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

Azo-hydrazone tautomerism in protonated aminoazobenzenes: Resonance Raman spectroscopy and quantum-chemical calculations

The protonation effect on the vibrational and electronic spectra of 4-aminoazobenzene and 4-(dimethylamino)azobenzene was investigated by resonance Raman spectroscopy, and the results were discussed on the basis of quantum-chemical calculations. Although this class of molecular systems has been investigated in the past concerning the azo-hydrazone tautomerism, the present work is the first to use CASSCF/CASPT2 calculations to unveil the structure of both tautomers as well the nature of the molecular orbitals involved in chromophoric moieties responsible for the resonance Raman enhancement patterns. More specifically both the resonance Raman and theoretical results show clearly that in the neutral species, the charge transfer transition involves mainly the azo moiety, whereas in the protonated forms there is a great difference, depending on the tautomer. In fact, for the azo tautomer the transition is similar to that observed in the corresponding neutral species, whereas in the hydrazone tautomer such a transition is much more delocalized due to the contribution of the quinoid structure. The characterization of protonated species and the understanding of the tautomerization mechanism are crucial for controlling molecular properties depending on the polarity and pH of the medium.

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.

On the Relaxation Mechanisms of 6-Azauracil

The nonadiabatic photochemistry of 6-azauracil has been studied by means of the CASPT2//CASSCF protocol and double-zeta plus polarization ANO basis sets. Minimum energy states, transition states, minimum energy paths, and surface intersections have been computed in order to obtain an accurate description of several potential energy hypersurfaces. It is concluded that, after absorption of ultraviolet radiation (248 nm), two main relaxation mechanisms may occur, via which the lowest (3)(pi pi*) state can be populated. The first one takes place via a conical intersection involving the bright (1)(pi pi*) and the lowest (1)(n pi*) states, ((1)pi pi*/(1)n pi*)(CI), from which a low energy singlet-triplet crossing, ((1)n pi*/(3)pi pi*)(STC), connecting the (1)(n pi*) state to the lowest (3)(pi pi*) triplet state is accessible. The second mechanism arises via a singlet-triplet crossing, ((1)pi pi*/(3)n pi*)(STC), leading to a conical intersection in the triplet manifold, ((3)n pi*/(3)pi pi*)(CI), evolving to the lowest (3)(pi pi*) state. Further radiationless decay to the ground state is possible through a (gs/(3)pi pi*)(STC).

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.

Abstract types and distributions in independent private value auctions

In this note, in an independent private values auction framework, I discuss the relationship between the set of types and the distribution of types. I show that any set of types, finite dimensional or not, can be extended to a larger set of types preserving incentive compatibility constraints, expected revenue and bidder’s expected utilities. Thus for example we may convexify a set of types making our model amenable to the large body of theory in economics and mathematics that relies on convexity assumptions. An interesting application of this extension procedure is to show that although revenue equivalence is not valid in general if the set of types is not convex these mechanism have underlying distinct allocation mechanism in the extension. Thus we recover in these situations the revenue equivalence.

A confusão no processo de escolha do consumidor

Dentro da literatura de Comportamento do Consumidor e Teoria da Decisão existe considerável corpo teórico que analisa sentimentos negativos e reações adversas no processo decisório de compras de produtos de alto e baixo envolvimento. Vários fenômenos são identificados como negativos no processo, principalmente a Confusão do Consumidor, que compreende três dimensões: i) muitas informações similares sobre produtos, ii) muitas informações sobre diferentes produtos e iii) informações falsas e ambíguas. Tal fenômeno, no entanto, parece ser moderado por um conjunto de variáveis, como o Envolvimento, a Experiência e a Restrição de Tempo (moderadoras da relação entre Confusão do Consumidor e Intenção de Compra). Este fato foi identificado através de entrevistas em profundidade. Os resultados das entrevistas permitiram identificar as variáveis moderadoras, assim como a existência do fenômeno e sua relação com a decisão final de compra. Na segunda fase da pesquisa, supõe-se que indivíduos com baixo Envolvimento e Restrição de Tempo possuam uma propensão maior à confusão. No Estudo 2 foram utilizados como moderadores o Envolvimento e a Restrição de Tempo, ambos manipulados por instrução, sendo as variáveis dependentes a Intenção de Compra e a Confusão do Consumidor. Os resultados do Estudo 2 permitiram inferir que existem diferenças significativas entre os grupos, quando analisada a variável Confusão do Consumidor, mas, em alguns grupos, a Intenção de Compra não era significativamente diferente. No Estudo 3 foram manipuladas a Experiência (forte e fraca) e a Confusão do Consumidor, sendo a variável dependente a Intenção de Compra. Os resultados do Estudo 3 também permitiram inferir que existem diferenças significativas entre os grupos na Intenção de compra, quando consideradas baixa ou alta confusão, assim como Experiência forte ou fraca. Na última fase da pesquisa foram destacadas as estratégias dos consumidores para lidar com o fenômeno Confusão do Consumidor. Tais estratégias, muitas vezes, são mediadoras de comportamentos posteriores, como a compra do produto. No Estudo 4 manipulou-se a Confusão do Consumidor em duas de suas dimensões. Foi possível destacar a preponderância da estratégia por busca de informações e postergação da decisão, quando o consumidor se depara com situações confusas.

