Studies on the resonance Raman spectra of polyaniline obtained with near-IR excitation

The effects of near-IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANIES) and base (PANI-EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm-1 in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm-` were associated to vC-N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm-1 in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to vC=N modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 run causes the deprotonation of PANI-ES and the formation of cross-linking segments having phenazine and/or oxazine rings. For PANI-EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright (c) 2007 John Wiley & Sons, Ltd.

Axial ligand influence on geometries, charge distributions and electronic structures of iron tetraazamacrocycle [Fe((II))TIM(X)(Y)](2+) complexes assessed by Density Functional Theory

We employed the Density Functional Theory along with small basis sets, B3LYP/LANL2DZ, for the study of FeTIM complexes with different pairs of axial ligands (CO, H(2)O, NH(3), imidazole and CH(3)CN). These calculations did not result in relevant changes of molecular quantities as bond lengths, vibrational frequencies and electronic populations supporting any significant back-donation to the carbonyl or acetonitrile axial ligands. Moreover, a back-donation mechanism to the macrocycle cannot be used to explain the observed changes in molecular properties along these complexes with CO or CH(3)CN. This work also indicates that complexes with CO show smaller binding energies and are less stable than complexes with CH(3)CN. Further, the electronic band with the largest intensity in the visible region (or close to this region) is associated to the transition from an occupied 3d orbital on iron to an empty pi* orbital located at the macrocycle. The energy of this Metal-to-Ligand Charge Transfer (MLCT) transition shows a linear relation to the total charge of the macrocycle in these complexes as given by Mulliken or Natural Population Analysis (NPA) formalisms. Finally, the macrocycle total charge seems to be influenced by the field induced by the axial ligands. (C) 2011 Elsevier Ltd. All rights reserved.

Reactivity of Beer Bitter Acids Toward the 1-Hydroxyethyl Radical as Probed by Spin-Trapping Electron Paramagnetic Resonance (EPR) and Electrospray Ionization-Tandem Mass Spectrometry (ESI-MS/MS)

The iso-alpha-acids or isohumulones are the major contributors to the bitter taste of beer, and it is well-recognized that they are degraded during beer aging. In particular, the trans-isohumulones seem to be less stable than the cis-isohumulones. The major radical identified in beer is the 1-hydroxyethyl radical; however, the reactivity between this radical and the isohumulones has not been reported until now. Therefore, we studied the reactivity of isohumulones toward the 1-hydroxyethyl radical through a competitive kinetic approach. It was observed that both cis- and trans-isohumulones and dihydroisohumulones are decomposed in the presence of 1-hydroxyethyl radicals, while the reactivities are comparable. On the other hand, the tetrahydroisohumulones did not react with 1-hydroxyethyl radicals. The apparent second-order rate constants for the reactions between the 1-hydroxyethyl radical and these compounds were determined by electron paramagnetic resonance (EPR) spectroscopy and electrospray ionization-tandem mass spectrometry [ESI(+)-MS/MS]. It follows that degradation of beer bitter acids is highly influenced by the presence of 1-hydroxyethyl radicals. The reaction products were detected by liquid chromatography electrospray ionization-ion trap-tandem mass spectrometry (LC-ESI-IT-MS/MS), and the formation of oxidized derivatives of the isohumulones was confirmed. These data help to understand the mechanism of beer degradation upon aging.

Anomalous spin-related quantum phase in mesoscopic hole rings

We have obtained numerically exact results for the spin-related geometric quantum phases that arise in p-type semiconductor ring structures. The interplay between gate-controllable (Rashba) spin splitting and quantum-confinement-induced mixing between hole-spin states causes a much higher sensitivity of magnetoconductance oscillations to external parameters than previously expected. Our results imply a much-enhanced functionality of hole-ring spin-interference devices and shed new light on recent experimental findings.

Sagnac rotational phase shifts in a mesoscopic electron interferometer with spin-orbit interactions

The Sagnac effect is an important phase coherent effect in optical and atom interferometers where rotations of the interferometer with respect to an inertial reference frame result in a shift in the interference pattern proportional to the rotation rate. Here, we analyze the Sagnac effect in a mesoscopic semiconductor electron interferometer. We include in our analysis the Rashba spin-orbit interactions in the ring. Our results indicate that spin-orbit interactions increase the rotation-induced phase shift. We discuss the potential experimental observability of the Sagnac phase shift in such mesoscopic systems.

