Electronic structure and optical properties of BaMoO(4) powders

Barium molybdate (BaMoO(4)) powders were synthesized by the co-precipitation method and processed in microwave-hydrothermal at 140 degrees C for different times. These powders were characterized by X-ray diffraction (XRD), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis) absorption spectroscopies and photoluminescence (PL) measurements. XRD patterns and FT-Raman spectra showed that these powders present a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 850.4 cm(-1), which is associated to the Mo-O antisymmetric stretching vibrations into the [MoO(4)] clusters. UV-vis absorption spectra indicated a reduction in the intermediary energy levels within band gap with the processing time evolution. First-principles quantum mechanical calculations based on the density functional theory were employed in order to understand the electronic structure (band structure and density of states) of this material. The powders when excited with different wavelengths (350 nm and 488 nm) presented variations. This phenomenon was explained through a model based in the presence of intermediary energy levels (deep and shallow holes) within the band gap. (C) 2009 Elsevier B.V. All rights reserved.

A new processing method of CaZn(2)(OH)(6)center dot 2H(2)O powders: Photoluminescence and growth mechanism

In this communication, we report on the formation of calcium hexahydroxodizincate dehydrate, CaZn(2)(OH)(6)center dot 2H(2)O (CZO) powders under microwave-hydrothermal (MH) conditions. These powders were analyzed by X-ray diffraction (XRD), Field-emission gum scanning electron microscopy (FEG-SEM), ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. XRD patterns confirmed that the pure CZO phase was obtained after MH processing performed at 130 degrees C for 2 h. FEG-SEM micrographs indicated that the morphological modifications as well as the growth of CZO microparticles are governed by Ostwald-ripening and coalescence mechanisms. UV-vis spectra showed that this material have an indirect optical band gap. The pure CZO powders exhibited an yellow PL emission when excited by 350 nm wavelength at room temperature. (C) 2009 Elsevier Masson SAS. All rights reserved.

Application of abrupt cut-off models in the analysis of the capacitance spectra of conjugated polymer devices

In this paper, a detailed study of the capacitance spectra obtained from Au/doped-polyaniline/Al structures in the frequency domain (0.05 Hz-10 MHz), and at different temperatures (150-340 K) is carried out. The capacitance spectra behavior in semiconductors can be appropriately described by using abrupt cut-off models, since they assume that the electronic gap states that can follow the ac modulation have response times varying rapidly with a certain abscissa, which is dependent on both temperature and frequency. Two models based on the abrupt cut-off concept, formerly developed to describe inorganic semiconductor devices, have been used to analyze the capacitance spectra of devices based on doped polyaniline (PANI), which is a well-known polymeric semiconductor with innumerous potential technological applications. The application of these models allowed the determination of significant parameters, such as Debye length (approximate to 20 nm), position of bulk Fermi level (approximate to 320 meV) and associated density of states (approximate to 2x10(18) eV(-1) cm(-3)), width of the space charge region (approximate to 70 nm), built-in potential (approximate to 780 meV), and the gap states` distribution.

Formation of beta-nickel hydroxide plate-like structures under mild conditions and their optical properties

Nanostructural beta-nickel hydroxide (beta-Ni(OH)(2)) plates were prepared using the microwave hydrothermal (MH) method at a low temperature and short reaction times. An ammonia solution was employed as the coordinating agent, which reacts with [Ni(H(2)O)(6)](2+) to control the growth of beta-Ni(OH)(2) nuclei. A trigonal beta-Ni(OH)(2) single phase was observed by X-ray diffraction (XRD) analyses, and the crystal cell was constructed with structural parameters and atomic coordinates obtained from Rietveld refinement. Field emission scanning electron microscopy (FE-SEM) images revealed that the samples consisted of hexagonal-shaped nanoplates with a different particle size distribution. Broad absorption bands assigned as transitions of Ni(2+) in oxygen octahedral sites were revealed by UV-vis spectra. Photoluminescence (PL) properties observed with a maximum peak centered in the blue-green region were attributed to different defects, which were produced during the nucleation process. We present a growth process scheme of the beta-Ni(OH)(2) nanoplates. (C) 2011 Elsevier Inc. All rights reserved.

