Estruturação do Eumenine Mastroparano por dinâmica molecular em misturas de TFE-água

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

H- 'H POT. +' e HE- 'H POT. +' confinados via método Hartree-Fock

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Estudo da segregação de dopantes no contorno de grão e sua influência nas propriedades elétricas de cerâmicas à base de 'SN''O IND.2'

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Circulation and salt intrusion in the Piaçaguera Channel, Santos (SP)

A análise de dados termohalinos e correntes medidos em uma estação fixa no Canal de Piaçaguera (Estuário de Santos) no inverno foi feita em termos de condições cíclicas da maré (quadratura e sizígia) e quase-estacionária, com o objetivo de caracterizar a estratificação da massa de água estuarina, sua circulação e transporte de sal forçados pela modulação quinzenal da maré. Foram utilizados métodos clássicos de análise de dados observacionais horários e quase sinóticos e de simulações analíticas de perfis estacionários de salinidade e do componente longitudinal da velocidade. Durante o ciclo de maré de quadratura as velocidades de enchente (v<0) e vazante (v>0) variaram de -0.20 m/s a 0.30 m/s, associadas à pequena variação de salinidade entre a superfície e o fundo (26.4 psu a 30.7 psu). No ciclo de sizígia a velocidade aumentou de -0.40 m/s a 0.45 m/s, mas a estratificação de salinidade permaneceu praticamente a mesma. Os perfis estacionários teóricos de salinidade e de velocidade apresentaram boa concordância (Skill próximo a 1,0) quando comparados aos perfis observacionais. Durante a modulação quinzenal da maré não houve alteração na classificação do canal estuarino (tipo 2a-parcialmente misturado e fracamente estratificado), pois a taxa de aumento da energia potencial não foi suficiente para ocasionar a erosão da haloclina. Esses resultados, associados à alta estabilidade vertical (RiL >20) e ao número de Richardson estuarino (1,6), permitem as seguintes conclusões: i) o mecanismo que forçou a circulação e os processos de mistura foi principalmente o balanço da descarga fluvial com a maré, associado ao componente baroclínico da força de gradiente de pressão; ii) não houve variações nas principais características termohalinas e da circulação devido à modulação quinzenal da maré; e iii) os perfis quase estacionários de salinidade e da velocidade foram adequadamente simulados com um modelo analítico clássico.

Influências das condições termodinâmicas nos eventos extremos de precipitação na cidade de Belém e região metropolitana

O objetivo desta dissertação foi verificar a importância dos fatores termodinâmicos na ocorrência de eventos extremos de precipitação na Cidade de Belém (PA) e região metropolitana, no período de agosto de 2008 a dezembro de 2009. Para tal, foram utilizados dados de precipitação e radiossondagens. Para análise das condições termodinâmicas e dinâmicas foram utilizadas imagens de satélite, cartas de superfície e análise do diagrama SKEW T LOG P. O estudo da termodinâmica da atmosfera foi realizado a luz das teorias da Energia Potencial Disponível para a Convecção (CAPE) e, também, da Energia de Inibição da Convecção (CINE). Foi utilizado o método dos decis para classificar os eventos extremos de precipitação a fim de associá-los aos valores da CAPE e da CINE com o objetivo de verificar o valor destes índices quando da ocorrência dos eventos extremos. Verificou-se que a região estudada possui forte atividade convectiva durante todo o ano, haja vista que seus valores médios mensais variam entre 900 J/kg e 1900 J/kg. Foi visto, também, que nem sempre CAPE alta e CINE baixa determinam precipitação. Esta situação determina o potencial para a convecção profunda, mas para converter este potencial em precipitação existe a necessidade da forçante dinâmica. Os resultados mostraram que quando o processo de precipitação dependeu, exclusivamente, da CAPE, foi necessário haver um valor alto para poder gerar convecção profunda e por consequência precipitação, enquanto, que no processo de precipitação com contribuição dinâmica não foi necessário um valor tão significativo da CAPE, neste caso, não ultrapassou a 1000 J/kg. A CINE esteve, sempre, menor no período chuvoso apresentando valores médios mensais menores que 300 J/kg. Isto não quer dizer que quanto menor a CINE maior será a precipitação. Quando a inibição está presente a instabilidade vai crescendo ao longo do dia determinando, com isso, nuvens com um desenvolvimento vertical mais acentuado, assim os pontos onde os inibidores enfraquecem primeiro, serão os pontos preferenciais para o disparo da tempestade. Logo, quando a instabilidade estiver alta e existir o mecanismo inibidor (CINE), em uma grande área, os locais mais propícios aos disparos das tempestades são os pontos onde a CINE e o NCE começam a diminuir e a inversão térmica, que por vezes acontece, começa a ser quebrada. Durante a execução desta pesquisa ficou claro que para a ocorrência de eventos extremos de precipitação, no período chuvoso, existe necessidade da influência da ITCZ e no período seco, conforme se observa no estudo de caso realizado para o mês de outubro o fator dinâmico que mais influencia é a Linha de Instabilidade (LI).

