Intermolecular and Intramolecular Charge Transfer in Functional Molecular Materials

This thesis is devoted to the investigation of inter and intramolecular charge transfer (CT) in molecular functional materials and specifically organic dyes and CT crystals. An integrated approach encompassing quantum-chemical calculations, semiempirical tools, theoretical models and spectroscopic measurements is applied to understand structure-property relationships governing the low-energy physics of these materials. Four main topics were addressed: 1) Spectral properties of organic dyes. Charge-transfer dyes are constituted by electron donor (D) and electron acceptor (A) units linked through bridge(s) to form molecules with different symmetry and dimensionality. Their low-energy physics is governed by the charge resonance between D and A groups and is effectively described by a family of parametric Hamiltonians known as essential-state models. These models account for few electronic states, corresponding to the main resonance structures of the relevant dye, leading to a simple picture that is completed introducing the coupling of the electronic system to molecular vibrations, treated in a non-adiabatic way, and an effective classical coordinate, describing polar solvation. In this work a specific essential-state model was proposed and parametrized for the dye Brilliant Green. The central issue in this work has been the definition of the diabatic states, a not trivial task for a multi-branched chromophore. In a second effort, we have used essential-state models for the description of the early-stage dynamics of excited states after ultrafast excitation. Crucial to this work is the fully non-adiabatic treatment of the coupled electronic and vibrational motion, allowing for a reliable description of the dynamics of systems showing a multistable, broken-symmetry excited state. 2) Mixed-stack CT salts. Mixed-stack (MS) CT crystals are an interesting class of multifunctional molecular materials, where D and A molecules arrange themselves to form stacks, leading to delocalized electrons in one dimension. The interplay between the intermolecular CT, electrostatic interactions, lattice phonons and molecular vibrations leads to intriguing physical properties that include (photoinduced) phase transitions, multistability, antiferromagnetism, ferroelectricity and potential multiferroicity. The standard microscopic model to describe this family of materials is the Modified Hubbard model accounting for electron-phonon coupling (Peierls coupling), electron-molecular vibrations coupling (Holstein coupling) and electrostatic interactions. We adopt and validate a method, based on DFT calculations on dimeric DA structures, to extract relevant model parameters. The approach offers a powerful tool to shed light on the complex physics of MS-CT salts. 3) Charge transfer in organic radical dipolar dyes. In collaboration with the group of Prof. Jaume Veciana (ICMAB- Barcellona), we have studied spectral properties of a special class of CT dyes with D-bridge-A structure where the acceptor group is a stable radical (of the perchlorotriphenylmethyl, PTM, family), leading to an open-shell CT dyes. These materials are of interest since they associate the electronic and optical properties of CT dyes with magnetic properties from the unpaired electron. The first effort was devoted to the parametrization of the relevant essential-state model. Two strategies were adopted, one based on the calculation of the low-energy spectral properties, the other based on the variation of ground state properties with an applied electric field. 4) The spectral properties of organic nanoparticles based on radical species are investigated in collaboration with Dr. I. Ratera (ICMAB- Barcellona). Intriguing spectroscopic behavior was observed pointing to the presence of excimer states. In an attempt to rationalize these findings, extensive calculations (TD-DFT and ZINDO) were performed. The results for the isolated dyes are validated against experimental spectra in solution. To address intermolecular interactions we studied dimeric structures in the gas phase, but the preliminary results obtained do not support excimer formation.

On the development of advanced techniques for mixed-elastohydrodynamic lubrification modelling of journal and sliding bearing systems.