Light emitting diodes containing Langmuir-Blodgett films of copolymer of a poly(p-phenylene-vinylene) derivative and poly(octaneoxide)

The properties of Langmuir and Langmuir-Blodgett (LB) films from a block copolymer with polyethylene oxide and phenylene-vinylene moieties are reported. The LB films were successfully transferred onto several types of substrates, with sufficient quality to allow for evaporation of a metallic electrode on top of the LB films to produce polymer light emitting diodes (PLEDs). The photoluminescence and electroluminescence spectra of the LB film and device were similar, featuring an emission at ca. 475 nm, from which we could infer that the emission mechanisms are essentially the same as in poly(p-phenylene) derivatives. Analogously to other PLEDs the current versus voltage characteristics of the LB-based device could be explained with the Arkhipov model according to which charge transport occurs among localized sites. The implications for nanotechnology of the level of control that may be achieved with LB devices will also be discussed.

Effect of Different Solvent Ratios (Water/Ethylene Glycol) on the Growth Process of CaMoO(4) Crystals and Their Optical Properties

In this paper, calcium molybdate (CaMoO(4)) crystals (meso- and nanoscale) were synthesized by the coprecipitation method using different solvent volume ratios (water/ethylene glycol). Subsequently, the obtained suspensions were processed in microwave-assisted hydrothermal/solvothermal systems at 140 degrees C for 1 h. These meso- and nanocrystals processed were characterized by X-ray diffraction (X R I)), Fourier transform Raman (FT-Raman), Fourier transform infrared (FT-IR). ultraviolet visible (UV-vis) absorption spectroscopies, held-emission gun scanning electron microscopy (FEG-SEM). transmission electron microscopy (TEM). and photoluminescence (PL) measurements. X RI) patterns and FT-Raman spectra showed that these meso- and nanocrystals have a scheelite-type tetragonal structure without the presence of deleterious phases. FT-IR spectra exhibited a large absorption band situated at around 827 cm(-1), which is associated with the Mo-O anti-symmetric stretching vibrations into the [MoO(4)] clusters. FEG-SEM micrographs indicated that the ethylene glycol concentration in the aqueous solution plays an important role in the morphological evolution of CaMoO(4) crystals. High-resolution TEM micrographs demonstrated that the mesocrystals consist of several aggregated nanoparticles with electron diffraction patterns of monocrystal. In addition, the differences observed in the selected area electron diffraction patterns of CaMoO(4) crystals proved the coexistence of both nano- and mesostructures, First-principles quantum mechanical calculations based on the density functional theory at the B3LYP level were employed in order to understand the band structure find density of states For the CaMoO(4). UV-vis absorption measurements evidenced a variation in optical band gap values (from 3.42 to 3.72 cV) for the distinct morphologies. The blue and green PI. emissions observed in these crystals were ascribed to the intermediary energy levels arising from the distortions on the [MoO(4)] clusters clue to intrinsic defects in the lattice of anisotropic/isotropic crystals.

Micro Far-Infrared Reflectivity of CaNb(2)O(6) Single Crystal Fibers Grown by the Laser-Heated Pedestal Growth Technique

CaNb(2)O(6) single crystal fibers were grown by the laser-heated pedestal growth technique, directly from the starting reagents. Optically transparent fibers were obtained in the form of rods with elliptical cross-section, free from cracks, impurities, and secondary phases, with an average diameter of 0.4 mm and about 20 mm of length. The fibers grew within the orthorhombic Pbcn columbite structure, with the growth axis nearly parallel to the crystallographic a-direction. The parameters b and c were parallel to the shorter and larger ellipsis axes. A special setup using a microscope was developed to obtain the far-infrared reflectivity spectra of these micrometer-sized fibers, allowing the identification and assignment of 34 of the 38 polar phonons foreseen for the material. From these phonons, the intrinsic dielectric constant ( = 18.2) and quality factor ( of 185 THz) could be estimated, showing the potential of the material for applications in microwave circuitry. These results, along with previous polarized Raman data (Cryst. Growth Des. 2010, 10, 1569), allow us to present a comprehensive set of optical phonon modes and to discuss the potential use of designed CaNb(2)O(6) microcrystals in compact optical devices.