Generic Bifurcations of Planar Filippov Systems via Geometric Singular Perturbations

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

Synchronization and Non-Smooth Dynamical Systems

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Vector and axial-vector correlators in a non-local chiral quark model

The behavior of the non-perturbative parts of the isovector-vector and isovector and isosinglet axial-vector correlators at Euclidean momenta is studied in the framework of a covariant chiral quark model with non-local quark-quark interactions. The gauge covariance is ensured with the help of the P-exponents, with the corresponding modification of the quark-current interaction vertices taken into account. The low- and high-momentum behavior of the correlators is compared with the chiral perturbation theory and with the QCD operator product expansion, respectively. The V-A combination of the correlators obtained in the model reproduces quantitatively the ALEPH and OPAL data on hadronic tau decays, transformed into the Euclidean domain via dispersion relations. The predictions for the electromagnetic pi(+/-) - pi(0) mass difference and for the pion electric polarizability are also in agreement with the experimental values. The topological susceptibility of the vacuum is evaluated as a function of the momentum, and its first moment is predicted to be chi'(0) approximate to (50 MeV)(2). In addition, the fulfillment of the Crewther theorem is demonstrated.

Pion interactions in the X(3872)

We consider pion interactions in an effective field theory of the narrow resonance X(3872), assuming it is a weakly bound molecule of the charm mesons D-0(D) over bar (*0) and D-*0(D) over bar (0). Since the hyperfine splitting of the D-0 and D-*0 is only 7 MeV greater than the neutral pion mass, pions can be produced near threshold and are nonrelativistic. We show that pion exchange can be treated in perturbation theory and calculate the next-to-leading-order correction to the partial decay width Gamma[X -> D-0(D) over bar (0)pi(0)].

One loop conformal invariance of the superstring in an AdS(5) x S-5 background

It is proven that the pure spinor superstring in an AdS(5) x S-5 background remains conformally invariant at one loop level in the sigma model perturbation theory.

Chiral corrections to baryon properties with composite pions

A calculational scheme is developed to evaluate chiral corrections to properties of composite baryons with composite pions. The composite baryons and pions are bound states derived from a microscopic chiral quark model. The model is amenable to standard many-body techniques such as the BCS and random phase approximation formalisms. An effective chiral model involving only hadronic degrees of freedom is derived from the macroscopic quark model by projection onto hadron states. Chiral loops are calculated using the effective hadronic Hamiltonian. A simple microscopic confining interaction is used to illustrate the derivation of the pion-nucleon form factor and the calculation of picnic self-energy corrections to the nucleon and Delta (1232) masses.

Operator ordering in quantum radiative processes

In this work we reexamine quantum electrodynamics of atomic electrons in the Coulomb gauge in the dipole approximation and calculate the shift of atomic energy levels in the context of Dalibard, Dupont-Roc and Cohen-Tannoudji formalism by considering the variation rates of physical observable. We then analyze the physical interpretation of the ordering of operators in the dipole approximation interaction Hamiltonian in terms of field fluctuations and self-reaction of atomic electrons, discussing the arbitrariness in the statistical functions in second-order bound-state perturbation theory. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Structure formation in the presence of dark energy perturbations

We study non-linear structure formation in the presence of dark energy. The influence of dark energy on the growth of large-scale cosmological structures is exerted both through its background effect on the expansion rate, and through its perturbations. In order to compute the rate of formation of massive objects we employ the spherical collapse formalism, which we generalize to include fluids with pressure. We show that the resulting non-linear evolution equations are identical to the ones obtained in the pseudo-Newtonian approach to cosmological perturbations, in the regime where an equation of state serves to describe both the background pressure relative to density, and the pressure perturbations relative to the density perturbations. We then consider a wide range of constant and time-dependent equations of state (including phantom models) parametrized in a standard way, and study their impact on the non-linear growth of structure. The main effect is the formation of dark energy structure associated with the dark matter halo: non-phantom equations of state induce the formation of a dark energy halo, damping the growth of structures; phantom models, on the other hand, generate dark energy voids, enhancing structure growth. Finally, we employ the Press-Schechter formalism to compute how dark energy affects the number of massive objects as a function of redshift (number counts).