Determination of vibrational polarizabilities and hyperpolarizabilities using field-induced coordinates

An analytical set of field-induced coordinates is defined and is used to show that the vibrational degrees of freedom required to completely describe nuclear relaxation polarizabilities and hyperpolarizabilities is reduced from 3N-6 to a relatively small number. As this number does not depend upon the size of the molecule, the process provides computational advantages. A method is provided to separate anharmonic contributions from harmonic contributions as well as effective mechanical from electrical anharmonicity. The procedures are illustrated by Hartree-Fock calculations, indicating that anharmonicity can be very important

Nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties by means of electrical property expansions: Application to HF, CH4, CF4, and SF6

Electrical property derivative expressions are presented for the nuclear relaxation contribution to static and dynamic (infinite frequency approximation) nonlinear optical properties. For CF4 and SF6, as opposed to HF and CH4, a term that is quadratic in the vibrational anharmonicity (and not previously evaluated for any molecule) makes an important contribution to the static second vibrational hyperpolarizability of CF4 and SF6. A comparison between calculated and experimental values for the difference between the (anisotropic) Kerr effect and electric field induced second-harmonic generation shows that, at the Hartree-Fock level, the nuclear relaxation/infinite frequency approximation gives the correct trend (in the series CH4, CF4, SF6) but is of the order of 50% too small

Variational calculation of static and dynamic vibrational nonlinear optical properties

The vibrational configuration interaction method used to obtain static vibrational (hyper)polarizabilities is extended to dynamic nonlinear optical properties in the infinite optical frequency approximation. Illustrative calculations are carried out on H2 O and N H3. The former molecule is weakly anharmonic while the latter contains a strongly anharmonic umbrella mode. The effect on vibrational (hyper)polarizabilities due to various truncations of the potential energy and property surfaces involved in the calculation are examined

Calculation of Franck-Condon factors including anharmonicity: simulation of the C2 H4+ X̃2B 3u←C2 H4X̃1 Ag band in the photoelectron spectrum of ethylene

Our new simple method for calculating accurate Franck-Condon factors including nondiagonal (i.e., mode-mode) anharmonic coupling is used to simulate the C2H4+X2B 3u←C2H4X̃1 Ag band in the photoelectron spectrum. An improved vibrational basis set truncation algorithm, which permits very efficient computations, is employed. Because the torsional mode is highly anharmonic it is separated from the other modes and treated exactly. All other modes are treated through the second-order perturbation theory. The perturbation-theory corrections are significant and lead to a good agreement with experiment, although the separability assumption for torsion causes the C2 D4 results to be not as good as those for C2 H4. A variational formulation to overcome this circumstance, and deal with large anharmonicities in general, is suggested

The aromatic fluctuation index (FLU): a new aromaticity index based on electron delocalization

In this work, the aromatic fluctuation index (FLU) that describes the fluctuation of electronic charge between adjacent atoms in a given ring is introduced as a new aromaticity measure. This new electronic criterion of aromaticity is based on the fact that aromaticity is related to the cyclic delocalized circulation of π electrons. It is defined not only considering the amount of electron sharing between contiguous atoms, which should be substantial in aromatic molecules, but also taking into account the similarity of electron sharing between adjacent atoms. For a series of rings in 15 planar polycyclic aromatic hydrocarbons, we have found that, in general, FLU is strongly correlated with other widely used indicators of local aromaticity, such as the harmonic-oscillator model of aromaticity, the nucleus independent chemical shift, and the para-delocalization index (PDI). In contrast to PDI, the FLU index can be applied to study the aromaticity of rings with any number of members and it can be used to analyze both the local and global aromatic character of rings and molecules

Are the maximum hardness and minimum polarizability principles always obeyed in nontotally symmetric vibrations?

An overview is given on a study which showed that not only in chemical reactions but also in the favorable case of nontotally symmetric vibrations where the chemical and external potentials keep approximately constant, the generalized maximum hardness principle (GMHP) and generalized minimum polarizability principle (GMPP) may not be obeyed. A method that allows an accurate determination of the nontotally symmetric molecular distortions with more marked GMPP or anti-GMPP character through diagonalization of the polarizability Hessian matrix is introduced

Variational calculation of vibrational linear and nonlinear optical properties

A variational approach for reliably calculating vibrational linear and nonlinear optical properties of molecules with large electrical and/or mechanical anharmonicity is introduced. This approach utilizes a self-consistent solution of the vibrational Schrödinger equation for the complete field-dependent potential-energy surface and, then, adds higher-level vibrational correlation corrections as desired. An initial application is made to static properties for three molecules of widely varying anharmonicity using the lowest-level vibrational correlation treatment (i.e., vibrational Møller-Plesset perturbation theory). Our results indicate when the conventional Bishop-Kirtman perturbation method can be expected to break down and when high-level vibrational correlation methods are likely to be required. Future improvements and extensions are discussed

