Chemical abundance analysis of the Be star HD 171054

In this work the results of a spectroscopic study of the southern field narrow-line Be star HD 171054 are presented. High dispersion and signal-to-noise ratio spectra allowed the estimation of the fundamental photospheric parameters such as the projected rotational velocity, effective temperature and superficial gravity from non-LTE stellar atmosphere models. From these parameters and microturbulence, the abundances of He, C, N, O, Mg, Al and Si for this object are estimated. Results show that C is depleted whereas N is overabundant compared with the sun and OB stars in the solar vicinity. Oxygen and helium are close to the solar value. Magnesium is down by 0.43 dex and aluminium and silicon are overabundant. (C) 2010 Elsevier B.V. All rights reserved.

Stability analysis of core-annular flow and neutral stability wave number

A general transition criterion is proposed in order to locate the core-annular flow pattern in horizontal and vertical oil-water flows. It is based on a rigorous one-dimensional two-fluid model of liquid-liquid two-phase flow and considers the existence of critical interfacial wave numbers related to a non-negligible interfacial tension term to which the linear stability theory still applies. The viscous laminar-laminar flow problem is fully resolved and turbulence effects on the stability are analyzed through experimentally obtained shape factors. The proposed general transition criterion includes in its formulation the inviscid Kelvin-Helmholtz`s discriminator. If a theoretical maximum wavelength is considered as a necessary condition for stability, a stability criterion in terms of the Eotvos number is achieved. Effects of interfacial tension, viscosity ratio, density difference, and shape factors on the stability of core-annular flow are analyzed in detail. The more complete modeling allowed for the analysis of the neutral-stability wave number and the results strongly suggest that the interfacial tension term plays an indispensable role in the correct prediction of the stable region of core-annular flow pattern. The incorporation of a theoretical minimum wavelength into the transition model produced significantly better results. The criterion predictions were compared with recent data from the literature and the agreement is encouraging. (C) 2007 American Institute of Chemical Engineers.

Theoretical Analysis of Aggregation in Block-Copolymer Films: The Optical Signature

We focus this work on the theoretical investigation of the block-copolymer poly [oxyoctyleneoxy-(2,6-dimethoxy-1,4phenylene-1,2-ethinylene-phenanthrene-2,4diyl) named as LaPPS19, recently proposed for optoelectronic applications. We used for that a variety of methods, from molecular mechanics to quantum semiempirical techniques (AMI, ZINDO/S-CIS). Our results show that as expected isolated LaPPS19 chains present relevant electron localization over the phenanthrene group. We found, however, that LaPPS19 could assemble in a pi-stacked form, leading to impressive interchain interaction; the stacking induces electronic delocalization between neighbor chains and introduces new states below the phenanthrene-related absorption; these results allowed us to associate the red-shift of the absorption edge, seen in the experimental results, to spontaneous pi-stack aggregation of the chains. (C) 2009 Wiley Periodicals, Inc. Int J Quantum Chem 110: 885-892, 2010

Empirical analysis of the Lieb-Oxford bound in ions and molecules

Universal properties of the Coulomb interaction energy apply to all many-electron systems. Bounds on the exchange-correlation energy, in particular, are important for the construction of improved density functionals. Here we investigate one such universal property-the Lieb-Oxford lower bound-for ionic and molecular systems. In recent work [J Chem Phys 127, 054106 (2007)], we observed that for atoms and electron liquids this bound may be substantially tightened. Calculations for a few ions and molecules suggested the same tendency, but were not conclusive due to the small number of systems considered. Here we extend that analysis to many different families of ions and molecules, and find that for these, too, the bound can be empirically tightened by a similar margin as for atoms and electron liquids. Tightening the Lieb-Oxford bound will have consequences for the performance of various approximate exchange-correlation functionals. (C) 2008 Wiley Periodicals Inc.