Escadas de spin integráveis

Neste trabalho definimos três modelos de escadas de spin integráveis novos que correspondem a variações de um modelo de escada de spin baseado na simetria SU(4). Os modelos são exatamente solúveis através do método do ansatz de Bethe e as equações do ansatz de Bethe, os autovalores de energia e o gap de spin são derivados e propriedades físicas interessantes são discutidas. Inicialmente apresentamos um modelo de escada de spin integrável que possui um parâmetro livre além do acomplamento ao longo dos degraus. Determinamos a dependência do parâmetro anisotrópico na transição de fase entre uma região com gap e outra sem gap. Nós também mostramos que o modelo é um caso especial de uma Hamiltoniana mais geral que possui três parâmetros livres. A susceptibilidade magnética em função da temperatura é obtida numericamente e sua dependência no parâmetro anisotrópico é determinada explicitamente. Uma comparação entre o gap de spin obtido através da curva de susceptibilidade magnética e aquele obtido das equações do ansatz de Bethe é feita e uma boa concordância encontrada. A conexão com alguns compostos é apresentada e mostramos que os nossos resultados ajustam bem a curva da susceptibilidade magnética dos compostos KCuCI3, CU2(C5H12N2hC14e (C5H12NhCuBr4. A seguir nós propomos dois tipos diferentes de modelos integráveis com impurezas. Mostramos em ambos os casos que uma transição de fase entre uma região com gap e outra sem gap ocorre para um valor crítico do acoplamento ao longo dos degraus. Além disso, a dependência das impurezas na transição de fase é determinada explicitamente. Em um dos modelos o gap diminui com o aumento da intensidade da impureza A. E, fixando a intensidade de impureza A, é observada uma redução do gap com o aumento da concentração de impurezas. Este resultado está qualitativamente de acordo com resultados experimentais.

Spin-offs: um estudo de casos em pequenas e médias empresas brasileiras de base tecnológica

Spin-off é o processo de geração de novas empresas a partir de organizações existentes. Em modelos de inovação como o Open Innovation, onde a empresa utiliza tecnologias desenvolvidas por fontes internas e externas, buscando a constante maximização do retorno do investimento em inovação, é possível através de mecanismos como o spin-off alavancar oportunidades de negócios oriundas da base tecnológica da organização. Com um estudo qualitativo do tipo multi-caso, exploratório e descritivo, o objetivo desta pesquisa foi investigar como ocorre o processo de geração e desenvolvimento de spin-offs em pequenas e médias empresas brasileiras de base tecnológica, identificando as motivações e barreiras para geração deste tipo de spin-off no Brasil, bem como a governança e forma de captura do valor gerado pelas novas empresas por parte das empresas-mãe. Foram identificados quatro casos que atendiam as características da pesquisa: a) empresa-filha fundada com a participação de colaboradores da empresa-mãe; b) o spin-off visou a comercialização de tecnologia desenvolvida ou possuída pela empresa-mãe; c) empresa-filha foi ou é suportada pela empresa-mãe. Observações em campo e entrevistas semi-estruturadas foram conduzidas junto aos sócios, gestores e colaboradores das empresas-mãe e das novas empresas geradas. As oito proposições levantadas apontam que os investimentos em pesquisa e desenvolvimento (P&D) e a cultura organizacional aberta ao empreendedorismo contribuem para a geração de spin-offs nas pequenas e médias empresas de base tecnológica. As principais motivações para a geração de spin-offs são: a) estratégia de diversificação da empresa-mãe; b) garantia de maior foco para uma tecnologia específica, que dentro da empresa-mãe não seria possível e c) completar a cadeia de valor da empresa-mãe. As iniciativas governamentais de apoio a criação de novas empresas são essenciais para o desenvolvimento de spin-offs, já que em todos os casos a maior dificuldade durante o processo era a obtenção de financiamento para o novo negócio. Outra evidência apontada foi o fato de quanto menor o porte da empresa geradora do spin-off tecnológico, maior se dar a relação entre esta e a nova empresa.

Modelo esférico quântico de vidro de spin na aproximação de recozimento

Apresentamos aqui o modelo esférico quântico de vidro de spin usando a aproximação de recozimento. São calculadas a energia livre, bem como a temperatura crítica em função do momentum de inércia e a entropia. São consideradas interações aleatórias de longo alcance (campo médio) com distribuição normal de média zero, e a energia cinética de cada spin. O cálculo é feito utilizando o formalismo funcional de Feynman de integrais de caminhos. O limite clássico é apresentado e coincide com o limite conhecido de teorias anteriores.

