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.

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.

Chinese Basic Pension Substitution Rate: A Monte Carlo Demonstration of the Individual Account Model

At the end of 2005, the State Council of China passed ”The Decision on adjusting the Individual Account of Basic Pension System”, which adjusted the individual account in the 1997 basic pension system. In this essay, we will analyze the adjustment above, and use Life Annuity Actuarial Theory to establish the basic pension substitution rate model. Monte Carlo simulation is also used to prove the rationality of the model. Some suggestions are put forward associated with the substitution rate according to the current policy.

The Dynamics of The Firm : In Search for a General Model

This paper describe a model from system theory that can be used as a base for better understanding of different situations in the firms evolution. This change model is derived from the theory of organic systems and divides the evolution of the system into higher complexity of the system structure in three distinctive phases. These phases are a formative phase, a normative phase and an integrative phase. After a summary of different types of models of the dynamics of the firm the paper makes a theoretical presentation of the model and how this model is adaptable for better understanding of the need for change in strategic orientation, organization form and leadership style over time.

Methodology for identifying parameters for the TRNSYS model Type 210 -wood pellet stoves and boilers

This report describes a method how to perform measurements on boilers and stoves and how to identify parameters from the measurements for the boiler/stove-model TRNSYS Type 210. The model can be used for detailed annual system simulations using TRNSYS. Experience from measurements on three different pellet stoves and four boilers were used to develop this methodology. Recommendations for the set up of measurements are given and the re-quired combustion theory for the data evaluation and data preparation are given. The data evalua-tion showed that the uncertainties are quite large for the measured flue gas flow rate and for boilers and stoves with high fraction of energy going to the water jacket also the calculated heat rate to the room may have large uncertainties. A methodology for the parameter identification process and identified parameters for two different stoves and three boilers are given. Finally the identified models are compared with measured data showing that the model generally agreed well with meas-ured data during both stationary and dynamic conditions.

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.

Uncertainties In Future Projections Of Extreme Rainfall: The Role Of Climate Model, Emission Scenario And Randomness

Climate change has resulted in substantial variations in annual extreme rainfall quantiles in different durations and return periods. Predicting the future changes in extreme rainfall quantiles is essential for various water resources design, assessment, and decision making purposes. Current Predictions of future rainfall extremes, however, exhibit large uncertainties. According to extreme value theory, rainfall extremes are rather random variables, with changing distributions around different return periods; therefore there are uncertainties even under current climate conditions. Regarding future condition, our large-scale knowledge is obtained using global climate models, forced with certain emission scenarios. There are widely known deficiencies with climate models, particularly with respect to precipitation projections. There is also recognition of the limitations of emission scenarios in representing the future global change. Apart from these large-scale uncertainties, the downscaling methods also add uncertainty into estimates of future extreme rainfall when they convert the larger-scale projections into local scale. The aim of this research is to address these uncertainties in future projections of extreme rainfall of different durations and return periods. We plugged 3 emission scenarios with 2 global climate models and used LARS-WG, a well-known weather generator, to stochastically downscale daily climate models’ projections for the city of Saskatoon, Canada, by 2100. The downscaled projections were further disaggregated into hourly resolution using our new stochastic and non-parametric rainfall disaggregator. The extreme rainfall quantiles can be consequently identified for different durations (1-hour, 2-hour, 4-hour, 6-hour, 12-hour, 18-hour and 24-hour) and return periods (2-year, 10-year, 25-year, 50-year, 100-year) using Generalized Extreme Value (GEV) distribution. By providing multiple realizations of future rainfall, we attempt to measure the extent of total predictive uncertainty, which is contributed by climate models, emission scenarios, and downscaling/disaggregation procedures. The results show different proportions of these contributors in different durations and return periods.

On choice of technique in the Robinson-Solow-Srinivasan model

We report results on the optimal \choice of technique" in a model originally formulated by Robinson, Solow and Srinivasan (henceforth, the RSS model) and further discussed by Okishio and Stiglitz. By viewing this vintage-capital model without discounting as a speci c instance of the general theory of intertemporal resource allocation associated with Brock, Gale and McKenzie, we resolve longstanding conjectures in the form of theorems on the existence and price support of optimal paths, and of conditions suÆcient for the optimality of a policy rst identi ed by Stiglitz. We dispose of the necessity of these conditions in surprisingly simple examples of economies in which (i) an optimal path is periodic, (ii) a path following Stiglitz' policy is bad, and (iii) there is optimal investment in di erent vintages at di erent times. (129 words)

On a uniform turnpike of the third kind in the Robinson-Solow-Srinivasan model

On using McKenzie’s taxonomy of optimal accumulation in the longrun, we report a “uniform turnpike” theorem of the third kind in a model original to Robinson, Solow and Srinivasan (RSS), and further studied by Stiglitz. Our results are presented in the undiscounted, discrete-time setting emphasized in the recent work of Khan-Mitra, and they rely on the importance of strictly concave felicity functions, or alternatively, on the value of a “marginal rate of transformation”, ξσ, from one period to the next not being unity. Our results, despite their specificity, contribute to the methodology of intertemporal optimization theory, as developed in economics by Ramsey, von Neumann and their followers.