The present thesis is focused on the development of a thorough mathematical modelling and computational solution framework aimed at the numerical simulation of journal and sliding bearing systems operating under a wide range of lubrication regimes (mixed, elastohydrodynamic and full film lubrication regimes) and working conditions (static, quasi-static and transient conditions). The fluid flow effects have been considered in terms of the Isothermal Generalized Equation of the Mechanics of the Viscous Thin Films (Reynolds equation), along with the massconserving p-Ø Elrod-Adams cavitation model that accordingly ensures the so-called JFO complementary boundary conditions for fluid film rupture. The variation of the lubricant rheological properties due to the viscous-pressure (Barus and Roelands equations), viscous-shear-thinning (Eyring and Carreau-Yasuda equations) and density-pressure (Dowson-Higginson equation) relationships have also been taken into account in the overall modelling. Generic models have been derived for the aforementioned bearing components in order to enable their applications in general multibody dynamic systems (MDS), and by including the effects of angular misalignments, superficial geometric defects (form/waviness deviations, EHL deformations, etc.) and axial motion. The bearing exibility (conformal EHL) has been incorporated by means of FEM model reduction (or condensation) techniques. The macroscopic in fluence of the mixedlubrication phenomena have been included into the modelling by the stochastic Patir and Cheng average ow model and the Greenwood-Williamson/Greenwood-Tripp formulations for rough contacts. Furthermore, a deterministic mixed-lubrication model with inter-asperity cavitation has also been proposed for full-scale simulations in the microscopic (roughness) level. According to the extensive mathematical modelling background established, three significant contributions have been accomplished. Firstly, a general numerical solution for the Reynolds lubrication equation with the mass-conserving p - Ø cavitation model has been developed based on the hybridtype Element-Based Finite Volume Method (EbFVM). This new solution scheme allows solving lubrication problems with complex geometries to be discretized by unstructured grids. The numerical method was validated in agreement with several example cases from the literature, and further used in numerical experiments to explore its exibility in coping with irregular meshes for reducing the number of nodes required in the solution of textured sliding bearings. Secondly, novel robust partitioned techniques, namely: Fixed Point Gauss-Seidel Method (PGMF), Point Gauss-Seidel Method with Aitken Acceleration (PGMA) and Interface Quasi-Newton Method with Inverse Jacobian from Least-Squares approximation (IQN-ILS), commonly adopted for solving uid-structure interaction problems have been introduced in the context of tribological simulations, particularly for the coupled calculation of dynamic conformal EHL contacts. The performance of such partitioned methods was evaluated according to simulations of dynamically loaded connecting-rod big-end bearings of both heavy-duty and high-speed engines. Finally, the proposed deterministic mixed-lubrication modelling was applied to investigate the in fluence of the cylinder liner wear after a 100h dynamometer engine test on the hydrodynamic pressure generation and friction of Twin-Land Oil Control Rings.

Real time motion estimation using a neural architecture implemented on GPUs

This work describes a neural network based architecture that represents and estimates object motion in videos. This architecture addresses multiple computer vision tasks such as image segmentation, object representation or characterization, motion analysis and tracking. The use of a neural network architecture allows for the simultaneous estimation of global and local motion and the representation of deformable objects. This architecture also avoids the problem of finding corresponding features while tracking moving objects. Due to the parallel nature of neural networks, the architecture has been implemented on GPUs that allows the system to meet a set of requirements such as: time constraints management, robustness, high processing speed and re-configurability. Experiments are presented that demonstrate the validity of our architecture to solve problems of mobile agents tracking and motion analysis.

Performance Factors in Women's Team Handball: Physical and Physiological Aspects—A Review

Team handball is an Olympic sport played professionally in many European countries. Nevertheless, a scientific knowledge regarding women's elite team handball demands is limited. Thus, the purpose of this article was to review a series of studies (n = 33) on physical characteristics, physiological attributes, physical attributes, throwing velocity, and on-court performances of women's team handball players. Such empirical and practical information is essential to design and implement successful short-term and long-term training programs for women's team handball players. Our review revealed that (a) players that have a higher skill level are taller and have a higher fat-free mass; (b) players who are more aerobically resistant are at an advantage in international level women team handball; (c) strength and power exercises should be emphasized in conditioning programs, because they are associated with both sprint performance and throwing velocity; (d) speed drills should also be implemented in conditioning programs but after a decrease in physical training volume; (e) a time-motion analysis is an effective method of quantifying the demands of team handball and provides a conceptual framework for the specific physical preparation of players. According to our results, there are only few studies on on-court performance and time-motion analysis for women's team handball players, especially concerning acceleration profiles. More studies are needed to examine the effectiveness of different training programs of women's team handball players' physiological and physical attributes.

Computer Networks Virtualization with GNS3: Evaluating a solution to optimize resources and achieve a distance learning

Designing educational resources allow students to modify their learning process. In particular, on-line and downloadable educational resources have been successfully used in engineering education the last years [1]. Usually, these resources are free and accessible from web. In addition, they are designed and developed by lecturers and used by their students. But, they are rarely developed by students in order to be used by other students. In this work-in-progress, lecturers and students are working together to implement educational resources, which can be used by students to improve the learning process of computer networks subject in engineering studies. In particular, network topologies to model LAN (Local Area Network) and MAN (Metropolitan Area Network) are virtualized in order to simulate the behavior of the links and nodes when they are interconnected with different physical and logical design.