Visualização do funil de enovelamento de proteínas

Pós-graduação em Biofísica Molecular - IBILCE

Controle coordenado de múltiplos dipositivos facts com vistas à estabilidade transitória de SEE

Pós-graduação em Engenharia Elétrica - FEIS

Energy and hydraulic efficiency in conventional water supply systems

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

The feasibility of using wind energy for rural populations lacking electric power in Brazil

In the wake of current global image involving environmental impacts, the use of wind power has had a remarkable growth in recent years as a technique for generating electricity. In fact, it is a source featuring strong dissemination of technology which provides decrease in costs and a greater access to low-income electricity. PROINFA (Incentive Program for Alternative Energy Sources) promotes a greater diffusion of new technologies for power generation, in particular wind-produced. Due to such a scenario on the exploitation of such energy source, current analysis discusses strategies for the development of domestic wind technology and the implications for electricity-lacking rural areas. Analysis shows a similar behavior between rural populations lacking electricity and the amount of potential energy available in the region. It is expected that this assay will contribute towards the establishment of public policies for wind-energy parks on rural farms in the North and Northeast regions of Brazil.

CIRCULATION AND SALT INTRUSION IN THE PIACAGUERA CHANNEL, SANTOS (SP)

Analysis of thermohaline properties and currents sampled at an anchor station in the Piacaguera Channel (Santos Estuary) in the austral winter was made in terms of tidal (neap and spring tidal cycles) and non-tidal conditions, with the objective to characterize the stratification, circulation and salt transport due to the fortnightly tidal modulation. Classical methods of observational data analysis of hourly and nearly synoptic observations and analytical simulations of nearly steady-state salinity and longitudinal velocity profiles were used. During the neap tidal cycle the flood (v<0) and ebb (v>0) velocities varied in the range of -0.20 m/s to 0.30 m/s associated with a small salinity variation from surface to bottom (26.4 psu to 30.7 psu). In the spring tidal cycle the velocities increased and varied in the range of -0.40 m/s to 0.45 m/s, but the salinity stratification remained almost unaltered. The steady-state salinity and velocity profiles simulated with an analytical model presented good agreement (Skill near 1.0), in comparison with the observational profiles. During the transitional fortnightly tidal modulation period there was no changes in the channel classification (type 2a - partially mixed and weakly stratified), because the potential energy rate was to low to enhance the halocline erosion. These results, associated with the high water column vertical stability (RiL > 20) and the low estuarine Richardson number (RiE = 1.6), lead to the conclusions: i) the driving mechanism for the estuary circulation and mixing was mainly balanced by the fresh water discharge and the tidal forcing associated with the baroclinic component of the gradient pressure force; ii) there was no changes in the thermohaline and circulation characteristics due to the forthnigtly tidal modulation; and iii) the nearly steady-state of the vertical salinity and velocity profiles were well simulated with a theoretical classical analytical model.

Photoisomerization for a model protonated Schiff base in solution: Sloped/peaked conical intersection perspective

The topographical character of conical intersections (CIs)-either sloped or peaked-has played a fundamental and important role in the discussion of the efficiency of CIs as photochemical "funnels." Here this perspective is employed in connection with a recent study of a model protonated Schiff base (PSB) cis to trans photoisomerization in solution [Malhado et al., J. Phys. Chem. A 115, 3720 (2011)]. In that study, the calculated reduced photochemical quantum yield for the successful production of trans product versus cis reactant in acetonitrile solvent compared to water was interpreted in terms of a dynamical solvent effect related to the dominance, for the acetonitrile case, of S-1 to S-0 nonadiabatic transitions prior to the reaching the seam of CIs. The solvent influence on the quantum yield is here re-examined in the sloped/peaked CI topographical perspective via conversion of the model's two PSB internal coordinates and a nonequilibrium solvent coordinate into an effective branching space description, which is then used to re-analyze the generalized Langevin equation/surface hopping results. The present study supports the original interpretation and enriches it in terms of topographical detail. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4754505]

