Materials properties from electron density distributions: Molecular magnetism and linear optical properties

The general goal of this thesis is correlating observable properties of organic and metal-organic materials with their ground-state electron density distribution. In a long-term view, we expect to develop empirical or semi-empirical approaches to predict materials properties from the electron density of their building blocks, thus allowing to rationally engineering molecular materials from their constituent subunits, such as their functional groups. In particular, we have focused on linear optical properties of naturally occurring amino acids and their organic and metal-organic derivatives, and on magnetic properties of metal-organic frameworks. For analysing the optical properties and the magnetic behaviour of the molecular or sub-molecular building blocks in materials, we mostly used the more traditional QTAIM partitioning scheme of the molecular or crystalline electron densities, however, we have also investigated a new approach, namely, X-ray Constrained Extremely Localized Molecular Orbitals (XC-ELMO), that can be used in future to extracted the electron densities of crystal subunits. With the purpose of rationally engineering linear optical materials, we have calculated atomic and functional group polarizabilities of amino acid molecules, their hydrogen-bonded aggregates and their metal-organic frameworks. This has enabled the identification of the most efficient functional groups, able to build-up larger electric susceptibilities in crystals, as well as the quantification of the role played by intermolecular interactions and coordinative bonds on modifying the polarizability of the isolated building blocks. Furthermore, we analysed the dependence of the polarizabilities on the one-electron basis set and the many-electron Hamiltonian. This is useful for selecting the most efficient level of theory to estimate susceptibilities of molecular-based materials. With the purpose of rationally design molecular magnetic materials, we have investigated the electron density distributions and the magnetism of two copper(II) pyrazine nitrate metal-organic polymers. High-resolution X-ray diffraction and DFT calculations were used to characterize the magnetic exchange pathways and to establish relationships between the electron densities and the exchange-coupling constants. Moreover, molecular orbital and spin-density analyses were employed to understand the role of different magnetic exchange mechanisms in determining the bulk magnetic behaviour of these materials. As anticipated, we have finally investigated a modified version of the X-ray constrained wavefunction technique, XC-ELMOs, that is not only a useful tool for determination and analysis of experimental electron densities, but also enables one to derive transferable molecular orbitals strictly localized on atoms, bonds or functional groups. In future, we expect to use XC-ELMOs to predict materials properties of large systems, currently challenging to calculate from first-principles, such as macromolecules or polymers. Here, we point out advantages, needs and pitfalls of the technique. This work fulfils, at least partially, the prerequisites to understand materials properties of organic and metal-organic materials from the perspective of the electron density distribution of their building blocks. Empirical or semi-empirical evaluation of optical or magnetic properties from a preconceived assembling of building blocks could be extremely important for rationally design new materials, a field where accurate but expensive first-principles calculations are generally not used. This research could impact the community in the fields of crystal engineering, supramolecular chemistry and, of course, electron density analysis.

PSO and neural networks: Optimal combination to solve non linear complex problems

Swarm colonies reproduce social habits. Working together in a group to reach a predefined goal is a social behaviour occurring in nature. Linear optimization problems have been approached by different techniques based on natural models. In particular, Particles Swarm optimization is a meta-heuristic search technique that has proven to be effective when dealing with complex optimization problems. This paper presents and develops a new method based on different penalties strategies to solve complex problems. It focuses on the training process of the neural networks, the constraints and the election of the parameters to ensure successful results and to avoid the most common obstacles when searching optimal solutions.

Simplified computational method for non-linear seismic analysis of bridges

After the experience gained during the past years it seems clear that nonlinear analysis of bridges are very important to compute ductility demands and to localize potential hinges. This is specially true for irregular bridges in which it is not clear weather or not it is possible to use a linear computation followed by a correction using a behaviour factor. To simplify the numerical effort several approximate methods have been proposed. Among them, the so-called Dynamic Plastic Hinge Method in which an evolutionary shape function is used to reduce the structure to a single degree of freedom system seems to mantein a good balance between accuracy and simplicity. This paper presents results obtained in a parametric study conducted under the auspicies of PREC-8 european research program.