Basis set and electron correlation effects on initial convergence for vibrational nonlinear optical properties of conjugated organic molecules

The level of ab initio theory which is necessary to compute reliable values for the static and dynamic (hyper)polarizabilities of three medium size π-conjugated organic nonlinear optical (NLO) molecules is investigated. With the employment of field-induced coordinates in combination with a finite field procedure, the calculations were made possible. It is stated that to obtain reasonable values for the various individual contributions to the (hyper)polarizability, it is necessary to include electron correlation. Based on the results, the convergence of the usual perturbation treatment for vibrational anharmonicity was examined

Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene

In this study we report on the electronic and vibrational (hyper)polarizabilities of donor–acceptorsubstituted azobenzene. It is observed that both electronic and vibrational contributions to the electric dipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected density functional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange correlation potentials amend the drawbacks of their conventional counterparts

Efficient topology estimation for large scale optical mapping

Large scale image mosaicing methods are in great demand among scientists who study different aspects of the seabed, and have been fostered by impressive advances in the capabilities of underwater robots in gathering optical data from the seafloor. Cost and weight constraints mean that lowcost Remotely operated vehicles (ROVs) usually have a very limited number of sensors. When a low-cost robot carries out a seafloor survey using a down-looking camera, it usually follows a predetermined trajectory that provides several non time-consecutive overlapping image pairs. Finding these pairs (a process known as topology estimation) is indispensable to obtaining globally consistent mosaics and accurate trajectory estimates, which are necessary for a global view of the surveyed area, especially when optical sensors are the only data source. This thesis presents a set of consistent methods aimed at creating large area image mosaics from optical data obtained during surveys with low-cost underwater vehicles. First, a global alignment method developed within a Feature-based image mosaicing (FIM) framework, where nonlinear minimisation is substituted by two linear steps, is discussed. Then, a simple four-point mosaic rectifying method is proposed to reduce distortions that might occur due to lens distortions, error accumulation and the difficulties of optical imaging in an underwater medium. The topology estimation problem is addressed by means of an augmented state and extended Kalman filter combined framework, aimed at minimising the total number of matching attempts and simultaneously obtaining the best possible trajectory. Potential image pairs are predicted by taking into account the uncertainty in the trajectory. The contribution of matching an image pair is investigated using information theory principles. Lastly, a different solution to the topology estimation problem is proposed in a bundle adjustment framework. Innovative aspects include the use of fast image similarity criterion combined with a Minimum spanning tree (MST) solution, to obtain a tentative topology. This topology is improved by attempting image matching with the pairs for which there is the most overlap evidence. Unlike previous approaches for large-area mosaicing, our framework is able to deal naturally with cases where time-consecutive images cannot be matched successfully, such as completely unordered sets. Finally, the efficiency of the proposed methods is discussed and a comparison made with other state-of-the-art approaches, using a series of challenging datasets in underwater scenarios

Basin-scale hydrodynamics in a Mediterranean reservoir. Implications for the phytoplankton dynamics

Procesos hidrodinámicos determinan, en un alto grado la calidad del agua en embalse, sin embargo dichos procesos han sido tradicionalmente olvidados en la gestión de embalse. En esta tesis se presentan evidencias de los principales procesos hidrodinámicos que ocurren en un embalse Mediterráneo a escala de cuenca a través de campañas experimentales y modelización numérica; y su influencia en la dinámica de poblaciones de fitoplancton. Dichos procesos son principalmente la generación de ondas internas o secas y la intrusión del río. La presencia de viento periódico genera secas forzadas, amplificando los modos cercanos al periodo del viento, de manera que modos verticales altos, considerados como raros en la naturaleza, tienden a dominar en el sistema.

Educação comprometida: vicissitudes de aprendizagem de um grupo de estudantes de uma escola pública na cidade de Campo Maior - Piauí

A educação não pode se caracterizar como sendo algo que estabelece diferenças e prioridades levando-se em consideração as vantagens de grupos de alunos que possuem excelente estrutura familiar, melhores condições de vida e freqüentam escolas particulares, com toda infraestrutura de ensino e dotadas de recursos didáticos avançados em detrimento de uma maioria da população que freqüenta escola pública, recebe ensino de péssima qualidade e ainda tem que trabalhar para sobreviver. Mesmo que sejam questionadas, tais diferenças existem, estão comprovadas e identificadas nos diversos relatórios e dados a respeito da educação e do sistema educacional brasileiro, principalmente os de caráter público. Os reflexos das distorções sociais e das dificuldades de acesso à escola púbica retratam uma realidade cruel acerca de um percentual considerável de alunos que tentam fazer da educação um instrumento de melhoria da qualidade de vida, superação de obstáculos e das dificuldades enfrentadas com a exclusão social, se forem retratados os aspectos sócio-culturais e econômicos. Em um contexto que envolve a realidade educacional dos alunos da Unidade Escolar José Olimpio da Paz, as dificuldades são visíveis, entretanto a superação dos obstáculos e das dificuldades se dá pelo comprometimento dos alunos em participar ativamente do processo ensino-aprendizagem no intuito de melhorarem e aumentarem cada vez mais seus conhecimentos, ao mesmo tempo em que o envolvimento dos professores em promover educação com qualidade, fazendo de sua prática pedagógica um instrumento de luta pelas transformações educacionais, culturais e sociais da comunidade, com foco direcionado para a melhoria da qualidade de vida dos alunos através da educação e da aprendizagem contribui, também e de modo decisivo, para a obtenção de resultados positivos através dos quais todos tenham razões de ganho com o envolvimento compromissado com educação de qualidade.