Photoluminescence study of new lanthanide complexes with benzeneseleninic acids

New lanthanide complexes with benzeneseleninic (ABSe) and 4-chloro-benzeneseleninic (ABSeCl) acids have been synthesized and characterized by elemental analysis, infrared and UV-visible spectroscopies. The emission spectra of the trivalent europium complexes presented the typical electronic (5)D(0) -> (7)F(j) transitions of the ion (J = 0-4). The ground-state geometries of the europium complexes have been calculated by using the Sparkle/AM1 model. From these results, the 4f-4f intensity parameters and energies of the ligand singlet and triplet excited states have been obtained. The lower emission quantum yield for the [Eu(ABSe)(3)(H(2)O)(2)](H(2)O)(2) compound, as compared to the [Eu(Al(3)SeCl)(3)(H(2)O)(2)] one, can be associated to the higher numbers of water molecules, in the first and second coordination spheres, that contribute to the luminescence quenching. The [Eu(Al(3)Se)(3)(H(2)O)(2)](H(2)O)(2) complex presents an intermediate state whose energy difference with respect to the first excited singlet state is resonant with three phonons from the water molecules, favouring a multiphonon relaxation process from the singlet state followed by a fast internal conversion process; this effect is less pronounced in the complex with the ABSeCl ligand. The luminescence decay curves of the gadolinium complexes indicate that the level responsible for the intramolecular energy transfer process has a triplet character for both compounds. The nephelauxetic effect in these compounds was investigated under the light of a recently proposed covalency scale based on the concept of overlap polarizability of the chemical bond. (C) 2009 Elsevier B.V. All rights reserved.

Electronic Structure and Chemical Bonding in the Ground and Low-Lying Electronic States of Ta(2)

The electronic structure and chemical bonding of the ground and low-lying Lambda - S and Omega states of Ta(2) were investigated at the multiconfiguration second-order perturbation theory (CASSCF//CASPT2) level. The ground state of Ta(2) is computed to be a X(3)Sigma(-)(g) state (R(e) = 2.120 angstrom, omega(e) = 323 cm(-1), and D(e) = 4.65 eV), with two low-lying singlet states close to it (a(1) Sigma(+)(g) : T(e) = 409 cm(-1), R(e) = 2.131 angstrom, and omega(e) = 313 cm(-1); b(1) Gamma(g): T(e) = 1, 038 cm(-1), R(e) = 2.127 angstrom, and omega(e) = 316 cm(-1)). These electronic states are derived from the same electronic configuration: vertical bar 13 sigma(2)(g)14 sigma(2)(g)7 delta(2)(g)13 pi(4)(u)>. The effective bond order of the X(3) Sigma(-)(g) state is 4.52, which indicates that the Ta atoms are bound by a quintuple chemical bond. The a(1) Sigma(+)(g) state interacts strongly with the X(3)Sigma(-)(g) g ground state by a second-order spin-orbit interaction, giving rise to the (1)0(g)(+) (ground state) (dominated by the X(3)Sigma(-)(g) Lambda - S ground state) and (9)0(g)(+) (dominated by the a(1) Sigma(+)(g) Lambda - S state) Omega states. These results are in line with those reported for the group 5B homonuclear transition metal diatomics. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1306-1315, 2011

I2: uma molécula didática

Iodine vapor is a very suitable substance to learn about molecular energy levels and transitions, and to introduce spectroscopic techniques. As a diatomic molecule its spectra are relatively simple and allow straightforward treatment of the data leading to the potential energy curves and to quantum mechanics concepts. The overtone bands, in the resonance Raman scattering, and the band progressions, in the electronic spectra, play an important role in the calculation of the Morse potential curves for the fundamental and excited electronic state. A weaker chemical bond in the electronic excited state, compared to the fundamental state, is evidenced by the increase in the equilibrium interatomic distance. The resonance Raman scattering of I2 is highlighted due to its importance for obtaining the anharmonicity constant in the fundamental electronic state.

Electronic Structure of the Ground and Low-Lying Electronic States of MoB and MoB(+)

Multiconfigurational second-order perturbation theory (CASSCF//CASPT2) and quadruple-zeta ANO-RCC basis sets were employed to investigate the ground and low-lying electronic states of MoB and MoB(+). Spectroscopic constants, potential energy curves, wavefunctions, Mulliken population analyses, and ionization energies are given. The ground state of MoB is of X(6)Pi symmetry (R(e) = 1.968 angstrom, omega(e) = 664 cm(-1), and mu = 2.7 D), giving rise to a Omega = 7/2 ground state after including spin-orbit coupling. For MoB(+), the ground state is computed to be of X(7)Sigma(+) symmetry (R(e) = 2.224 angstrom, omega(e) = 141 cm(-1), and mu = 1.2 D), with an adiabatic ionization energy of 7.19 eV and a vertical one of 7.53 eV. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111: 3362-3370, 2011

