Desenvolupament, implementació i aplicació de noves metodologies per a l'estudi de la reactivitat química i de les propietats òptiques no lineals

El coneixement de la superfície d'energia potencial (PES) ha estat essencial en el món de la química teòrica per tal de discutir tant la reactivitat química com l'estructura i l'espectroscòpia molecular. En el camp de la reactivitat química es hem proposat continuar amb el desenvolupament de nova metodologia dins el marc de la teoria del funcional de la densitat conceptual. En particular aquesta tesis es centrarà en els següents punts: a) El nombre i la naturalesa dels seus punts estacionaris del PES poden sofrir canvis radicals modificant el nivell de càlcul utilitzats, de tal manera que per estar segurs de la seva naturalesa cal anar a nivells de càlcul molt elevats. La duresa és una mesura de la resistència d'un sistema químic a canviar la seva configuració electrònica, i segons el principi de màxima duresa on hi hagi un mínim o un màxim d'energia trobarem un màxim o un mínim de duresa, respectivament. A l'escollir tot un conjunt de reaccions problemàtiques des del punt de vista de presència de punts estacionaris erronis, hem observat que els perfils de duresa són més independents de la base i del mètode utilitzats, a més a més sempre presenten el perfil correcte. b) Hem desenvolupat noves expressions basades en les integracions dels kernels de duresa per tal de determinar la duresa global d'una molècula de manera més precisa que la utilitzada habitualment que està basada en el càlcul numèric de la derivada segona de l'energia respecte al número d'electrons. c) Hem estudiat la validesa del principis de màxima duresa i de mínima polaritzabiliat en les vibracions asimètriques en sistemes aromàtics. Hem trobat que per aquests sistemes alguns modes vibracionals incompleixen aquests principis i hem analitzat la relació d'aquest l'incompliment amb l'efecte de l'acoblament pseudo-Jahn-Teller. A més a més, hem postulat tot un conjunt de regles molt senzilles que ens permetien deduir si una molècula compliria o no aquests principis sense la realització de cap càlcul previ. Tota aquesta informació ha estat essencial per poder determinar exactament quines són les causes del compliment o l'incompliment del MHP i MPP. d) Finalment, hem realitzat una expansió de l'energia funcional en termes del nombre d'electrons i de les coordenades normals dintre del conjunt canònic. En la comparació d'aquesta expansió amb l'expansió de l'energia del nombre d'electrons i del potencial extern hem pogut recuperar d'una altra forma diferent tot un conjunt de relacions ja conegudes entre alguns coneguts descriptors de reactivitat del funcional de la densitat i en poden establir tot un conjunt de noves relacions i de nous descriptors. Dins del marc de les propietats moleculars es proposa generalitzar i millorar la metodologia pel càlcul de la contribució vibracional (Pvib) a les propietats òptiques no lineals (NLO). Tot i que la Pvib no s'ha tingut en compte en la majoria dels estudis teòrics publicats de les propietats NLO, recentment s'ha comprovat que la Pvib de diversos polímers orgànics amb altes propietats òptiques no lineals és fins i tot més gran que la contribució electrònica. Per tant, tenir en compte la Pvib és essencial en el disseny dels nous materials òptics no lineals utilitzats en el camp de la informàtica, les telecomunicacions i la tecnologia làser. Les principals línies d'aquesta tesis sobre aquest tema són: a) Hem calculat per primera vegada els termes d'alt ordre de Pvib de diversos polímers orgànics amb l'objectiu d'avaluar la seva importància i la convergència de les sèries de Taylor que defineixen aquestes contribucions vibracionals. b) Hem avaluat les contribucions electròniques i vibracionals per una sèrie de molècules orgàniques representatives utilitzant diferents metodologies, per tal de poder de determinar quina és la manera més senzilla per poder calcular les propietats NLO amb una precisió semiquantitativa.

The changing structure of diets in the European Union in relation to healthy eating guidelines

Objective: Our objective in this paper is to assess diets in the European Union (EU) in relation to the recommendations of the recent World Health Organization/Food and Agriculture Organization expert consultation and to show how diets have changed between 1961 and 2001. Data and methods: Computations make use of FAOSTAT data on food availability at country level linked to a food composition database to convert foods to nutrients. We further explore the growing similarity of diets in the EU by making use of a consumption similarity index. The index provides a single number measure of dietary overlap between countries. Results: The data confirm the excessive consumption by almost all countries of saturated fats, cholesterol and sugars, and the convergence of nutrient intakes across the EU. Whereas in 1961 diets in several European countries were more similar to US diets than to those of other European countries, this is no longer the case; moreover, while EU diets have become more homogeneous, the EU as a whole and the USA have become less similar over time. Conclusions: Although the dominant cause of greater similarity in EU diets over the period studied is increased intakes in Mediterranean countries of saturated fats, cholesterol and sugar, also important are reductions in saturated fat and sugar in some Northern European countries. This suggests that healthy eating messages are finally having an impact on diets; a distinctly European diet may also be emerging.

