Excited-State Dynamics in fac-[Re(CO)(3)(Me(4)phen)(L)](+)

Excited-state dynamics in fac-[Re(CO)(3)(Me(4)phen)(cis-L)](+) (Me(4)phen = 3,4,7,8-tetramethyl-1,10-phenanthroline, L = 4-styrylpyridine (stpy) or 1,2-bis(4-pyridyl)ethylene (bpe)) were investigated by steady-state and time-resolved techniques. A complex equilibrium among three closely lying excited states, 3IL(cis-L), (3)MLCT(Re -> me4phen), and (3)IL(Me4phen), has been established. Under UV irradiation, cis-to-trans isomerization of coordinated cis-L is observed with a quantum yield of 0.15 in acetonitrile solutions. This photoreaction competes with radiative decay from (3)MLCT(Re -> Me4phen) and (3)IL(Me4phen) excited states, leading to a decrease in the emission quantum yield relative to the nonisomerizable complex fac-[Re(CO)(3)(Me(4)phen)(bpa)](+) (bpa = 1,2-bis(4-pyridyl)ethane). From temperature-dependent time-resolved emission measurements in solution and in poly(methyl methacrylate) (PMMA) films, energy barriers (Delta E(a)) for interconversion between (3)MLCT(Re -> me4Phen) and (3)IL(Me4phen) emitting states were determined. For L = cis-stpy, Delta E(a) = 11 (920 cm(-1)) and 15 kJ mol(-1) (1254 cm(-1)) in 5:4 propionitrile/butyronitrile and PMMA, respectively. For L = cis-bpe, Delta E(a) = 13 kJ mol(-1) (1087 cm(-1)) in 5:4 propionitrile/butyronitrile. These energy barriers are sufficient to decrease the rate constant for internal conversion from higher-lying (3)IL(me4phen) state to (3)MLCT(Re -> Me4phen), k(i) congruent to 10(6) s(-1). The decrease in rate allows for the observation of intraligand phosphorescence, even in fluid medium at room temperature. Our results provide additional insight into the role of energy gap and excited-state dynamics on the photochemical and photophysical properties of Re(I) polypyridyl complexes.

Essays on firm dynamics in the Swedish wholesale trade sector

This thesis consists of a summary and five self-contained papers addressing dynamics of firms in the Swedish wholesale trade sector. Paper [1] focuses upon determinants of new firm formation in the Swedish wholesale trade sector, using two definitions of firms’ relevant markets, markets defined as administrative areas, and markets based on a cost minimizing behavior of retailers. The paper shows that new entering firms tend to avoid regions with already high concentration of other firms in the same branch of wholesaling, while right-of-the-center local government and quality of the infrastructure have positive impacts upon entry of new firms. The signs of the estimated coefficients remain the same regardless which definition of relevant market is used, while the size of the coefficients is generally higher once relevant markets delineated on the cost-minimizing assumption of retailers are used. Paper [2] analyses determinant of firm relocation, distinguishing between the role of the factors in in-migration municipalities and out-migration municipalities. The results of the analysis indicate that firm-specific factors, such as profits, age and size of the firm are negatively related to the firm’s decision to relocate. Furthermore, firms seems to be avoiding municipalities with already high concentration of firms operating in the same industrial branch of wholesaling and also to be more reluctant to leave municipalities governed by right-of-the- center parties. Lastly, firms seem to avoid moving to municipalities characterized with high population density. Paper [3] addresses determinants of firm growth, adopting OLS and a quantile regression technique. The results of this paper indicate that very little of the firm growth can be explained by the firm-, industry- and region-specific factors, controlled for in the estimated models. Instead, the firm growth seems to be driven by internal characteristics of firms, factors difficult to capture in conventional statistics. This result supports Penrose’s (1959) suggestion that internal resources such as firm culture, brand loyalty, entrepreneurial skills, and so on, are important determinants of firm growth rates. Paper [4] formulates a forecasting model for firm entry into local markets and tests this model using data from the Swedish wholesale industry. The empirical analysis is based on directly estimating the profit function of wholesale firms and identification of low- and high-return local markets. The results indicate that 19 of 30 estimated models have more net entry in high-return municipalities, but the estimated parameters is only statistically significant at conventional level in one of our estimated models, and then with unexpected negative sign. Paper [5] studies effects of firm relocation on firm profits of relocating firms, employing a difference-in-difference propensity score matching. Using propensity score matching, the pre-relocalization differences between relocating and non-relocating firms are balanced, while the difference-in-difference estimator controls for all time-invariant unobserved heterogeneity among firms. The results suggest that firms that relocate increase their profits significantly, in comparison to what the profits would be had the firms not relocated. This effect is estimated to vary between 3 to 11 percentage points, depending on the length of the analyzed period. 

