Solvatochromic and lonochromic Effects of Iron(II)bis-(1,10-phenanthroline)dicyano: a Theoretical Study

Solvatochromic and ionochromic effects of the iron(II)bis(1,10-phenanthroline)dicyano (Fe(phen)(2)(CN)(2)) complex were investigated by means of combined DFT/TDDFT calculations using the PBE and B3LYP functionals. Extended solvation models of Fe(phen)(2)(CN)(2) in acetonitrile and aqueous solution, as well as including interaction with Mg(2+), were constructed. The calculated vertical excitation energies reproduce well the observed solvatochromism in acetonitrile and aqueous solutions, the ionochromism in acetonitrile in the presence of Mg(2+), and the absence of ionochromic effect in aqueous solution. The vertical excitation energies and the nature of the transitions were reliably predicted after inclusion of geometry relaxation upon aqueous micro- and global solvation and solvent polarization effect in the TDDFT calculations. The two intense UV-vis absorption bands occurring for all systems studied are interpreted as transitions from a hybrid Fe(II)(d)/cyano N(p) orbital to a phenanthroline pi* orbital rather than a pure metal-to-ligand-charge transfer (MLCT). The solvatochromic and ionochromic blue band shifts of Fe(phen)(2)(CN)(2) were explained with preferential stabilization of the highest occupied Fe(II)(d)/cyano N(p) orbitals as a result of specific interactions with water solvent molecules or Mg(2+) ions in solution. Such interactions occur through the CN(-) groups in the complex, and they have a decisive role for the observed blue shifts of UV-vis absorption bands.

Electronic Structure and Chemical Bonding in the Lowest Electronic States of TcN

Multiconfiguration second-order perturbation theory, with the inclusion of relativistic effects and spin-orbit Coupling, was employed to investigate the nature of the ground and low-lying Lambda-S and Omega states of the TcN molecule. Spectroscopic constants, effective bond order, and potential energy curves for 13 low-lying Lambda-S states and 5 Omega states are given, The computed ground state of TcN is of Omega = 3 symmetry (R(e) = 1.605 angstrom and omega(e) = 1085 cm(-1)), originating mainly from the (3)Delta Lambda-S ground state. This result is contrasted with the nature of the ground state for other VIIB transtion-metal mononitrides, including X(3)Sigma(-) symmetry for MnN and Omega = 0(+) symmetry for ReN, derived also from a X(3)Sigma(-) state.

Electronic structure and chemical bonding in the ground states of Tc(2) and Re(2)

Multiconfiguration second-order perturbation theory, including relativistic effects and spin-orbit coupling, has been employed to investigate the nature of the chemical bonding in the ground state of Tc(2) and Re(2). The Tc(2) ground state is found to be a 0(g)(+) state, with an effective bond order (EBO) of 4.4, and a dissociation energy of 3.25 eV. The Re(2) ground state is a 1(g) state, with EBO = 4.3. Almost degenerate to it, is a 0(g)(+) state (T(e) = 77 cm(-1)), with EBO = 4.1. Experimental evidence also indicates that the ground state is of 1(g) nature. The dissociation energy is computed to be 5.0 eV in agreement with an experimental estimate of 4 +/- 1 eV.

Effects of adding La and Ce to hydrotalcite-type Ni/Mg/Al catalyst precursors on ethanol steam reforming reactions

Catalyst precursors composed of Ni/Mg/Al oxides with added La and Ce were tested in ethanol steam reforming (ESR) reactions. La and Ce were added by anion-exchange. The oxides were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) analysis. The catalyst precursors consist of a mixture of oxides, with the nickel in the form of NiO strongly interacting with the support Mg/Al. The XPS analysis showed a lanthanum-support interaction, but no interaction of Ce species with the support. The reaction data obtained with the active catalysts showed that the addition of Ce and La resulted in better H(2) production at 550 degrees C. The CeNi catalyst provided the higher ethanol conversion, with lower acetaldehyde production, possibly clue to a favoring of water adsorption on the weakly interacting clusters of CeO(2) on the surface. (C) 2010 Elsevier B.V. All rights reserved.