Structural and spectroscopic characterization of poly(styrene sulfonate) films doped with neodymium ions

This work reports the structural and spectroscopy characterization of poly(styrene sulfonate) (PSS) films doped with neodymium (Nd) ions. Nd-PSS films were processed using the acid of poly(styrene sulfonate) - H-PSS and neodymium nitrate - Nd(NO(3))(3); the maximum incorporation of Nd ions in the polymeric matrix was equal 19.3%. The absorption in the UV-Vis-NIR spectral region presents typical electronic transitions of Nd 3, ions, with well resolved peaks. The infrared spectra present the transition bands of PSS with characteristic line shape broadening, and the presence of vibrational modes of N-O groups in the range of 1400-720 cm(-1), prove the permanence of Nd(NO(3))(x), with x = 1, 2 and/or 3. in the H-PSS matrix. UV-Vis site selective photoluminescence data indicate that the incorporation of Nd 31 introduces a blue shift in PSS emission (325-800 nm), decreasing the interaction between adjacent PSS lateral groups (aromatic rings). Nd(3+) reabsorption and energy transfer effects between the PSS matrix and Nd(3+) were also observed. The IR emission of Nd-PSS films at 1076 rim ((4)F(3/2) -> (4)I(11/2)) present constant efficiency, independent on Nd(3+) concentration. The Judd-Ofelt theory was employed to analyze radiative properties. The excitation spectra prove the energy transfer between the polymeric matrix and Nd(3+). Complex impedance data was used to probe relaxation processes during the charge transport within the polymeric matrix. (C) 2008 Elsevier B.V. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Energy transfer processes in Yb(3+)-Tm(3+) co-doped sodium alumino-phosphate glasses with improved 1.8 mu m emission

Sodium alumino-phosphate glasses co-doped with Yb(3+) and Tm(3+) ions have been prepared with notably low OH(-) content, and characterized from the viewpoint of their spectroscopic properties. In these glasses, Yb(3+) acts as an efficient sensitizer of excitation energy at 0.98 mu m - which can be provided by high power and low cost diode lasers, and subsequently undergoes non-resonant energy transfer to Tm(3+) ions ((2)F(5/2), (3)H(6) --> (2)F(7/2), (3)H(5)). Through this process, the emitting level (3)F(4) is rapidly populated, generating improved emission at 1.8 mu m ((3)F(4) --> (3)H(6)). In order to guarantee the efficiency of such favorable energy transfer, energy losses via multiphonon decay, Yb-Yb radiative trapping, and non- radiative transfer to OH(-) groups were evaluated, and minimized when possible. The dipole - dipole energy transfer microscopic parameters corresponding to Yb(3+) --> Tm(3+), Yb(3+) --> Yb(3+) and Tm(3+) --> Tm(3+) transfers, calculated by the Forster-Dexter model, are C(Yb-Tm) = 2.9 x 10(-40) cm(6) s(-1), C(Yb-Yb) = 42 x 10(-40) cm(6) s(-1) and C(Tm-Tm) = 43 x 10(-40) cm(6) s(-1), respectively.

Structural-electronic aspects related to the near-infrared light emission of Fe-doped silicon films

The need of efficient (fast and low consumption) optoelectronic devices has always been the driving force behind the investigation of materials with new or improved properties. To be commercially attractive, however, these materials should be compatible with our current micro-electronics industry and/or telecommunications system. Silicon-based compounds, with their matured processing technology and natural abundance, partially comply with such requirements-as long as they emit light. Motivated by these issues, this work reports on the optical properties of amorphous Si films doped with Fe. The films were prepared by sputtering a Si+Fe target and were investigated by different spectroscopic techniques. According to the experimental results, both the Fe concentration and the thermal annealing of the samples induce changes in their atomic structure and optical-electronic properties. In fact, after thermal annealing at similar to 750 degrees C, the samples partially crystallize with the development of Si and/or beta-FeSi(2) crystallites. In such a case, certain samples present light emission at similar to 1500 nm that depends on the presence of beta-FeSi(2) crystallites and is very sensitive to the annealing conditions. The most likely reasons for the light emission (or absence of it) in the considered Fe-doped Si samples are presented and discussed in view of their main structural-electronic characteristics. (C) 2011 Elsevier Ltd. All rights reserved.