En nombre de un amor imaginario y los orígenes de la República del Ecuador (Dossier: Bicentenario, rastros y revelaciones de la Independencia)

El autor analiza esta novela histórica de Jorge Velasco Mackenzie, en torno a los orígenes de la nación ecuatoriana, entre la historia y la fábula. Reflexiona sobre el proceso de escribir como una forma de interpelar presupuestos consagrados, valores, símbolos e identidades. Handelsman destaca que el trabajo de la Misión Geodésica Francesa, de 1736, cambió la cosmovisión de la sociedad colonial ecuatoriana, escolástica, por otra de carácter más empírico, pero que el nuevo motor del saber moderno trajo también distorsiones y omisiones de otras verdades (como el que los indígenas perdieran su protagonismo milenario como conocedores de su hábitat). Pone en relieve, igualmente, la imposibilidad de expresar en una segunda lengua lo que se vive en geografías ajenas. Personaje importante es Isabel Godin, quien no puede liberarse del mundo oscuro, complejo y ambivalente que constituye la memoria. En suma, la novela desmitifica la autoridad de las ciencias naturales y físicas, y abre la posibilidad de repensar, reescribir y resignificar la historia del país.

What kind of European Banking Union? Bruegel Policy Contribution [2012/12?]June 25, 2012

This paper discusses the creation of a European Banking Union. First, we discuss questions of design. We highlight seven fundamental choices that decision makers will need to make: Which EU countries should participate in the banking union? To which categories of banks should it apply? Which institution should be tasked with supervision? Which one should deal with resolution? How centralised should the deposit insurance system be? What kind of fiscal backing would be required? What governance framework and political institutions would be needed? In terms of geographical scope, we see the coverage of the banking union of the euro area as necessary and of additional countries as desirable, even though this would entail important additional economic difficulties. The system should ideally cover all banks within the countries included, in order to prevent major competitive and distributional distortions. Supervisory authority should be granted either to both the ECB and a new agency, or to a new agency alone. National supervisors, acting under the authority of the European supervisor, would be tasked with the supervision of smaller banks in accordance with the subsidiarity principle. A European resolution authority should be established, with the possibility of drawing on ESM resources. A fully centralized deposit insurance system would eventually be desirable, but a system of partial reinsurance may also be envisaged at least in a first phase. A banking union would require at least implicit European fiscal backing, with significant political authority and legitimacy. Thus, banking union cannot be considered entirely separately from fiscal union and political union. The most difficult challenge of creating a European banking union lies with the short-term steps towards its eventual implementation. Many banks in the euro area, and especially in the crisis countries, are currently under stress and the move towards banking union almost certainly has significant distributional implications. Yet it is precisely because banks are under such stress that early and concrete action is needed. An overarching principle for such action is to minimize the cost to the tax payers. The first step should be to create a European supervisor that will anchor the development of the future banking union. In parallel, a capability to quickly assess the true capital position of the system’s most important banks should be created, for which we suggest establishing a temporary European Banking Sector Task Force working together with the European supervisor and other authorities. Ideally, problems identified by this process should be resolved by national authorities; in case fiscal capacities would prove insufficient, the European level would take over in the country concerned with some national financial participation, or in an even less likely adverse scenario, in all participating countries at once. This approach would require the passing of emergency legislation in the concerned countries that would give the Task Force the required access to information and, if necessary, further intervention rights. Thus, the principle of fiscal responsibility of respective member states for legacy costs would be preserved to the maximum extent possible, and at the same time, market participants and the public would be reassured that adequate tools are in place to address any eventuality.

Path to eurobonds. Bruegel Working Paper 2012/10, July 2012

This paper discusses proposals for common euro area sovereign securities. Such instruments can potentially serve two functions: in the short-term, stabilize financialmarkets and banks and, in the medium-term, help improve the euro area economic governance framework through enhanced fiscal discipline and risk-sharing. Many questions remain onwhether financial instruments can ever accomplish such goals without bold institutional and political decisions, and,whether, in the absence of such decisions, they can create new distortions. The proposals discussed are also not necessarily competing substitutes; rather, they can be complements to be sequenced along alternative paths that possibly culminate in a fully-fledged Eurobond. The specific path chosen by policymakers should allow for learning and secure the necessary evolution of institutional infrastructures and political safeguards.