Effects of the partial replacement of La by M (M=Ce, Ca and Sr) in La(2-x)M(x)CuO(4) perovskites on catalysis of the water-gas shift reaction

The performance of La(2-x)M(x)CuO(4) perovskites (where M = Ce, Ca or Sr) as catalysts for the water-gas shift reaction was investigated at 290 degrees C and 360 degrees C. The catalysts were characterized by EDS, XRD, N(2) adsorption-desorption, XPS and XANES. The XRD results showed that all the perovskites exhibited a single phase (the presence of perovskite structure), suggesting the incorporation of metals in the perovskite structure. The XPS and XANES results showed the presence of Cu(2+) on the surface. The perovskites that exhibited the best catalytic performance were La(2-x)Ce(x)CuO(4) perovslcites, with CO conversions of 85%-90%. Moreover, these perovskites have higher surface areas and larger amounts of Cu on the surface. And Ce has a higher filled energy level than the other metals, increasing the energy of the valence band of Ce and providing more electrons for the reaction. Besides, the La(1.80)Ca(0.20)CuO(4) perovskite showed a good catalytic performance.

Mass transport effects in the borohydride oxidation reaction-Influence of the residence time on the reaction onset and faradaic efficiency

The borohydride oxidation reaction (BOR) was studied on Pt and Au electrodes by cyclic voltammetry in dilute alkaline borohydride solutions (0.1 M NaOH + 10(-3) mol L(-1) NaBH(4)). More specifically, the electrodes were considered as either Vulcan XC72-supported Pt or Au (noted as Pt/C and Au/C, respectively) active layers or smooth Pt or Au surfaces, the latter possibly being covered by a layer of (non-metalized) Vulcan XC72 carbon powder. The BOR onset potential and the number of electrons (n(e-)) exchanged per BH(4)(-) anion (faradaic efficiency) were investigated for these electrodes, to determine whether the residence time of reaction intermediates (at the electrode surface or inside the porous layer) does influence the overall reaction pathway/completion. For the carbon-supported platinum, n(e-) strongly depends on the thickness of the active layer. While thin (ca. 0.5 mu m-thick) Pt/C active layers yield n(e-) < 4, thick layers (approximately 3 mu m) yield n(e-)approximate to 8, which can be ascribed to the sufficient residence time of the molecules formed within the active layer (H(2), by heterogeneous hydrolysis, or BOR intermediates) enabling further (near-complete) oxidation. This puts into evidence that not only the nature of the electrocatalyst is important to reach high BOR efficiency, but also the structure/thickness of the active layer. The same trend applies for Au/C active layers and for smooth Pt or Au surfaces covered with a layer of (inactive) Vulcan XC72. In addition, the BOR onset usually shifts negative when the reaction intermediates are trapped, which suggests that some of the intermediates are more easily oxidized than BH(4)(-) itself; based on literature data, BH(3)OH(-) species is a likely candidate. (C) 2011 Elsevier B.V. All rights reserved.

Effects of starch gelatinization and oxidation on the rheological behavior of chitosan/starch blends

Chitosan/starchblends represent an interesting alternative for the preparation of biocompatible drug delivery systems, packing materials and edible films. This paper reports on the effects of starch gelatinization and oxidation on the rheological behavior of chitosan/starch blends. The results show that the modifications in the starch structure cause changes in G` (storage modulus) and G `` (lossmodulus) as a function of frequency. For chitosan/starch, G `` is higher than G`, showing a viscous behavior. However, for chitosan/gelatinized starch and chitosan/oxidized starch, an increase in the angular frequency promotes a modulus crossover at omega = 0.02 and 0.04 rad s(-1), respectively. The viscosity curves as a function of shear rate show that both modifications cause an increase in viscosity, and all blends show a non-Newtonian behavior. (C) 2011 Society of Chemical Industry

Interaction of giant extracellular Glossoscolex paulistus hemoglobin (HbGp) with zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS): Effects of oligomeric dissociation