Foreign funding to an emerging market: the Monetary Premium Theory and the Brazilian Case, 1991 - 1998

We develop a framework to explain the private capital flows between the rest of the world and an emerging economy. The model, based on the monetary premium theory, relates an endogenous supply of foreign capitals to an endogenous differential of interest rates; its estimation uses the econometric techniques initiated by Heckman. Four questions regarding the capital flows phenomenon are explored, including the statistical process that governs the events of default and the impact of the probability of default on the interest rate differential. Using the methodology, we analyse the dynamics of foreign capital movements in Brazil during the 1991- 1998 period.

Essays on monetary and banking theory

Esta tese de Doutorado é dedicada ao estudo de instabilidade financeira e dinâmica em Teoria Monet ária. E demonstrado que corridas banc árias são eliminadas sem custos no modelo padrão de teoria banc ária quando a popula ção não é pequena. É proposta uma extensão em que incerteza agregada é mais severa e o custo da estabilidade financeira é relevante. Finalmente, estabelece-se otimalidade de transições na distribui ção de moeda em economias em que oportunidades de trocas são escassas e heterogêneas. Em particular, otimalidade da inflação depende dos incentivos dinâmicos proporcionados por tais transi ções. O capí tulo 1 estabelece o resultado de estabilidade sem custos para economias grandes ao estudar os efeitos do tamanho populacional na an álise de corridas banc árias de Peck & Shell. No capí tulo 2, otimalidade de dinâmica é estudada no modelo de monet ário de Kiyotaki & Wright quando a sociedade é capaz de implementar uma polí tica inflacion ária. Apesar de adotar a abordagem de desenho de mecanismos, este capí tulo faz um paralelo com a an álise de Sargent & Wallace (1981) ao destacar efeitos de incentivos dinâmicos sobre a interação entre as polí ticas monet ária e fiscal. O cap ítulo 3 retoma o tema de estabilidade fi nanceira ao quanti car os custos envolvidos no desenho ótimo de um setor bancário à prova de corridas e ao propor uma estrutura informacional alternativa que possibilita bancos insolventes. A primeira an álise mostra que o esquema de estabilidade ótima exibe altas taxas de juros de longo prazo e a segunda que monitoramento imperfeito pode levar a corridas bancárias com insolvência.

Forecasting multivariate time series under present-value-model short- and long-run co-movement restrictions

It is well known that cointegration between the level of two variables (e.g. prices and dividends) is a necessary condition to assess the empirical validity of a present-value model (PVM) linking them. The work on cointegration,namelyon long-run co-movements, has been so prevalent that it is often over-looked that another necessary condition for the PVM to hold is that the forecast error entailed by the model is orthogonal to the past. This amounts to investigate whether short-run co-movememts steming from common cyclical feature restrictions are also present in such a system. In this paper we test for the presence of such co-movement on long- and short-term interest rates and on price and dividend for the U.S. economy. We focuss on the potential improvement in forecasting accuracies when imposing those two types of restrictions coming from economic theory.

Isolated capital cities and misgovernance: theory and evidence

Motivated by a novel stylized fact { countries with isolated capital cities display worse quality of governance { we provide a framework of endogenous institutional choice based on the idea that elites are constrained by the threat of rebellion, and that this threat is rendered less e ective by distance from the seat of political power. In established democracies, the threat of insurgencies is not a binding constraint, and the model predicts no correlation between isolated capitals and misgovernance. In contrast, a correlation emerges in equilibrium in the case of autocracies. Causality runs both ways: broader power sharing (associated with better governance) means that any rents have to be shared more broadly, hence the elite has less of an incentive to protect its position by isolating the capital city; conversely, a more isolated capital city allows the elite to appropriate a larger share of output, so the costs of better governance for the elite, in terms of rents that would have to be shared, are larger. We show evidence that this pattern holds true robustly in the data. We also show that isolated capitals are associated with less power sharing, a larger income premium enjoyed by capital city inhabitants, and lower levels of military spending by ruling elites, as predicted by the theory.

Contributions to the Theory of Optimal Tests

This paper considers tests which maximize the weighted average power (WAP). The focus is on determining WAP tests subject to an uncountable number of equalities and/or inequalities. The unifying theory allows us to obtain tests with correct size, similar tests, and unbiased tests, among others. A WAP test may be randomized and its characterization is not always possible. We show how to approximate the power of the optimal test by sequences of nonrandomized tests. Two alternative approximations are considered. The rst approach considers a sequence of similar tests for an increasing number of boundary conditions. This discretization allows us to implement the WAP tests in practice. The second method nds a sequence of tests which approximate the WAP test uniformly. This approximation allows us to show that WAP similar tests are admissible. The theoretical framework is readily applicable to several econometric models, including the important class of the curved-exponential family. In this paper, we consider the instrumental variable model with heteroskedastic and autocorrelated errors (HAC-IV) and the nearly integrated regressor model. In both models, we nd WAP similar and (locally) unbiased tests which dominate other available tests.

Demand- side resistance to creative destruction in schumpeterian growth theory

The Schumpelerian model of endogeno~s growlh is generalized with lhe introduction of stochastic resislance. by agenls other Ihan producers. to lhe innovations which drive growth. This causes a queue to be formcd of innovations, alrcady discovered, bUI waiting to be adopled~ A slationary stochastic equilibrium (SSE) is obtained when the queue is stable~ It is shown that in the SSE, such resistance will always reduce lhe average growth iate hut it may increa~e wclfare in certain silualions. In an example, Ihis is when innovatiuns are small anti monopoly power great. The cont1icl hetween this welfare motive for resistance and those of rent-seeking innovalors.may well explain why growth rates differ.