UWB Monocycle Generator based on the non-linear effects of an SOA-integrated structure

In this letter, we propose and experimentally demonstrate a novel and single structure to generate ultra-wideband (UWB) pulses by means of the cross-phase modulation present in a semiconductor optical amplifier unified structure. The key components of this system is an integrated Mach-Zehnder interferometer with two semiconductor optical amplifiers and an optical processing unit. The fusion of these two components permits the generation and customization of UWB monocycle pulses. The polarity of the output pulses is easily modified through the single selection of a specific input port. Moreover, the capacity of transmitting several data sequences is demonstrated and the potentiality to adapt the system to different modulation formats is analyzed.

Real-Time Dynamic PGD Calculation of Non-Linear Soil Behavior

El estudio sísmico en los últimos 50 años y el análisis del comportamiento dinámico del suelo revelan que el comportamiento del suelo es altamente no lineal e histéretico incluso para pequeñas deformaciones. El comportamiento no lineal del suelo durante un evento sísmico tiene un papel predominante en el análisis de la respuesta de sitio. Los análisis unidimensionales de la respuesta sísmica del suelo son a menudo realizados utilizando procedimientos lineales equivalentes, que requieren generalmente pocos parámetros conocidos. Los análisis de respuesta de sitio no lineal tienen el potencial para simular con mayor precisión el comportamiento del suelo, pero su aplicación en la práctica se ha visto limitada debido a la selección de parámetros poco documentadas y poco claras, así como una inadecuada documentación de los beneficios del modelado no lineal en relación al modelado lineal equivalente. En el análisis del suelo, el comportamiento del suelo es aproximado como un sólido Kelvin-Voigt con un módulo de corte elástico y amortiguamiento viscoso. En el análisis lineal y no lineal del suelo se están considerando geometrías y modelos reológicos más complejos. El primero está siendo dirigido por considerar parametrizaciones más ricas del comportamiento linealizado y el segundo mediante el uso de multi-modo de los elementos de resorte-amortiguador con un eventual amortiguador fraccional. El uso del cálculo fraccional está motivado en gran parte por el hecho de que se requieren menos parámetros para lograr la aproximación exacta a los datos experimentales. Basándose en el modelo de Kelvin-Voigt, la viscoelasticidad es revisada desde su formulación más estándar a algunas descripciones más avanzada que implica la amortiguación dependiente de la frecuencia (o viscosidad), analizando los efectos de considerar derivados fraccionarios para representar esas contribuciones viscosas. Vamos a demostrar que tal elección se traduce en modelos más ricos que pueden adaptarse a diferentes limitaciones relacionadas con la potencia disipada, amplitud de la respuesta y el ángulo de fase. Por otra parte, el uso de derivados fraccionarios permite acomodar en paralelo, dentro de un análogo de Kelvin-Voigt generalizado, muchos amortiguadores que contribuyen a aumentar la flexibilidad del modelado para la descripción de los resultados experimentales. Obviamente estos modelos ricos implican muchos parámetros, los asociados con el comportamiento y los relacionados con los derivados fraccionarios. El análisis paramétrico de estos modelos requiere técnicas numéricas eficientemente capaces de simular comportamientos complejos. El método de la Descomposición Propia Generalizada (PGD) es el candidato perfecto para la construcción de este tipo de soluciones paramétricas. Podemos calcular off-line la solución paramétrica para el depósito de suelo, para todos los parámetros del modelo, tan pronto como tales soluciones paramétricas están disponibles, el problema puede ser resuelto en tiempo real, porque no se necesita ningún nuevo cálculo, el solucionador sólo necesita particularizar on-line la solución paramétrica calculada off-line, que aliviará significativamente el procedimiento de solución. En el marco de la PGD, parámetros de los materiales y los diferentes poderes de derivación podrían introducirse como extra-coordenadas en el procedimiento de solución. El cálculo fraccional y el nuevo método de reducción modelo llamado Descomposición Propia Generalizada han sido aplicado en esta tesis tanto al análisis lineal como al análisis no lineal de la respuesta del suelo utilizando un método lineal equivalente. ABSTRACT Studies of earthquakes over the last 50 years and the examination of dynamic soil behavior reveal that soil behavior is highly nonlinear and hysteretic even at small strains. Nonlinear behavior of soils during a seismic event has a predominant role in current site response analysis. One-dimensional seismic ground response analysis are often performed using equivalent-linear procedures, which require few, generally well-known parameters. Nonlinear analyses have the potential to more accurately simulate soil behavior, but their implementation in practice has been limited because of poorly documented and unclear parameter selection, as well as inadequate documentation of the benefits of nonlinear modeling relative to equivalent linear modeling. In soil analysis, soil behaviour is approximated as a Kelvin-Voigt solid with a elastic shear modulus and viscous damping. In linear and nonlinear analysis more complex geometries and more complex rheological models are being considered. The first is being addressed by considering richer parametrizations of the linearized behavior and the second by using multi-mode spring-dashpot elements with eventual fractional damping. The use of fractional calculus is motivated in large part by the fact that fewer parameters are required to achieve accurate approximation of experimental data. Based in Kelvin-Voigt model the viscoelastodynamics is revisited from its most standard formulation to some more advanced description involving frequency-dependent damping (or viscosity), analyzing the effects of considering fractional derivatives for representing such viscous contributions. We will prove that such a choice results in richer models that can accommodate different constraints related to the dissipated power, response amplitude and phase angle. Moreover, the use of fractional derivatives allows to accommodate in parallel, within a generalized Kelvin-Voigt analog, many dashpots that contribute to increase the modeling flexibility for describing experimental findings. Obviously these rich models involve many parameters, the ones associated with the behavior and the ones related to the fractional derivatives. The parametric analysis of all these models require efficient numerical techniques able to simulate complex behaviors. The Proper Generalized Decomposition (PGD) is the perfect candidate for producing such kind of parametric solutions. We can compute off-line the parametric solution for the soil deposit, for all parameter of the model, as soon as such parametric solutions are available, the problem can be solved in real time because no new calculation is needed, the solver only needs particularize on-line the parametric solution calculated off-line, which will alleviate significantly the solution procedure. Within the PGD framework material parameters and the different derivation powers could be introduced as extra-coordinates in the solution procedure. Fractional calculus and the new model reduction method called Proper Generalized Decomposition has been applied in this thesis to the linear analysis and nonlinear soil response analysis using a equivalent linear method.