The present work focuses on the interaction between the zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp). Electronic optical absorption, fluorescence emission and circular dichroism spectroscopy techniques, together with Gel-filtration chromatography, were used in order to evaluate the oligomeric dissociation as well as the autoxidation of HbGp as a function of the interaction with HPS. A peculiar behavior was observed for the HPS-HbGp interaction: a complex ferric species formation equilibrium was promoted, as a consequence of the autoxidation and oligomeric dissociation processes. At pH 7.0, HPS is more effective up to 1 mM while at pH 9.0 the surfactant effect is more intense above 1 mM. Furthermore, the interaction of HPS with HbGp was clearly less intense than the interaction of this hemoglobin with cationic (CTAC) and anionic (SDS) surfactants. Probably, this lower interaction with HPS is due to two factors: (i) the lower electrostatic attraction between the HPS surfactant and the protein surface ionic sites when compared to the electrostatic interaction between HbGp and cationic and anionic surfactants, and (ii) the low cmc of HPS, which probably reduces the interaction of the surfactant in the monomeric form with the protein. The present work emphasizes the importance of the electrostatic contribution in the interaction between ionic surfactants and HbGp. Furthermore, in the whole HPS concentration range used in this study, no folding and autoxidation decrease induced by this surfactant were observed. This is quite different from the literature data on the interaction between surfactants and tetrameric hemoglobins, that supports the occurrence of this behavior for the intracellular hemoglobins at low surfactant concentration range. Spectroscopic data are discussed and compared with the literature in order to improve the understanding of hemoglobin-surfactant interaction as well as the acid isoelectric point (pI) influence of the giant extracellular hemoglobins on their structure-activity relationship. (c) 2007 Elsevier B.V. All rights reserved.

How does employment density influence individuals’ wages? : A micro data approach.

We estimate the effect of employment density on wages in Sweden in a large geocoded data set on individuals and workplaces. Employment density is measured in four circular zones around each individual’s place of living. The data contains a rich set of control variables that we use in an instrumental variables framework. Results show a relatively strong but rather local positive effect of employment density on wages. Beyond 5 kilometers the effect becomes negative. This might indicate that the effect of agglomeration economies falls faster with distance than the effects of congestion.

Göra illa för att hjälpa eller hjälpa till att göra illa? : Arbetslösas reservationslöner, jobbchanser och återanställningsinkomster

Hurting to help or helping to hurt? The reservation wages of unemployed, job chances and reemployment incomes in Sweden Economic incentives and their impact on the job search behaviour of the unemployed have been a central focus in the academic and political debate in Sweden. A key concept has been the reservation wages of the unemployed, the lowest income at which an unemployed person would be willing to accept a job offer. Unemployment benefit systems have been argued to raise and maintain reservation wages at high levels that lower job chances. This has been supported by a large number of international studies. From this perspective lower reservation wages would function as protection against long term unemployment and the scarring effects associated with it. High reservation wages might however, based on the same behavioural assumptions, have a human capital preserving effect. The possibility to hold out for the right job should reduce human capital losses compared to accepting the first available job offer. In this article we use Swedish longitudinal micro data combining interview and register data in order to investigate three central aspects reservation wages in a Swedish context: factors influencing the setting of reservation wages, the effect of reservation wage on job chances and the impact of reservation wages on reemployment incomes. Our findings show that benefit level and pre-unemployment position in the wage structure are central factors for setting the reservation wage. The effects of reservation wages were however not the expected. No effects were found on job chances, while a strong positive effect was found on reemployment income. This together indicates that high reservation wages have a human capital preserving effect in Sweden.

O uso comercial da internet por micro, pequenas e médias empresas de Porto Alegre : um estudo exploratório sobre as empresas do trade point Porto Alegre

Uma grande evolução aconteceu no mundo com o surgimento da Internet. Ela causou um espantoso aumento das comunicações, que passaram a ser em tempo real e com uma abrangência mundial. Foi a democratização da informação. A Internet serve como uma grande ferramenta para as empresas, principalmente com a globalização dos mercados, fenômeno que cresce cada dia mais e atinge a todos. A globalização fez com que as organizações se tornassem globais, e a Internet funciona como um elo de ligação entre empresas, fornecedores e consumidores. Este trabalho consistiu na realização de uma pesquisa survey exploratória com o objetivo de verificar e descrever o uso potencial da Internet como ferramenta de auxílio à realização de negócios de caráter global, nas micro, pequenas e médias empresas de Porto Alegre. A amostra das empresas pesquisadas foi extraída do Trade Point Porto Alegre, por ser essa uma entidade que tem por objetivo auxiliar as empresas a realizarem operações globais. Com relação ao mercado global, o trabalho identificou que quase todas as empresas acreditam que ele tenha oportunidades de negócios. Os principais meios para entrar nesse mercado são a participação em feiras e rodadas de negócios, contato pessoal e o Trade Point. A Internet já está disseminada no meio empresarial, todas as empresas já a conhecem, e boa parte das empresas realizam operações que podem ser auxiliadas pela rede, como comunicação, promoção de produtos e acompanhamento pós-venda. Identificou-se que as microempresas são as que menos acreditam no mercado internacional, mas apontaram que a Internet pode ajudá-las em suas atividades. Já as pequenas empresas são as que atuam no mercado internacional e acreditam que a Internet possa ajudá-las em algumas atividades. Por fim, as médias empresas, também atuam no mercado internacional, principalmente com as exportações, e são as que já estão utilizando a Internet. O Trade Point se mostrou um serviço bem requisitado pelas empresas, principalmente as que atuam com o comércio internacional. As principais vantagens citadas foram a centralização de informações e a geração de novos negócios.