OSCILLATOR STRENGTHS AND LIFETIMES FOR THE P XII

Semi-empirical weighted oscillator strengths (gf) and lifetimes presented in this work for all experimentally known electric dipole P XII spectral lines and energy levels were computed within a multiconfiguration Hartree-Fock relativistic approach. In this calculation, the electrostatic parameters were optimized by a least-squares procedure in order to improve the adjustment to experimental energy levels. The method produces lifetime and gf values that are in agreement with intensity observations used for the interpretation of spectrograms of solar and laboratory plasmas.

On spectra of abelian group rings

In this paper we study the spectrum of integral group rings of finitely generated abelian groups G from the scheme-theoretic viewpoint. We prove that the (closed) singular points of Spec Z[G], the (closed) intersection points of the irreducible components of Spec Z[G] and the (closed) points over the prime divisors of vertical bar t(G)vertical bar coincide. We also determine the formal completion of Spec Z[G] at a singular point.

Tryptophan oxidation by singlet molecular oxygen [O-2 ((1)Delta(g))]: Mechanistic studies using O-18-labeled hydroperoxides, mass spectrometry, and light emission measurements

Proteins have been considered important targets for reactive oxygen species. Indeed, tryptophan (W) has been shown to be a highly susceptible amino acid to many oxidizing agents, including singlet molecular oxygen [O-2 ((1)Delta(g))]. In this study, two cis- and trans-tryptophan hydroperoxide (WOOH) isomers were completely characterized by HPLC/mass spectrometry and NMR analyses as the major W-oxidation photoproducts. These photoproducts underwent thermal decay into the corresponding alcohols. Additionally, WOOHs were shown to decompose under heating or basification, leading to the formation of N-formylkynurenine (FMK). Using O-18-labeled hydroperoxides ((WOOH)-O-18-O-18), it was possible to confirm the formation of two oxygen-labeled FMK molecules derived from (WOOH)-O-18-O-18 decomposition. This result demonstrates that both oxygen atoms in FMK are derived from the hydroperoxide group. In addition, these reactions are chemiluminescent (CL), indicating a dioxetane cleavage pathway. This mechanism was confirmed since the CL spectrum of the WOOH decomposition matched the FMK fluorescence spectrum, unequivocally identifying FMK as the emitting species.

Cholesterol Hydroperoxides Generate Singlet Molecular Oxygen [O(2) ((1)Delta(g))]: Near-IR Emission, (18)O-Labeled Hydroperoxides, and Mass Spectrometry

In mammalian membranes, cholesterol is concentrated in lipid rafts. The generation of cholesterol hydroperoxides (ChOOHs) and their decomposition products induces various types of cell damage. The decomposition of some organic hydroperoxides into peroxyl radicals is known to be a potential source of singlet molecular oxygen [O(2) ((1)Delta(g))] in biological systems. We report herein on evidence of the generation of O(2) ((1)Delta(g)) from ChOOH isomers in solution or in liposomes containing ChOOHs, which involves a cyclic mechanism from a linear tetraoxide intermediate originally proposed by Russell. Characteristic light emission at 1270 nm, corresponding to O(2) ((1)Delta(g)) monomolecular decay, was observed for each ChOOH isomer or in liposomes containing ChOOHs. Moreover, the presence of O(2) ((1)Delta(g)) was unequivocally demonstrated using the direct spectral characterization of near-infrared light emission. Using (18)O-labeled cholesterol hydroperoxide (Ch(18)O(18)OH), we observed the formation of (18)O-labeled O(2) ((1)Delta(g)) [(18)O(2) ((1)Delta(g))] by the chemical trapping of (18)O(2) ((1)Delta(g)) with 9,10-diphenylanthracene (DPA) and detected the corresponding (18)O-labeled DPA endoperoxide (DPA(18)O(18)O) and the (18)O-labeled products of the Russell mechanism using high-performance liquid chromatography coupled to tandem mass spectrometry. Photoemission properties and chemical trapping clearly demonstrate that the decomposition of Ch(18)O(18)OH generates (18)O(2) ((1)Delta(g)), which is consistent with the Russell mechanism and points to the involvement of O(2) ((1)Delta(g)) in cholesterol hydroperoxide-mediated cytotoxicity.