Non-linear photoluminescence from purified aqueous PbS nanocrystals

A simple and effective method for purifying photoluminescent water-soluble surface passivated PbS nanocrystals has been developed. Centrifuging at high speeds removes PbS nanocrystals that exhibit strong red band edge photoluminescence from an original solution containing multiple nanocrystalline species with broad photoluminescence spectra. The ability to purify the PbS nanocrystals allowed two-photon photoluminescence spectroscopy to be performed on water-soluble PbS nanocrystals and be attributed to band edge recombination. (c) 2006 Elsevier B.V. All rights reserved.

Non-Linear oil firm force coefficients for a journal bearing operating under aligned and misaligned conditions

It is well established that hydrodynamic journal bearings are responsible for self-excited vibrations and have the effect of lowering the critical speeds of rotor systems. The forces within the oil film wedge, generated by the vibrating journal, may be represented by displacement and velocity coefficient~ thus allowing the dynamical behaviour of the rotor to be analysed both for stability purposes and for anticipating the response to unbalance. However, information describing these coefficients is sparse, misleading, and very often not applicable to industrial type bearings. Results of a combined analytical and experimental investigation into the hydrodynamic oil film coefficients operating in the laminar region are therefore presented, the analysis being applied to a 120 degree partial journal bearing having a 5.0 in diameter journal and a LID ratio of 1.0. The theoretical analysis shows that for this type of popular bearing, the eight linearized coefficients do not accurately describe the behaviour of the vibrating journal based on the theory of small perturbations, due to them being masked by the presence of nonlinearity. A method is developed using the second order terms of Taylor expansion whereby design charts are provided which predict the twentyeight force coefficients for both aligned, and for varying amounts of journal misalignment. The resulting non-linear equations of motion are solved using a modified Newton-Raphson method whereby the whirl trajectories are obtained, thus providing a physical appreciation of the bearing characteristics under dynamically loaded conditions.

