L'antagonisme entre les besoins croissants d'énergie au niveau mondial et l'obligation de ralentir le réchauffement climatique fait partie des défis auquel l'humanité fait face. Dans le but d'assurer un confort thermique suffisant, les domaines de l'habitat, de l'automobile ou encore des bâtiments agricoles consomment de grandes quantités d'énergie. Pour réduire ces besoins, une des solutions proposées vise à améliorer l'isolation thermique de ces bâtiments grâce à l'utilisation de matériaux innovants. Un des objectifs majeurs est d'améliorer l'isolation des fenêtres qui représentent une partie importante des pertes énergétiques. Les recherches décrites dans cette thèse ont permis de développer des matériaux transparents aux rayonnements solaires visibles tout en étant des boucliers efficaces contre les rayonnements ultra-violets et proche-infrarouges. De tels matériaux sont le fruit de la combinaison entre des motifs à clusters de métaux de transition présentant des propriétés d'absorption recherchées et une matrice hôte permettant la mise en forme de ces matériaux (processabilité). La synthèse, ainsi que la méthodologie de modulation des propriétés d'absorption et d'intégration des clusters dans différentes matrices de type sol-gel ou polymères sont présentées. Un intérêt tout particulier est porté sur les relations qui s'établissent entre la structure des motifs à clusters et leurs propriétés d'absorption grâce aux comparaisons faites entre des études expérimentales et des études de chimie quantique utilisant la théorie de la fonctionnelle de la densité (DFT). In fine, l'augmentation du niveau de compréhension des relations structures-propriétés d'absorption des motifs à clusters étudiés permettra d'envisager l'étude de nouvelles compositions pour des matériaux encore plus efficaces à l'avenir pour le contrôle solaire. / The antagonism between growing global energy needs and the obligation to slow the global warming is one of the challenges humanity faces. In order to ensure sufficient thermal comfort, the housing, automotive or agricultural buildings sectors are major energy consumers. To reduce these needs, one of the proposed solutions aims to improve the thermal insulation of these buildings through the use of innovative materials. One of the major objectives is to improve the insulation of the windows which represent a significant part of the energy losses. The research described in this thesis has made it possible to develop transparent materials for visible solar radiation while being effective shields against ultraviolet and near-infrared radiation. Such materials are the result of the combination between transition metal cluster patterns having desired absorption properties and a host matrix for shaping these materials (processability). The syntheses as well as the methodology for modulating the absorption and integration properties of clusters in different sol-gel or polymer matrices are presented. Of particular interest is the relationship between the structure of cluster pattern and their absorption properties through comparisons between experimental studies and quantum chemistry studies using density functional theory (DFT). In fine, the increase in the level of understanding of the structure-absorption properties of the clusters studied will make it possible to consider the study of new compositions for even more efficient materials in the future for solar control.

Density functional theory is the most commonly used computational tool to study properties of solids and molecules. Self-interaction error, that arises due to improper cancellation of the self-Hartree and the self exchange correlation energy, has long been identified as a major limitation of practical density functional approximations. We develop and test the performance of different self-interaction corrected functionals in accurately predicting a wide range of properties. This work focuses on use of the Fermi-L\"{o}wdin orbital self-interaction correction (FLOSIC) method to study neutral water complexes and interaction of ions with water clusters. The strongly constrained and appropriately normed (SCAN) density functional approximation (DFA) has been found to give the correct energy ordering of low-lying isomers of water hexamers, resolves the density anomaly between water and ice, and improves the relative lattice energy of ice polymorphs and the infrared spectra of liquid water. However, SCAN is not without its drawbacks. The binding energies of water clusters and lattice energies of ice phases are overestimated by SCAN. We find that by explicitly removing the self-interaction error, the hydrogen-bond binding energy of water clusters can be significantly improved. In particular, self-interaction correction to the SCAN functional (FLOSIC-SCAN) improves binding energies without altering the correct energetic ordering of the low-lying water hexamers. So, orbital-by-orbital removal of self-interaction error applied on top of a proper DFA can lead to an improved description of water complexes. To gain further insight into the performance of different functionals on the relative stability of water clusters, we decompose the total interaction energy into many-body components. We see that the major portion of error in SCAN comes from the two-body interaction, and the FLOSIC-SCAN improves two-body interactions over SCAN and predicts higher-order many-body interactions with about the same accuracy as SCAN. The SCAN functional gives good account of monomer deformation energy (one-body energy), PBE estimated it too low and self-interaction corrected methods FLOSIC-PBE and FLOSIC-SCAN estimated too high monomer deformation energies. Improvement in the total interaction energy by FLOSIC-PBE and FLOSIC-SCAN is happening because of error cancellation by one-body interaction energy. Aqueous solutions of ions are of particular interest due to their profound applications in environmental chemistry, solvation mechanics, the desalination process, etc. This motivated us to study ion-water systems, which include hydronium ion-water clusters, hydroxyl ion-water clusters, halide ion-water clusters, and alkali ion-water clusters. The erroneous delocalization of the extra-electron in anions obtained with DFAs is basis-set dependent. DFAs like LSDA, PBE, or SCAN can bind only a fraction of the excess electron in the complete basis set limit, implying that a moderate-sized localized basis would be a good choice for them. But, accurate description of hydrogen bonds often requires a large basis with some extra diffuse functions. So, in negatively charged hydrogen-bonded systems like deprotonated water clusters, the suitable choice of basis-set is both difficult and ambiguous. We explore this issue systematically in this work. Further, we have found that the better performance by application of FLOSIC is seen in all systems that are connected at least with one hydrogen bond and the error in the binding energy decreases with increase in the size of an ion or equivalently decreases with the length of the hydrogen bond. Moreover, within the same ion-water system, error in the binding energy decreases with increase in the size of the cluster. Non-hydrogen-bonded water-alkali clusters are not affected by the self-interaction errors. / Physics