Symmetric Push-Sum Protocol for decentralised aggregation

Gossip (or Epidemic) protocols have emerged as a communication and computation paradigm for large-scale networked systems. These protocols are based on randomised communication, which provides probabilistic guarantees on convergence speed and accuracy. They also provide robustness, scalability, computational and communication efficiency and high stability under disruption. This work presents a novel Gossip protocol named Symmetric Push-Sum Protocol for the computation of global aggregates (e.g., average) in decentralised and asynchronous systems. The proposed approach combines the simplicity of the push-based approach and the efficiency of the push-pull schemes. The push-pull schemes cannot be directly employed in asynchronous systems as they require synchronous paired communication operations to guarantee their accuracy. Although push schemes guarantee accuracy even with asynchronous communication, they suffer from a slower and unstable convergence. Symmetric Push- Sum Protocol does not require synchronous communication and achieves a convergence speed similar to the push-pull schemes, while keeping the accuracy stability of the push scheme. In the experimental analysis, we focus on computing the global average as an important class of node aggregation problems. The results have confirmed that the proposed method inherits the advantages of both other schemes and outperforms well-known state of the art protocols for decentralized Gossip-based aggregation.

A search for invariant relative satellite motion

This report presents the canonical Hamiltonian formulation of relative satellite motion. The unperturbed Hamiltonian model is shown to be equivalent to the well known Hill-Clohessy-Wilshire (HCW) linear formulation. The in°uence of perturbations of the nonlinear Gravitational potential and the oblateness of the Earth; J2 perturbations are also modelled within the Hamiltonian formulation. The modelling incorporates eccentricity of the reference orbit. The corresponding Hamiltonian vector ¯elds are computed and implemented in Simulink. A numerical method is presented aimed at locating periodic or quasi-periodic relative satellite motion. The numerical method outlined in this paper is applied to the Hamiltonian system. Although the orbits considered here are weakly unstable at best, in the case of eccentricity only, the method ¯nds exact periodic orbits. When other perturbations such as nonlinear gravitational terms are added, drift is signicantly reduced and in the case of the J2 perturbation with and without the nonlinear gravitational potential term, bounded quasi-periodic solutions are found. Advantages of using Newton's method to search for periodic or quasi-periodic relative satellite motion include simplicity of implementation, repeatability of solutions due to its non-random nature, and fast convergence. Given that the use of bounded or drifting trajectories as control references carries practical di±culties over long-term missions, Principal Component Analysis (PCA) is applied to the quasi-periodic or slowly drifting trajectories to help provide a closed reference trajectory for the implementation of closed loop control. In order to evaluate the e®ect of the quality of the model used to generate the periodic reference trajectory, a study involving closed loop control of a simulated master/follower formation was performed. 2 The results of the closed loop control study indicate that the quality of the model employed for generating the reference trajectory used for control purposes has an important in°uence on the resulting amount of fuel required to track the reference trajectory. The model used to generate LQR controller gains also has an e®ect on the e±ciency of the controller.

Plane wave approximation in linear elasticity

We consider the approximation of solutions of the time-harmonic linear elastic wave equation by linear combinations of plane waves. We prove algebraic orders of convergence both with respect to the dimension of the approximating space and to the diameter of the domain. The error is measured in Sobolev norms and the constants in the estimates explicitly depend on the problem wavenumber. The obtained estimates can be used in the h- and p-convergence analysis of wave-based finite element schemes.