A theoretical study of SnF2+, SnCl2+, and SnO2+ and their experimental search

We present a detailed theoretical study of the stability of the gas-phase diatomic dications SnF2+, SnCl2+, and SnO2+ using ab initio computer calculations. The ground states of SnF2+, SnCl2+, and SnO2+ are thermodynamically stable, respectively, with dissociation energies of 0.45, 0.30, and 0.42 eV. Whereas SnF2+ dissociates into Sn2+ + F, the long range behaviour of the potential energy curves of SnCl2+ and SnO2+ is repulsive and wide barrier heights due to avoided crossing act as a kind of effective dissociation energy. Their equilibrium internuclear distances are 4.855, 5.201, and 4.852 a(0), respectively. The double ionisation energies (T-e) to form SnF2+, SnCl2+, and SnO2+ from their respective neutral parents are 25.87, 23.71, and 25.97 eV. We combine our theoretical work with the experimental results of a search for these doubly positively charged diatomic molecules in the gas phase. SnO2+ and SnF2+ have been observed for prolonged oxygen (O-16(-)) ion beam sputtering of a tin metal foil and of tin (II) fluoride (SnF2) powder, respectively, for ion flight times of about 10(-5) s through a magnetic-sector mass spectrometer. In addition, SnCl2+ has been detected for O-16(-) ion surface bombardment of stannous (tin (II)) chloride (SnCl2) powder. To our knowledge, SnF2+ is a novel gas-phase molecule, whereas SnCl2+ had been detected previously by electron-impact ionization mass spectrometry, and SnO2+ had been observed before by spark source mass spectrometry as well as by atom probe mass spectrometry. We are not aware of any previous theoretical studies of these molecular systems. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4758475]

Circulation and salt intrusion in the Piaçaguera Channel, Santos (SP)

Analysis of thermohaline properties and currents sampled at an anchor station in the Piaçaguera Channel (Santos Estuary) in the austral winter was made in terms of tidal (neap and spring tidal cycles) and non-tidal conditions, with the objective to characterize the stratification, circulation and salt transport due to the fortnightly tidal modulation. Classical methods of observational data analysis of hourly and nearly synoptic observations and analytical simulations of nearly steady-state salinity and longitudinal velocity profiles were used. During the neap tidal cycle the flood (v<0) and ebb (v>0) velocities varied in the range of -0.20 m/s to 0.30 m/s associated with a small salinity variation from surface to bottom (26.4 psu to 30.7 psu). In the spring tidal cycle the velocities increased and varied in the range of -0.40 m/s to 0.45 m/s, but the salinity stratification remained almost unaltered. The steady-state salinity and velocity profiles simulated with an analytical model presented good agreement (Skill near 1.0), in comparison with the observational profiles. During the transitional fortnightly tidal modulation period there was no changes in the channel classification (type 2a - partially mixed and weakly stratified), because the potential energy rate was to low to enhance the halocline erosion. These results, associated with the high water column vertical stability (RiL >20) and the low estuarine Richardson number (RiE=1.6), lead to the conclusions: i) the driving mechanism for the estuary circulation and mixing was mainly balanced by the fresh water discharge and the tidal forcing associated with the baroclinic component of the gradient pressure force; ii) there was no changes in the thermohaline and circulation characteristics due to the forthnigtly tidal modulation; and iii) the nearly steady-state of the vertical salinity and velocity profiles were well simulated with a theoretical classical analytical model.

Dissociative electron attachment to chloromethane.

A low energy electron may attach to a molecule, forming a metastable resonance, which may dissociate into a stable anion and a neutral radical. Chloromethane has been a good target for dissociative electron attachment studies, since it is a small molecule with a clear dissociative ‘sigma*’ shape resonance. We present potential energy curves for CH3Cl and its anion, as a function of the C-Cl distance. Due to the resonant nature of the anion, a correct description requires a treatment based on scattering calculations. In order to compute elastic cross sections and phase shifts we employed the Schwinger multichannel method, implemented with pseudopotentials of Bachelet, Hamann and Schlüter, at the static-exchange plus polarization approximation. At the equilibrium geometry, the resonance was found arround 3.3 eV, in accordance to experience. The incoming electron is captured by a ‘sigma*’ orbital located at the C-Cl bond, which will relax in the presence of this extra electron. We took this bond as the reaction coordinate, and performed several scattering calculations for a series of nuclear conformations. The phase shift obtained in each calculation was fitted by a two component function, consisting in the usual Breit-Wigner profile, which captures the resonant character, and a second order polynomial in the wave number, which accounts for the background contribution. That way, we obtained position and width of the resonance, which allowed us to build the potential energy curve. For larger distances, the anion becomes stable and usual electronic structure calculations suffice. Furthermore, the existence of a dipole-bound anion state is revealed when we employed a set of very diffuse functions. The knowledge on the behaviour of the neutral and anionic electronic states helps us in elucidating how the dissociation takes place.