Migration in the Central Mediterranean. Jean Monnet Occasional Papers 02/2013

In the last decade irregular immigration has emerged as a “security” challenge (in the language of International Relations military “threat”) in the Mediterranean region particularly in the central, sub-region1. The designation of this issue as a “security challenge” or “threat” is itself controversial and will be discussed further down. This paper focuses on the situation in the central Mediterranean involving mainly four countries namely Italy, Libya, Malta and Tunisia all of which have long standing historic links and bilateral relations and participate in the so called “5+5” Dialogue in the Western Mediterranean. Two of these Central Mediterranean countries (Italy, Malta) are EU member states and Tunisia has a long standing relationship with the EU [Association Agreement, Barcelona Process (EMP), Neighbourhood Policy (ENP), Union for the Mediterranean (UfM)] while Libya so far has no formal relations at all with the EU. This paper analyses some of the aspects of migration in the central Mediterranean focusing on the link between the domestic and international politics of the issue in Italy and Malta and contrasting the different approaches taken. For example, although Italy and Malta both resort to self-help and both try to involve the EU in helping them tackle the problem, they do this in a markedly different way: Italy uses the EU as a supplement to its independent and bilateral efforts while Malta looks to the EU as the major solution to the problem. Lacking the power and influence to deal with the issue, Malta tends to see the problem as primarily a multilateral issue or one that can only be tackled in concert with stronger powers in the region preferably within an EU context. On the other hand, Italy has been keen in involving the EU but decided to go it alone when this option turned out to be a dead end. In this paper I also try to show the extent (or limitations) to which multilateral initiatives such as the “5+5” and Euro operation really play a decisive role in incentivizing or facilitating inter-state cooperation or joint solutions. This paper also refers to the EU acquis, the notion of solidarity (norms) and the extent to which it is implemented as well as a number of connected issues. The subjects of this paper, the Mediterranean Boat People, have been referred to by various names in the literature, all of which may be more or less deficient in actually defining them all. They have been referred to as “illegal” or “irregular” immigrants, “refugees” in search of international protection, “migrants at sea” and “boat people”. The use of “boat people” dispenses with the need of having to define the various categories of migrants involved and is thus preferred in this paper.

The Relationship between Energy and Socio-Economic Development in the Southern and Eastern Mediterranean. MEDPRO Technical Report No. 27/February 2013

This report aims to identify, explain and detail the links and interactions in southern and eastern Mediterranean countries (SEMCs) between energy supply and demand and socio-economic development, as well as the potential role of energy supply and demand policies on both. Another related aim is to identify and analyse, in a quantitative and qualitative way, the changing role of energy (both demand and supply) in southern Mediterranean economies, focusing on its positive and negative impact on socio-economic development. This report investigates in particular: o The most important channels through which resource wealth can contribute to or hamper economic and social development in the analysed region; o Mechanisms and channels of relations between energy supply and demand policies and economic and social development. The burdens of energy subsidies and ‘oil syndrome’ are of particular relevance for the region. An integrated socio-economic development and energy policy scenario approach showing the potential benefits and synergies within countries and the region is developed in the final part of the report.

Table 2.- Bryozoa collected during the LAMPOS expeditions between Punta Arenas and the northernmost tip of the Antarctic Peninsula

The 78 bryozoan species collected by the German R/V "Polarstern" during the LAMPOS cruise in April 2002, encompassing the Scotia Arc archipelagos between Tierra del Fuego and the Antarctic Peninsula, were studied to discern the biogeographical patterns of the Magellan region of South America, the Scotia Arc archipelagos and the Antarctic. The resulting dendrogram shows three clusters: an isolated one with the three easternmost archipelagos and the other two linking some of the northern and southern Scotia Arc archipelagos with Tierra del Fuego. A more comprehensive analysis using all the species previously recorded from the Scotia Arc archipelagos and adjacent areas (214 spp.) produced a clearer zoogeographical pattern without isolated clusters of localities. The Antarctic Peninsula plus the Scotia Arc archipelagos form a large cluster distinct from the Magellan-Falkland Subantarctic area. A third analysis making use of 78 genera present in the study area plus Australia and New Zealand reinforces this pattern, showing two clusters: one uniting South America and the Australian-New Zealand realm and the other linking the Scotia Arc archipelagos with the Antarctic Peninsula. These results indicate that the Scotia Arc archipelagos represent merely a very narrow bridge connecting two different bryozoan faunas with only a few bryozoan species in common between the study areas.

Mental health recovery and occupational therapy in Australia and New Zealand

Every individual with mental illness has the right to be safe and cared for. Most people will receive the love and care from their families and friends, but they will also expect mental-health professionals, occupational therapists and the community to work together to provide the necessary services to support their recovery from mental illness. This article highlights the development of the recovery approach for people with mental illness in Australia and New Zealand. The implications of recovery concepts for occupational therapy, in the areas of individualized approach, participation of service users and carers, person-centred assessment and intervention, intersectoral links and mental-health promotion, are discussed. There are a number of key areas requiring further research and debate, notably the most effective means of implementing and evaluating recovery-focused interventions.