The Aqua-Planet Experiment (APE): CONTROL SST Simulation

Climate simulations by 16 atmospheric general circulation models (AGCMs) are compared on an aqua-planet, a water-covered Earth with prescribed sea surface temperature varying only in latitude. The idealised configuration is designed to expose differences in the circulation simulated by different models. Basic features of the aqua-planet climate are characterised by comparison with Earth. The models display a wide range of behaviour. The balanced component of the tropospheric mean flow, and mid-latitude eddy covariances subject to budget constraints, vary relatively little among the models. In contrast, differences in damping in the dynamical core strongly influence transient eddy amplitudes. Historical uncertainty in modelled lower stratospheric temperatures persists in APE. Aspects of the circulation generated more directly by interactions between the resolved fluid dynamics and parameterized moist processes vary greatly. The tropical Hadley circulation forms either a single or double inter-tropical convergence zone (ITCZ) at the equator, with large variations in mean precipitation. The equatorial wave spectrum shows a wide range of precipitation intensity and propagation characteristics. Kelvin mode-like eastward propagation with remarkably constant phase speed dominates in most models. Westward propagation, less dispersive than the equatorial Rossby modes, dominates in a few models or occurs within an eastward propagating envelope in others. The mean structure of the ITCZ is related to precipitation variability, consistent with previous studies. The aqua-planet global energy balance is unknown but the models produce a surprisingly large range of top of atmosphere global net flux, dominated by differences in shortwave reflection by clouds. A number of newly developed models, not optimised for Earth climate, contribute to this. Possible reasons for differences in the optimised models are discussed. The aqua-planet configuration is intended as one component of an experimental hierarchy used to evaluate AGCMs. This comparison does suggest that the range of model behaviour could be better understood and reduced in conjunction with Earth climate simulations. Controlled experimentation is required to explore individual model behaviour and investigate convergence of the aqua-planet climate with increasing resolution.

Convergent evolution of floral signals underlies the success of Neotropical orchids

The great majority of plant species in the tropics require animals to achieve pollination, but the exact role of floral signals in attraction of animal pollinators is often debated. Many plants provide a floral reward to attract a guild of pollinators, and it has been proposed that floral signals of non-rewarding species may converge on those of rewarding species to exploit the relationship of the latter with their pollinators. In the orchid family (Orchidaceae), pollination is almost universally animal-mediated, but a third of species provide no floral reward, which suggests that deceptive pollination mechanisms are prevalent. Here, we examine floral colour and shape convergence in Neotropical plant communities, focusing on certain food-deceptive Oncidiinae orchids (e.g. Trichocentrum ascendens and Oncidium nebulosum) and rewarding species of Malpighiaceae. We show that the species from these two distantly related families are often more similar in floral colour and shape than expected by chance and propose that a system of multifarious floral mimicry—a form of Batesian mimicry that involves multiple models and is more complex than a simple one model–one mimic system—operates in these orchids. The same mimetic pollination system has evolved at least 14 times within the species-rich Oncidiinae throughout the Neotropics. These results help explain the extraordinary diversification of Neotropical orchids and highlight the complexity of plant–animal interactions.

Anisotropic model for granulated sea ice dynamics

A continuum model describing sea ice as a layer of granulated thick ice, consisting of many rigid, brittle floes, intersected by long and narrow regions of thinner ice, known as leads, is developed. We consider the evolution of mesoscale leads, formed under extension, whose lengths span many floes, so that the surrounding ice is treated as a granular plastic. The leads are sufficiently small with respect to basin scales of sea ice deformation that they may be modelled using a continuum approach. The model includes evolution equations for the orientational distribution of leads, their thickness and width expressed through second-rank tensors and terms requiring closures. The closing assumptions are constructed for the case of negligibly small lead ice thickness and the canonical deformation types of pure and simple shear, pure divergence and pure convergence. We present a new continuum-scale sea ice rheology that depends upon the isotropic, material rheology of sea ice, the orientational distribution of lead properties and the thick ice thickness. A new model of lead and thick ice interaction is presented that successfully describes a number of effects: (i) because of its brittle nature, thick ice does not thin under extension and (ii) the consideration of the thick sea ice as a granular material determines finite lead opening under pure shear, when granular dilation is unimportant.

How do atmospheric rivers form?