Exchange rate dynamics in Brazil

The paper aims to investigate on empirical and theoretical grounds the Brazilian exchange rate dynamics under floating exchange rates. The empirical analysis examines the short and long term behavior of the exchange rate, interest rate (domestic and foreign) and country risk using econometric techniques such as variance decomposition, Granger causality, cointegration tests, error correction models, and a GARCH model to estimate the exchange rate volatility. The empirical findings suggest that one can argue in favor of a certain degree of endogeneity of the exchange rate and that flexible rates have not been able to insulate the Brazilian economy in the same patterns predicted by literature due to its own specificities (managed floating with the use of international reserves and domestic interest rates set according to inflation target) and to externally determined variables such as the country risk. Another important outcome is the lack of a closer association of domestic and foreign interest rates since the new exchange regime has been adopted. That is, from January 1999 to May 2004, the US monetary policy has no significant impact on the Brazilian exchange rate dynamics, which has been essentially endogenous primarily when we consider the fiscal dominance expressed by the probability of default.

Monetary dynamics in a general equilibrium version of the Baumol-Tobin model

I study the welfare cost of inflation and the effect on prices after a permanent increase in the interest rate. In the steady state, the real money demand is homogeneous of degree one in income and its interest-rate elasticity is approximately equal to −1/2. Consumers are indifferent between an economy with 10% p.a. inflation and one with zero inflation if their income is 1% higher in the first economy. A permanent increase in the interest rate makes the price level to drop initially and inflation to adjust slowly to its steady state level.

Labor earnings dynamics in post-stabilization Brazil

This paper analyzes both the levels and evolution of wage inequality in the Brazilian formal labor market using administrative data from the Brazilian Ministry of Labor (RAIS) from 1994 to 2009. After the covariance structure of the log of real weekly wages is estimated and the variance of the log of real weekly wages is decomposed into its permanent and transitory components, we verify that nearly 60% of the inequality within age and education groups is explained by the permanent component, i.e., by time-invariant individual productive characteristics. During this period, wage inequality decreased by 29%. In the rst years immediately after the macroeconomic stabilization (1994

A comparative study of the credit card market dynamics in Mexico and Brazil

This research analyzes and compares the attractiveness of the Brazilian and Mexican credit card markets from a financial firm’s perspective. The market dynamics in Latin America’s two economic powerhouses are fleshed out with qualitative and quantitative data, using a strategic framework to structure the analysis. Since its adoption by both countries in 1956, credit card usage has experienced many years of double digit growth. However, penetration levels remain low compared with most developed countries. Brazil has a more developed credit card infrastructure, with more potential profit, and issuers might face fewer competitive challenges.  Alternatively, Mexico, is witnessing a more favorable economy, a friendlier business and regulatory environment, combined with fewer financial products that compete with the credit card. Therefore, this paper concludes that Brazil and Mexico both offer market opportunities for credit card companies that can navigate the different technological, demographic, macroeconomic, and regulatory shifts in each country.

Fast dynamics in the optical storage with Langmuir-Blodgett films of a diazocrown ether molecule

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

Vortex-Antivortex Dynamics in a Mesoscopic Superconducting Prism with a Centered Antidot

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Vortex dynamics in mesoscopic superconducting square of variable surface

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

Vortex-antivortex annihilation dynamics in a square mesoscopic superconducting cylinder

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

Hartman-Grobman decomposition when in presence of jumps in the relative degree of the dynamics in an energy harvesting device

This work deals with the nonlinear piezoelectric coupling in vibration-based energy harvesting, done by A. Triplett and D.D. Quinn in J. of Intelligent Material Syst. and Structures (2009). In that paper the first order nonlinear fundamental equation has a three dimensional state variable. Introducing both observable and control variables in such a way the controlled system became a SISO system, we can obtain as a corollary that for a particular choice of the observable variable it is possible to present an explicit functional relation between this variable one, and the variable representing the charge harvested. After-by observing that the structure in the Input-Output decomposition essentially changes depending on the relative degree changes, presenting bifurcation branches in its zero dynamics-we are able in to identify this type of bifurcation indicating its close relation with the Hartman - Grobman theorem telling about decomposition into stable and the unstable manifolds for hyperbolic points.

Neospora caninum infection dynamics in dairy cattle

Neospora caninum is considered in many countries as one of the key abortion agents in cattle. This study aims to investigate the parasite behavior in dairy cattle in the municipality of Avar,, SP, Brazil, where abortions frequently occur. An ELISA was performed to compare two samplings on a total of 615 animals; tests were performed in the same herds with a gap of 3 years. An increase in the percentage of reactive animals was observed, ranging from 21.6% at the first sampling to 38.9% at the second sampling. of the 176 animals tested at both samplings, 61.93% retained a non-reactive status, 15.9% retained a reactive status, 19.88% switched from non-reactive to reactive and 2.27% switched from reactive to non-reactive. of the 100 animals with reproductive disturbances, 50% presented anti-Neospora antibodies, thereby indicating the presence of the protozoa. When comparing cows and their respective female offspring, a predominance of horizontal infection was observed. Moreover, considering the significant percentage of animals that switched from non-reactive to reactive and the abundant presence of dogs among the herds, the N. caninum transmission may be attributed to presence of carnivores.