Detailed analysis of the charge transfer complex N,N-dimethylaniline-SO(2) by Raman spectroscopy and density functional theory calculations

Although the amine sulfur dioxide chemistry was well characterized in the past both experimentally and theoretically, no systematic Raman spectroscopic study describes the interaction between N,N-dimethylaniline (DMA) and sulfur dioxide (SO(2)). The formation of a deep red oil by the reaction of SO(2) with DMA is an evidence of the charge transfer (CT) nature of the DMA-SO(2) interaction. The DMA -SO(2) normal Raman spectrum shows the appearance of two intense bands at 1110 and 1151 cm(-1), which are enhanced when resonance is approached. These bands are assigned to nu(s)(SO(2)) and nu(phi-N) vibrational modes, respectively, confirming the interaction between SO(2) and the amine via the nitrogen atom. The dimethyl group steric effect favors the interaction of SO(2) with the ring pi electrons, which gives rise to a pi-pi* low-energy CT electronic transition, as confirmed by time-dependent density functional theory (TDDFT) calculations. In addition, the calculated Raman DMA-SO(2) spectrum at the B3LYP/6-311++g(3df,3pd) level shows good agreement with the experimental results (vibrational wavenumbers and relative intensities), allowing a complete assignment of the vibrational modes. A better understanding of the intermolecular interactions in this model system can be extremely useful in designing new materials to absorb, detect, or even quantify SO(2). Copyright (C) 2009 John Wiley & Sons, Ltd.

Optical energy storage properties of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) persistent luminescence materials

The details of the mechanism of persistent luminescence were probed by investigating the trap level structure of Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials (R: Y, La-Lu, excluding Pm and Eu) with thermoluminescence (TL) measurements and Density Functional Theory (DFT) calculations. The TL results indicated that the shallowest traps for each Sr(2)MgSi(2)O(7):Eu(2+),R(3+) material above room temperature were always ca. 0.7 eV corresponding to a strong TL maximum at ca. 90 A degrees C. This main trap energy was only slightly modified by the different co-dopants, which, in contrast, had a significant effect on the depths of the deeper traps. The combined results of the trap level energies obtained from the experimental data and DFT calculations suggest that the main trap responsible for the persistent luminescence of the Sr(2)MgSi(2)O(7):Eu(2+),R(3+) materials is created by charge compensation lattice defects, identified tentatively as oxygen vacancies, induced by the R(3+) co-dopants.

Isomers on the [H, S(2), Cl] potential energy surface: A high level investigation

This study reports a systematic state-of-the-art characterization of new sulfur-chlorine species on the [H, S(2), Cl] potential energy surface. Coupled cluster theory singles and doubles with perturbative contributions of connected triples, using the series of correlation consistent basis sets with extrapolations to the complete basis set limit (CBS), were employed to quantify the energetic quantities involved in the isomerization processes on this surface. The structures and vibrational frequencies are unique for some species and represent the most accurate investigation to date. These molecules are potentially a new route of coupling the sulfur and chlorine chemistries in the atmosphere, and conditions of high concentration of H(2)S (HS) like in volcanic eruptions might contribute to their formation. Also an assessment of the MP2/CBS approach relative to CCSD(T)/CBS provides insights on the expected performance of MP2/CBS on the characterization of polysulfides, and also of more complex systems containing disulfide bridges. (C) 2009 Elsevier B.V. All rights reserved.

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.

Investigating the Nature of Noble Gas-Copper Bonds by the Quantum Theory of Atoms in Molecules

We investigated noble gas copper bonds in linear complexes represented by the NgCuX general formula in which Ng and X stand for a noble gas (neon, argon, krypton, or xenon) and a halogen (fluorine, chlorine or bromine), respectively, by coupled cluster methods and modified cc-pVQZ basis sets. The quantum theory of atoms in molecules (QTAIM) shows a linear relation between the dissociation energy or noble gas-copper bonds and the amount of electronic charge transferred mainly from the noble gas to copper during complexation. Large changes in the QTAIM quadrupole moments of copper and noble gases resulting from this bonding and a comparison between NgCuX and NgNaCl systems indicate that these noble gas-copper bonds should be better interpreted as predominantly covalent. Finally, QTAIM atomic dipoles of noble gases in NgNaCl systems agree satisfactorily with atomic dipoles given by a simple model for these NgNa van der Waals bonds.