Identifying the source of atmospheric rivers: Are they rivers of moisture exported from the subtropics or footprints left behind by poleward travelling storms? The term atmospheric river is used to describe corridors of strong water vapor transport in the troposphere. Filaments of enhanced water vapor, commonly observed in satellite imagery extending from the subtropics to the extratropics, are routinely used as a proxy for identifying these regions of strong water vapor transport. The precipitation associated with these filaments of enhanced water vapor can lead to high impact flooding events. However, there remains some debate as to how these filaments form. In this paper we analyse the transport of water vapor within a climatology of wintertime North Atlantic extratropical cyclones. Results show that atmospheric rivers are formed by the cold front which sweeps up water vapor in the warm sector as it catches up with the warm front. This causes a narrow band of high water vapor content to form ahead of the cold front at the base of the warm conveyor belt airflow. Thus, water vapor in the cyclone's warm sector, and not long-distance transport of water vapor from the subtropics, is responsible for the generation of filaments of high water vapor content. A continuous cycle of evaporation and moisture convergence within the cyclone replenishes water vapor lost via precipitation. Thus, rather than representing a direct and continuous feed of moist air from the subtropics into the centre of a cyclone (as suggested by the term atmospheric river), these filaments are, in-fact, the result of water vapor exported from the cyclone and thus they represent the footprints left behind as cyclones travel polewards from subtropics.

Discontinuous Galerkin methods for the p-biharmonic equation from a discrete variational perspective

We study discontinuous Galerkin approximations of the p-biharmonic equation for p∈(1,∞) from a variational perspective. We propose a discrete variational formulation of the problem based on an appropriate definition of a finite element Hessian and study convergence of the method (without rates) using a semicontinuity argument. We also present numerical experiments aimed at testing the robustness of the method.

Outer Trust-Region Method for Constrained Optimization

Given an algorithm A for solving some mathematical problem based on the iterative solution of simpler subproblems, an outer trust-region (OTR) modification of A is the result of adding a trust-region constraint to each subproblem. The trust-region size is adaptively updated according to the behavior of crucial variables. The new subproblems should not be more complex than the original ones, and the convergence properties of the OTR algorithm should be the same as those of Algorithm A. In the present work, the OTR approach is exploited in connection with the ""greediness phenomenon"" of nonlinear programming. Convergence results for an OTR version of an augmented Lagrangian method for nonconvex constrained optimization are proved, and numerical experiments are presented.

Using immune genetic algorithm to optimize the reactive power

A novel algorithm, immune genetic algorithm (IGA) is proposed for reactive power optimization of power system. While retaining excellent characteristics of genetic algorithm (GA), through imitating the biological immune system, the algorithm evaluates and selects the optimal solutions by the affinities between antigens and antibodies. With the regulation of the activating and suppressing of antibodies, IGA can achieve the dynamic balance between individual diversity and population convergence, and avoid getting into the local optimal solution. The proposed IGA is applied to the IEEE 30-bus system, and the results show that it is superior to the GA with good population convergence and fast computing speed.

The Australian screen producer in transition

The role of the screen producer is ramifying. Not only are there numerous producer categories, but the screen producer function is also found on a continuum across film, television, advertising, corporate video and the burgeoning digital media sector. In recent years, fundamental changes to distribution and consumption practices and technologies should have had a correlate impact on screen production practices and on the role of existing screen producers. At the same time, new and recent producers are learning and practising their craft in af ield that has already been transformed by digitization and media convergence. Our analysis of the work, experience and outlook of screen producers in this chapter is based on data collected in the Australian Screen Producer Survey (ASPS), a nationwide survey conducted by the ARC Centre of Excellence for Creative Industries and Innovation, the media marketing firm Bergent Research and the Centre for Screen Business at the Australian Film, Television and Radio School (AFTRS) in 2008/2009 and 2011.2 We analyse the results to better understand the practice of screen production in a period of industry transition, and to recognize the persistence of established production cultures that serve to distinguish different industry sectors.

Are regional incomes in Malaysia converging?

This paper analyses patterns in regional inequality within and between Malaysia's 14 states, drawing upon estimates of Kuznets/Williamson curves, σ- and β-convergence and spatial spillovers. The path of regional inequality contradicts Kuznets predictions. Regional inequality initially fell but has subsequently risen with further economic development. While Malaysian governments have been successful at reducing poverty, they have been unable to curtail regional inequality in the long run. © 2014 The Author(s).

A novel Physarum-Based ant colony system for solving the real-world traveling salesman problem

The solutions to Traveling Salesman Problem can be widely applied in many real-world problems. Ant colony optimization algorithms can provide an approximate solution to a Traveling Salesman Problem. However, most ant colony optimization algorithms suffer premature convergence and low convergence rate. With these observations in mind, a novel ant colony system is proposed, which employs the unique feature of critical tubes reserved in the Physaurm-inspired mathematical model. A series of experiments are conducted, which are consolidated by two realworld Traveling Salesman Problems. The experimental results show that the proposed new ant colony system outperforms classical ant colony system, genetic algorithm, and particle swarm optimization algorithm in efficiency and robustness.