Psilocybin impairs high-level but not low-level motion perception

The hallucinogenic serotonin(IA&2A) agonist psilocybin is known for its ability to induce illusions of motion in otherwise stationary objects or textured surfaces. This study investigated the effect of psilocybin on local and global motion processing in nine human volunteers. Using a forced choice direction of motion discrimination task we show that psilocybin selectively impairs coherence sensitivity for random dot patterns, likely mediated by high-level global motion detectors, but not contrast sensitivity for drifting gratings, believed to be mediated by low-level detectors. These results are in line with those observed within schizophrenic populations and are discussed in respect to the proposition that psilocybin may provide a model to investigate clinical psychosis and the pharmacological underpinnings of visual perception in normal populations.

Measuring community strength and social capital

Five case study communities in both metropolitan and regional urban locations in Australia are used as test sites to develop measures of 'community strength' on four domains: Natural Capital; Produced Economic Capital; Human Capital; and Social and Institutional Capital. The paper focuses on the fourth domain. Sample surveys of households in the five case study communities used a survey instrument with scaled items to measure four aspects of social capital - formal norms, informal norms, formal structures and informal structures - that embrace the concepts of trust, reciprocity, bonds, bridges, links and networks in the interaction of individuals with their community inherent in the notion social capital. Exploratory principal components analysis is used to identify factors that measure those aspects of social and institutional capital, while a confirmatory analysis based on Cronbach's alpha explores the robustness of the measures. Four primary scales and 15 subscales are identified when defining the domain of social and institutional capital. Further analysis reveals that two measures - anomie, and perceived quality of life and wellbeing - relate to certain primary scales of social capital.

Changes in morphology and physiology of an East Mediterranean sponge in different habitats

The sponge Tetilla sp. (Tetractinomorpha: Tetillidae) is a common species in the eastern Mediterranean. This sponge inhabits four different habitat types differing in wave impact and irradiance levels. Two of these habitats (a shallow cave and deep water) are characterized by relatively calm water, whereas the other two (shallow exposed site and tide pools) are in turbulent water with high energy flow. The present study examined the influence of physical (depth, illumination and water motion) and biotic factors on morphology, skeletal plasticity and reproductive traits among the four spatially separated populations. Sponges from tidal pools had significantly larger body volume than sponges from deep water and from shallow caves (ANOVA: tidal-deep P< 0.0001; tidal-shallow caves P< 0.05). Sponges from exposed habitats were significantly larger than deep-water sponges (ANOVA: P=0.01). In addition, individuals from tide pools and from the exposed habitat had a significantly higher proportion of structural silica than sponges from the calmer deep water and from the cave sites. Oxea spicules in sponges from the calm habitats were significantly shorter than in those from the tidal pools and the exposed habitats. The percentage of spicules out of a sponge's dry weight in individuals transplanted from deep (calm) to shallow (turbulent) water significantly increased by 21.9&PLUSMN; 12.9%. The new spicule percentage did not differ significantly from that of sponges originally from shallow water. Oocyte diameter differed significantly between habitats. The maximal size of mature eggs was found in deep-water sponges in June (97&PLUSMN; 5 μ m). In the shallow habitats, a smaller maximal oocyte diameter was found in the cave, in May (56.5&PLUSMN; 3 μ m). Furthermore, oocyte density in shallow-water sponges was highest in May and decreased in June (with 88.2&PLUSMN; 9 and 19.3&PLUSMN; 9 oocytes mm(-2), respectively). At the same time (June), oocyte density of deep-water sponges had just reached its maximum (155&PLUSMN; 33.7 oocytes mm(-2)). The difference in oocyte size and density between deep- and shallow-water individuals indicates an earlier gamete release in the shallow sponge population. The results suggest that plasticity in skeletal design of this sponge indicates a trade off between spicule production and investment in reproduction.

Interfaces between cardiovascular and kidney disease among Aboriginal Australians

Rates of kidney disease among several indigenous groups have been shown to be substantially higher than corresponding non-indigenous groups. This excess has been clearly shown among Aboriginal Australians with respect to both end-stage kidney disease and early kidney disease. Rates of cardiovascular disease among Aboriginal Australians are also very high, as are rates of diabetes, smoking, and possibly overweight and obesity. These factors have been traditionally linked with cardiovascular and renal disease as part of a broader metabolic syndrome. However, the links and interfaces between cardiovascular and kidney disease in this environment extend beyond these traditional factors. The factors associated with atherosclerosis have expanded in recent years to include markers of inflammation, some infection, antioxidants, and other non-traditional risk factors. Given the high rates of acute infection and poor living conditions endured by many indigenous people, one might expect these non-traditional risk factors to be highly prevalent. In this review, we explore the relationships between markers of inflammation, some serological markers of infection, and other selected markers and both cardiovascular and renal disease. In doing so, we demonstrate links between kidney and cardiovascular disease at a number of levels, beyond the traditional cardiovascular/renal risk factors. Many of these factors are beyond the control of the individual or even community; addressing these issues a broader focus and biopsychosocial model. (C) 2005 by the National Kidney Foundation, Inc.