Approaching the non-linear Shannon limit

We review the recent progress of information theory in optical communications, and describe the current experimental results and associated advances in various individual technologies which increase the information capacity. We confirm the widely held belief that the reported capacities are approaching the fundamental limits imposed by signal-to-noise ratio and the distributed non-linearity of conventional optical fibres, resulting in the reduction in the growth rate of communication capacity. We also discuss the techniques which are promising to increase and/or approach the information capacity limit.

Challenges of developing non-linear devices to achieve the linear Shannon limit

To achieve the Shannon Capacity Limit, we need to develop practical, effective and deployable non-linear devices to invert the non-linear effects of the transmission line. In this work, we will summarise the progress we are making to realise these, specifically looking at optical phase conjugation and phase regenerators as methods to improve non-linear tolerances. © 2014 IEEE.

Approaching the non-linear Shannon limit

We review the recent progress of information theory in optical communications, and describe the current experimental results and associated advances in various individual technologies which increase the information capacity. We confirm the widely held belief that the reported capacities are approaching the fundamental limits imposed by signal-to-noise ratio and the distributed non-linearity of conventional optical fibres, resulting in the reduction in the growth rate of communication capacity. We also discuss the techniques which are promising to increase and/or approach the information capacity limit.

Oceans of energy? The non-linear trajectory of the emerging wave energy technology

This paper addresses the construction and structuring of a technological niche – i.e. a protected space where promising but still underperforming technologies are stabilized and articulated with societal needs – and discusses the processes that influence niche development and may enable niche breakout. In theoretical terms the paper is grounded on the multi-level approach to sustainability transitions, and particularly on the niche literature. But it also attempts to address the limitations of this literature in what concerns the spatial dimension of niche development. It is argued that technological niches can transcend the narrow territorial boundaries to which they are often confined, and encompass communities and actions that span several spatial levels, without losing some territorial embeddedness. It is further proposed that these features shape the niche trajectory and, therefore, need to be explicitly considered by the niche theoretical framework. To address this problem the paper builds on and extends the socio-cognitive perspective to technology development, introducing a further dimension – space – which broadens the concept of technological niche and permits to better capture the complexity of niche behaviour. This extended framework is applied to the case of an emerging renewable energy technology – wave energy - which exhibits a particularly slow and non-linear development trajectory. The empirical analysis starts by examining how an “overall niche space” in wave energy was spatially constructed over time. Then it investigates in greater detail the niche development processes that took place in Portugal, a country that was among the pioneers in the field, and whose actors have been, from very early stages, engaged in the activities conducted at various spatial levels. Through this combined analysis, the paper seeks to understand whether and how niche development is shaped by processes taking place at different spatial levels. More specifically it investigates the interplay between territorial and relational elements in niche development, and how these different dynamics influence the performance of the niche processes and impact on the overall niche trajectory. The results confirm the niche multi-spatial dynamics, showing that it is shaped by the interplay between a niche relational space constructed by actors’ actions and interactions on/across levels, and the territorial effects introduced by these actors’ embeddedness in particular geographical and institutional settings. They contribute to a more precise understanding of the processes that can accelerate or slow down the trajectory of a technological niche. In addition, the results shed some light into the niche activities conducted in/originating from a specific territorial setting - Portugal - offering some insights into the behaviour of key actors and its implications for the positioning of the country in the emerging field, which can be relevant for the formulation of strategies and policies for this area.

Stability and convergence of an implicit numerical method for the non-linear fractional reaction-subdiffusion process

In this paper, we consider the following non-linear fractional reaction–subdiffusion process (NFR-SubDP): Formula where f(u, x, t) is a linear function of u, the function g(u, x, t) satisfies the Lipschitz condition and 0Dt1–{gamma} is the Riemann–Liouville time fractional partial derivative of order 1 – {gamma}. We propose a new computationally efficient numerical technique to simulate the process. Firstly, the NFR-SubDP is decoupled, which is equivalent to solving a non-linear fractional reaction–subdiffusion equation (NFR-SubDE). Secondly, we propose an implicit numerical method to approximate the NFR-SubDE. Thirdly, the stability and convergence of the method are discussed using a new energy method. Finally, some numerical examples are presented to show the application of the present technique. This method and supporting theoretical results can also be applied to fractional integrodifferential equations.