New Relativistic Atomic Natural Orbital Basis Sets for Lanthanide Atoms with Applications to the Ce Diatom and LuF3

New basis sets of the atomic natural orbital (ANO) type have been developed for the lanthanide atoms La-Lu. The ANOs have been obtained from the average density matrix of the ground and lowest excited states of the atom, the positive ions, and the atom in an electric field. Scalar relativistic effects are included through the use of a Douglas-Kroll-Hess Hamiltonian. Multiconfigurational wave functions have been used with dynamic correlation included using second-order perturbation theory (CASSCF/CASPT2). The basis sets are applied in calculations of ionization energies and some excitation energies. Computed ionization energies have an accuracy better than 0.1 eV in most cases. Two molecular applications are inluded as illustration: the cerium diatom and the LuF3 molecule. In both cases it is shown that 4f orbitals are not involved in the chemical bond in contrast to an earlier claim for the latter molecule.

Low-lying singlet and triplet electronic states of RhB

The low-lying X-1 Sigma(+), a(3)Delta, A(1)Delta, b(3)Sigma(+), B-1 Pi, c(3)Pi, C-1 Phi, D-1 Sigma(+), E-1 Pi, d(1)Phi, and e(3)Pi electronic states of RhB have been investigated at the ab initio level, using the multistate multiconfigurational second-order perturbation (MS-CASPT2) theory, with extended atomic basis sets and inclusion of scalar relativistic effects. Among the eleven electronic states included in this work, only three (the X-1 Sigma(+), D-1 Sigma(+), and E-1 Pi states) have been investigated experimentally. Potential energy curves, spectroscopic constants, dipole moments, binding energies, and chemical bonding aspects are presented for all electronic states.

A theoretical study of the binding and electronic spectrum of the Mo-2 molecule

Multiconfigurational SCF and second-order perturbation theory have been employed to study seven low-lying singlet and triplet electronic states of the Mo-2 molecule. The bond order of the ground state has been analyzed based on the effective bond order (EBO), indicating that a fully developed sextuple bond is formed between the two Mo atoms. The experimentally observed excited states a(3)Sigma(+)(u) and A(1)Sigma(+)(u) have been determined and the so-called (3)Lambda excited state identified as the b(3)Sigma(+)(u) state, in agreement with experimental expectations. (C) 2007 Elsevier B.V. All rights reserved.

Adhesion of an endodontic sealer to dentin and gutta-percha: shear and push-out bond strength measurements and SEM analysis

The use of an adequate method for evaluation of the adhesion of root canal filling materials provides more reliable results to allow comparison of the materials and substantiate their clinical choice. The aims of this study were to compare the shear bond strength (SBS) test and push-out test for evaluation of the adhesion of an epoxy-based endodontic sealer (AH Plus) to dentin and gutta-percha, and to assess the failure modes on the debonded surfaces by means of scanning electron microscopy (SEM). Three groups were established (n=7): in group 1, root cylinders obtained from human canines were embedded in acrylic resin and had their canals prepared and filled with sealer; in group 2, longitudinal sections of dentin cylinders were embedded in resin with the canal surface smoothed and turned upwards; in group 3, gutta-percha cylinders were embedded in resin. Polyethylene tubes filled with sealer were positioned on the polished surface of the specimens (groups 2 and 3). The push-out test (group 1) and the SBS test (groups 2 and 3) were performed in an Instron universal testing machine running at crosshead speed of 1 mm/min. Means (±SD) in MPa were: G1 (8.8±1.13), G2 (5.9±1.05) and G3 (3.8±0.55). Statistical analysis by ANOVA and Student's t-test (a=0.05) revealed statistically significant differences (p<0.01) among the groups. SEM analysis showed a predominance of adhesive and mixed failures of AH Plus sealer. The tested surface affected significantly the results with the sealer reaching higher bond strength to dentin than to gutta-percha with the SBS test. The comparison of the employed methodologies showed that the SBS test produced significantly lower bond strength values than the push-out test, was skilful in determining the adhesion of AH Plus sealer to dentin and gutta-percha, and required specimens that could be easily prepared for SEM, presenting as a viable alternative for further experiments.