Reestruturação via cisão (spin-off) ou venda de ativos : um estudo aplicado ao caso brasileiro

Dissertação apresentada à pós-graduação em economia para obtenção do título de mestre em economia e finanças

Ondas de spin em super-redes ferromagnéticas com campo de anisotropia

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Espectro das ondas de spin lineares e não-lineares em multicamadas magnéticas anisotrópicas

Conselho Nacional de Desenvolvimento Científico e Tecnológico

Ondas de spin em nanofilmes nagnéticos acoplados quasiperiodicamente

We studied the spin waves modes that can propagate in magnetic multilayers composed of ferromagnetic metallic films in the nanometer scale. The ferromagnetic films (iron) are separated and coupled through the nonmagnetic spacer films (chromium). The films that make up the multilayer are stacked in a quasiperiodic pattern, following the Fibonacci and double period sequences. We used a phenomenological theory taking into account: the Zeeman energy (between the ferromagnetic films and the external magnetic field), the energy of the magneto-crystalline anisotropy (present in the ferromagnetic films), the energy of the bilinear and biquadratic couplings (between the ferromagnetic films) and the energy of the dipole-dipole interaction (between the ferromagnetic films), to describe the system. The total magnetic energy of the system is numerically minimized and the equilibrium angles of the magnetization of each ferromagnetic film are determined. We solved the equation of motion of the multilayer to find the dispersion relation for the system and, as a consequence, the spin waves modes frequencies. Our theoretical results show that, in the case of trilayers (Fe/Cr/Fe), our model reproduces with excellent agreement experimental results of Brillouin light scattering, known from the literature, by adjusting the physical parameters of the nanofilms. Furthermore, we generalize the model to N ferromagnetic layers which allowed us to determine how complex these systems become when we increase the number of components. It is worth noting that our theoretical calculations generalize all the results known from the literature

Ondas de spin em quasi-cristais magnônicos

In this paper we investigate the spectra of band structures and transmittance in magnonic quasicrystals that exhibit the so-called deterministic disorders, specifically, magnetic multilayer systems, which are built obeying to the generalized Fibonacci (only golden mean (GM), silver mean (SM), bronze mean (BM), copper mean (CM) and nickel mean (NM) cases) and k-component Fibonacci substitutional sequences. The theoretical model is based on the Heisenberg Hamiltonian in the exchange regime, together with the powerful transfer matrix method, and taking into account the RPA approximation. The magnetic materials considered are simple cubic ferromagnets. Our main interest in this study is to investigate the effects of quasiperiodicity on the physical properties of the systems mentioned by analyzing the behavior of spin wave propagation through the dispersion and transmission spectra of these structures. Among of these results we detach: (i) the fragmentation of the bulk bands, which in the limit of high generations, become a Cantor set, and the presence of the mig-gap frequency in the spin waves transmission, for generalized Fibonacci sequence, and (ii) the strong dependence of the magnonic band gap with respect to the parameters k, which determines the amount of different magnetic materials are present in quasicrystal, and n, which is the generation number of the sequence k-component Fibonacci. In this last case, we have verified that the system presents a magnonic band gap, whose width and frequency region can be controlled by varying k and n. In the exchange regime, the spin waves propagate with frequency of the order of a few tens of terahertz (THz). Therefore, from a experimental and technological point of view, the magnonic quasicrystals can be used as carriers or processors of informations, and the magnon (the quantum spin wave) is responsible for this transport and processing

Resonant excitation of Mn local vibrational modes in the higher order Raman spectra of nanocrystalline Ga(1-x)Mn(x)N films

The effect of manganese on the vibrational properties of Ga(1-x)Mn(x)N (0 <= x <= 0.18) films has been investigated by Raman scattering using 488.0 and 632.8 nm photon excitations. The first-order transverse and longitudinal optical GaN vibrational bands were observed in the whole composition range using both excitations, while the corresponding overtones, as well as a prominent peak located in 1238 cm(-1) (153.5 meV) were only observed in the Mn-containing films under 488.0 nm excitation. We propose that the peak observed at 1238 cm(-1) is due to resonant Mn local vibrational modes, the excitation process being related to electronic transitions involving the Mn acceptor band.

Towards coherent optical control of a single hole spin: Rabi rotation of a trion conditional on the spin state of the hole

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