Estimating the term structure of volatility and fixed income derivative pricing

Estimating the parameters of the instantaneous spot interest rate process is of crucial importance for pricing fixed income derivative securities. This paper presents an estimation for the parameters of the Gaussian interest rate model for pricing fixed income derivatives based on the term structure of volatility. We estimate the term structure of volatility for US treasury rates for the period 1983 - 1995, based on a history of yield curves. We estimate both conditional and first differences term structures of volatility and subsequently estimate the implied parameters of the Gaussian model with non-linear least squares estimation. Results for bond options illustrate the effects of differing parameters in pricing.

A integração micro macroeconomia modelos e justificativas

O objetivo desta pesquisa é o de mostrar que a necessidade de fundamentar a macroeconomia na micro, é um falso problema, pois na medida em que certas decisões microeconômicas afetam a macroeconomia é verdade também que decisões macroeconômicas afetam a realidade microeconômica. O reconhecimento destes fatos nos permitirá construir modelos econômicos mais relevantes , bem como entender mais adequadamente a estrutura dos sistema econômico e as implicações para aplicação de políticas econômicas.

The value of local partners in Brazil: the effects of ownership clusters and business group membership on firm value in emerging markets

Este estudo analisa como a classe de acionistas afeta o valor das empresas brasileiras listadas na bolsa de valores no ponto de vista da governança corporativa. O trabalho examina a interação entre o valor das empresas e cinco tipos de concentrações acionárias comumente presente em mercados emergentes: famílias, agentes públicos, investidores estrangeiros, executivos e investidores financeiros nacionais. A análise empírica demonstra que o mix e a concentração de participação acionária afeta significativamente o valor das empresas. Utilizando uma compilação única de dados em painel de 2004 a 2008, a presente pesquisa também desenvolve hipóteses sobre o efeito da participação em grupos econômicos para o valor das empresas. A investigação encontra evidências de que, apesar de sua importância para o desenvolvimento de empresas brasileiras, o capital familiar, instituições públicas, e investidores estrangeiros estão cedendo lugar a monitores mais especializados e menos concentrados, como executivos e instituições financeiras nacionais. Estes resultados indicam que a governança corporativa no Brasil pode estar alcançando níveis de maturidade mais elevados. Adicionalmente, apesar de não haver indicação da existência de correlação entre a participação em grupos econômicos e o valor das empresas, os resultados indicam que a presença de um tipo específico de acionista em uma empresa do grupo facilita investimentos futuros desta classe de acionista em outras empresas do mesmo grupo, sinalizando que os interesses acionários são provavelmente perpetuados dentro de uma mesma rede de empresas. Finalmente, a pesquisa demonstra que enquanto o capital familiar prefere investir em empresas com ativa mobilidade do capital, investidores internacionais e instituições públicas procuram investimentos em equity com menor mobilidade de capital, o que lhes garante mais transparência com relação ao uso dos recursos e fundos das empresas.

Micro evidence on brazilian price stickiness and its consequences for sectoral real exchange rate and inflation persistence

The purpose of this thesis is to investigate the price-setting behavior in Brazil and, in particular, the effects on inflation and good-level real exchange rate persistence. This thesis is composed by three Chapters. In the first Chapter, we present the main stylized facts about the behavior of retail prices in Brazil using micro data from the CPI index computed by the Fundação Getulio Vargas. Moreover we construct time series of price-setting statistics and relate them to macroeconomic variables using regression analyses. In Chapter 2, we investigated the relevance of heterogeneity in countries price stickiness on good-level real exchange rate persistence, considering a newly constructed panel data set of relative prices of 115 common products between the U.S. and Brazil. Chapter 3 is devoted to the relation between sectoral price stickiness and inflation persistence.