Tensile bond strength and SEM analysis of enamel etched with Er:YAG laser and phosphoric acid: a comparative study In vitro

Er:YAG laser has been studied as a potential tool for restorative dentistry due to its ability to selectively remove oral hard tissue with minimal or no thermal damage to the surrounding tissues. The purpose of this study was to evaluate in vitro the tensile bond strength (TBS) of an adhesive/composite resin system to human enamel surfaces treated with 37% phosphoric acid, Er:YAG laser (lambda=2.94 mum) with a total energy of 16 J (80 mJ/pulse, 2Hz, 200 pulses, 250 ms pulse width), and Er:YAG laser followed by phosphoric acid etching. Analysis of the treated surfaces was performed by scanning electron microscopy (SEM) to assess morphological differences among the groups. TBS means (in MPa) were as follows: Er:YAG laser + acid (11.7 MPa) > acid (8.2 MPa) > Er:YAG laser (6.1 MPa), with the group treated with laser+acid being significantly from the other groups (p=0.0006 and p= 0.00019, respectively). The groups treated with acid alone and laser alone were significantly different from each other (p=0.0003). The SEM analysis revealed morphological changes that corroborate the TBS results, suggesting that the differences in TBS means among the groups are related to the different etching patterns produced by each type of surface treatment. The findings of this study indicate that the association between Er:YAG laser and phosphoric acid can be used as a valuable resource to increase bond strength to laser-prepared enamel.

Chemical evolution of the Galactic bulge as traced by microlensed dwarf and subgiant stars IV. Two bulge populations

Based on high-resolution (R approximate to 42 000 to 48 000) and high signal-to-noise (S/N approximate to 50 to 150) spectra obtained with UVES/VLT, we present detailed elemental abundances (O, Na, Mg, Al, Si, Ca, Ti, Cr, Fe, Ni, Zn, Y, and Ba) and stellar ages for 12 new microlensed dwarf and subgiant stars in the Galactic bulge. Including previous microlensing events, the sample of homogeneously analysed bulge dwarfs has now grown to 26. The analysis is based on equivalent width measurements and standard 1-D LTE MARCS model stellar atmospheres. We also present NLTE Li abundances based on line synthesis of the (7)Li line at 670.8 nm. The results from the 26 microlensed dwarf and subgiant stars show that the bulge metallicity distribution (MDF) is double-peaked; one peak at [Fe/H] approximate to -0.6 and one at [Fe/H] approximate to +0.3, and with a dearth of stars around solar metallicity. This is in contrast to the MDF derived from red giants in Baade's window, which peaks at this exact value. A simple significance test shows that it is extremely unlikely to have such a gap in the microlensed dwarf star MDF if the dwarf stars are drawn from the giant star MDF. To resolve this issue we discuss several possibilities, but we can not settle on a conclusive solution for the observed differences. We further find that the metal-poor bulge dwarf stars are predominantly old with ages greater than 10 Gyr, while the metal-rich bulge dwarf stars show a wide range of ages. The metal-poor bulge sample is very similar to the Galactic thick disk in terms of average metallicity, elemental abundance trends, and stellar ages. Speculatively, the metal-rich bulge population might be the manifestation of the inner thin disk. If so, the two bulge populations could support the recent findings, based on kinematics, that there are no signatures of a classical bulge and that the Milky Way is a pure-disk galaxy. Also, recent claims of a flat IMF in the bulge based on the MDF of giant stars may have to be revised based on the MDF and abundance trends probed by our microlensed dwarf stars.

Zone trapping/merging zones in flow analysis: A novel approach for rapid assays involving relatively slow chemical reactions

A novel strategy for accomplishing zone trapping in flow analysis is proposed. The sample and the reagent solutions are simultaneously inserted into convergent carrier streams and the established zones merge together before reaching the detector, where the most concentrated portion of the entire sample zone is trapped. The main characteristics, potentialities and limitations of the strategy were critically evaluated in relation to an analogous flow system with zone stopping. When applied to the spectrophotometric determination of nitrite in river waters, the main figures of merit were maintained, exception made for the sampling frequency which was calculated as 189h(-1), about 32% higher relatively to the analogous system with zone stopping. The sample inserted volume can be increased up to 1.0 mL without affecting sampling frequency and no problems with pump heating or malfunctions were noted after 8-h operation of the system. In contrast to zone stopping, only a small portion of the sample zone is halted with zone trapping, leading to these beneficial effects. (C) 2011 Elsevier B.V. All rights reserved.