Experimental investigation into the effect of stress on dissolution and growth of very soluble brittle salts in aqueous solution

Das Studium der Auflösungs- und Wachstumsprozesse an Feststoff-Flüssigkeits-Grenzflächen unter nicht-hydrostatischen Beanspruchungen ist wesentlich für das Verständnis von Defor-mationsprozessen, die in der Erde ablaufen. Unter diesen genannten Prozessen gehört die Drucklösung zu den wichtigsten duktilen Deformationsprozessen, von der Diagenese bishin zur niedrig- bis mittelgradigen metamorphen Bedingungen. Bisher ist allerdings wenig darüber bekannt, welche mechanischen, physikalischen oder chemischen Potentialenergie-Gradienten die Drucklösung steuern. I.a. wird angenommen, daß die Drucklösung durch Un-terschiede kristallplastischer Verformungsenergien oder aber durch Unterschiede der Normal-beanspruchung an Korngrenzen gesteuert wird. Unterschiede der elastischen Verformungs-energien werden dabei allerdings als zu gering erachtet, um einen signifikanten Beitrag zu leisten. Aus diesem Grund werden sie als mögliche treibende Kräfte für die Drucklösung vernachlässigt. Andererseits haben neue experimentelle und theoretische Untersuchungen gezeigt, daß die elastische Verformung in der Tat einen starken Einfluß auf Lösungs- und Wachstumsmechanismen von Kristallen in einer Lösung haben kann. Da die in der Erdkruste vorherrschenden Deformationsmechanismen überwiegend im elastischen Verformungsbereich der Gesteine ablaufen, ist es sehr wichtig, das Verständnis für die Effekte, die die elastische Verformung verursacht, zu erweitern, und ihre Rolle während der Deformation durch Drucklösung zu definieren. Die vorliegende Arbeit beschäftigt sich mit Experimenten, bei denen der Effekt der mechanisch kompressiven Beanspruchung auf Lösungs- und Wachstumsprozesse von Einzelkristallen unterschiedlicher, sehr gut löslicher, elastisch/spröder Salze untersucht wurde. Diese Salze wurden als Analoga gesteinsbildender Minerale wie Quarz und Calcit ausgewählt. Der Einfluß von Stress auf die Ausbildung der Oberflächenmikrostrukturen in einer untersättigten Lösung wurde an Kaliumalaun untersucht.Lösungsrillen (20 – 40 µm breit, 10 – 40 µm tief und 20 – 80 µm Abstand) entwickelten sich in den Bereichen, in denen die Beanspruchung im Kristall am größten war. Sie verschwanden wieder, sobald der Kristall entlastet wurde. Diese Rillen entwickelten sich parallel zu niedrig indizierten kristallographischen Richtungen und sub-perpendikular zu den Trajektorien, die der maximalen, lokalen kompressiven Beanspruchung entsprachen. Die Größe der Lösungsrillen hing von der lokalen Oberflächenbeanspruchung, der Oberflächenenergie und dem Untersättigungsgrad der wässrigen Lösung ab. Die mikrostrukturelle Entwicklung der Kristalloberflächen stimmte gut mit den theoretischen Vorhersagen überein, die auf den Modellen von Heidug & Leroy (1994) und Leroy & Heidug (1994) basieren. Der Einfluß der Beanspruchung auf die Auflösungsrate wurde an Natriumchlorat-Einzelkristallen untersucht. Dabei wurde herausgefunden, daß sich gestresste Kristalle schneller lösen als Kristalle, auf die keine Beanspruchung einwirkt. Der experimentell beobachtete Anstieg der Auflösungsrate der gestressten Kristalle war ein bis zwei Größenordnungen höher als theoretisch erwartet. Die Auflösungsrate stieg linear mit dem Stress an, und der Anstieg war um so größer, je stärker die Lösung untersättigt war. Außerdem wurde der Effekt der Bean-spruchung auf das Kristallwachstum an Kaliumalaun- und Kaliumdihydrogenphosphat-Ein-zelkristallen untersucht. Die Wachstumsrate der Flächen {100} und {110} von Kalium-alaun war bei Beanspruchung stark reduziert. Für all diese Ergebnisse spielte die Oberflächenrauhigkeit der Kristalle eine Schlüsselrolle, indem sie eine nicht-homogene Stressverteilung auf der Kristalloberfläche verursachte. Die Resultate zeigen, daß die elastische Verformung eine signifikante Rolle während der Drucklösung spielen kann, und eine signifikante Deformation in der oberen Kruste verursachen kann, bei Beanspruchungen, die geringer sind, als gemeinhin angenommen wird. Somit folgt, daß die elastische Bean-spruchung berücksichtigt werden muß, wenn mikrophysikalische Deformationsmodelle entwickelt werden sollen.