A dislocation based theory for the deformation hardening behavior of DP steels : Impact of martensite content and ferrite grain size

A dislocation model, accurately describing the uniaxial plastic stress-strain behavior of dual phase (DP) steels, is proposed and the impact of martensite content and ferrite grain size in four commercially produced DP steels is analyzed. It is assumed that the plastic deformation process is localized to the ferrite. This is taken into account by introducing a non-homogeneity parameter, f(e), that specifies the volume fraction of ferrite taking active part in the plastic deformation process. It is found that the larger the martensite content the smaller the initial volume fraction of active ferrite which yields a higher initial deformation hardening rate. This explains the high energy absorbing capacity of DP steels with high volume fractions of martensite. Further, the effect of ferrite grain size strengthening in DP steels is important. The flow stress grain size sensitivity for DP steels is observed to be 7 times larger than that for single phase ferrite.

Evaluation of Bulk and Surfaces Absorption Edge Energy of Sol-Gel-Dip-Coating SnO2 Thin Films

The absorption edge and the bandgap transition of sol-gel-dip-coating SnO2 thin films, deposited on quartz substrates, are evaluated from optical absorption data and temperature dependent photoconductivity spectra. Structural properties of these films help the interpretation of bandgap transition nature, since the obtained nanosized dimensions of crystallites are determinant on dominant growth direction and, thus, absorption energy. Electronic properties of the bulk and (110) and (101) surfaces are also presented, calculated by means of density functional theory applied to periodic calculations at B3LYP hybrid functional level. Experimentally obtained absorption edge is compared to the calculated energy band diagrams of bulk and (110) and (101) surfaces. The overall calculated electronic properties in conjunction with structural and electro-optical experimental data suggest that the nature of the bandgap transition is related to a combined effect of bulk and (101) surface, which presents direct bandgap transition.

Prediction of Soil Properties from the Concepts of Energy Transfer in Dynamic Penetration Tests

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Extension of PT-symmetric quantum mechanics to the Dirac theory with position-dependent mass

We present a new method to construct the exactly solvable PT-symmetric potentials within the framework of the position-dependent effective mass Dirac equation with the vector potential coupling scheme in 1 + 1 dimensions. In order to illustrate the procedure, we produce three PT-symmetric potentials as examples, which are PT-symmetric harmonic oscillator-like potential, PT-symmetric potential with the form of a linear potential plus an inversely linear potential, and PT-symmetric kink-like potential, respectively. The real relativistic energy levels and corresponding spinor components for the bound states are obtained by using the basic concepts of the supersymmetric quantum mechanics formalism and function analysis method. (C) 2007 Elsevier B.V. All rights reserved.

Exotic dark spinor fields

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Transient stability analysis of electric energy systems via a fuzzy ART-ARTMAP neural network

This work presents a methodology to analyze transient stability (first oscillation) of electric energy systems, using a neural network based on ART architecture (adaptive resonance theory), named fuzzy ART-ARTMAP neural network for real time applications. The security margin is used as a stability analysis criterion, considering three-phase short circuit faults with a transmission line outage. The neural network operation consists of two fundamental phases: the training and the analysis. The training phase needs a great quantity of processing for the realization, while the analysis phase is effectuated almost without computation effort. This is, therefore the principal purpose to use neural networks for solving complex problems that need fast solutions, as the applications in real time. The ART neural networks have as primordial characteristics the plasticity and the stability, which are essential qualities to the training execution and to an efficient analysis. The fuzzy ART-ARTMAP neural network is proposed seeking a superior performance, in terms of precision and speed, when compared to conventional ARTMAP, and much more when compared to the neural networks that use the training by backpropagation algorithm, which is a benchmark in neural network area. (c) 2005 Elsevier B.V. All rights reserved.

New approach to ideal inductors stored energy nature

Nonlinear load compensation required the definition of new concepts of electric power. With basis on these new concepts the nature of the stored energy stored in ideal inductors is theoreticaly characterized in this work. Computer simulation and theory agree when applied to an isolated alternator.

Robust fault diagnosis in power distribution systems based on fuzzy ARTMAP neural network-aided evidence theory

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

On the performance of a dual-mode non-linear vibration energy harvesting device

The research trend for harvesting energy from the ambient vibration sources has moved from using a linear resonant generator to a non-linear generator in order to improve on the performance of a linear generator; for example, the relatively small bandwidth, intolerance to mistune and the suitability of the device for low-frequency applications. This article presents experimental results to illustrate the dynamic behaviour of a dual-mode non-linear energy-harvesting device operating in hardening and bi-stable modes under harmonic excitation. The device is able to change from one mode to another by altering the negative magnetic stiffness by adjusting the separation gap between the magnets and the iron core. Results for the device operating in both modes are presented. They show that there is a larger bandwidth for the device operating in the hardening mode compared to the equivalent linear device. However, the maximum power transfer theory is less applicable for the hardening mode due to occurrence of the maximum power at different frequencies, which depends on the non-linearity and the damping in the system. The results for the bi-stable mode show that the device is insensitive to a range of excitation frequencies depending upon the input level, damping and non-linearity.