as well as the ordinary scattering profile. The coordination number of oxygen around Mo is found to be 6.1 at the distance of 0.187 nm. This implies that the MoO6 octahedral unit is a more probable structural entity in the glass rather than MoO4 tetrahedra which has been proposed based on infrared spectroscopy. The pre-peak shoulder observed at about 10 nm(-1) may be attributed to density fluctuation originating from the MoO6 octahedral units connected with the corner sharing linkage, in which the correlation length is about 0.8 nm. The value of the coordination number of I- around Cu+ is estimated as 4.3 at 0.261 nm, suggesting an arrangement similar to that in molten CuI.