[pt] A acirrada competição em um mercado globalizado tornou de extrema importância que as empresas adquiram vantagens competitivas para conseguirem conquistar a preferência dos consumidores. Uma das formas de se obter tal vantagem em relação aos concorrentes é através da diferenciação. Para isso, as organizações devem se empenhar nas suas atividades de inovação. Contudo, gerar inovação é uma tarefa árdua para ser feita de forma isolada e por isso, algumas empresas têm se organizado em clusters (no Brasil conhecido como arranjos produtivos locais – APL) para facilitar a busca por inovação, produtividade e melhores resultados financeiros. Nessa perspectiva, o objetivo desta pesquisa é comparar a produtividade e o desempenho da inovação de produtos, de empresas brasileiras inseridas ou não em clusters, considerando as estratégias de P&D interno e externo implementadas. Através de uma equação de modelos estruturais, usando a técnica de multigrupo, pôde-se chegar a resultados que suportam um impacto positivo do P&D externo e interno no desempenho de inovação, além de suportar a hipótese de que desempenho de inovação, independente de estar ou não inserida em um cluster, impacta positivamente na produtividade das empresas. Concluiu-se, de acordo com os resultados, o aumento da intensidade de P&D tanto interno como externo são fundamentais para se aumentar o desempenho de inovação da firma. Este por sua vez, quanto maior for, maior será a produtividade da firma. Por outro lado o efeito moderador da capacidade absortiva mostrou-se benéfico apenas para empresas inseridas em cluster. / [en] Fierce competition in a globalized market has made it extremely important for companies to acquire competitive advantages in order to achieve consumer preference. One of the ways to obtain such an advantage in relation to competitors is through differentiation. To this end, organizations must engage in their innovation activities. However, generating innovation is an arduous task to be done in isolation and for this reason some companies have organized themselves into clusters (in Brazil known as local productive arrangements - APL) to facilitate the search for innovation, productivity and better financial results. In this perspective, the objective of this research is to compare the productivity and performance of product innovation, of Brazilian companies inserted or not in clusters, considering the implemented internal and external R&D strategies. Through an Structural Equation Modelling, using the multigroup technique, it was possible to obtain results that support the positive effect of internal and external R&D in the innovation performance, in addition to supporting the hypothesis that innovation performance, regardless of whether or not inserted in a cluster, positively impacts the productivity of companies. It was concluded, according to the results, the increase in the intensity of R&D, both internal and external, are fundamental to increase the firm s innovation performance. This in turn, the higher it is, the greater the productivity of the firm. On the other hand, the moderating effect of absorptive capacity proved beneficial only for companies in a cluster.

Many of the insightful writings on clusters identify the role of entrepreneurs as key agents in the formation of firms and clusters. This thesis argues instead that local entrepreneurship is not ceased once firms and clusters are established; local entrepreneurship is about the continuous (re)creation of both businesses and clusters in global spaces. Global spaces for local entrepreneurship emphasises how firms collectively become an agent of continuous renewal. Firms enact an organising context materialising in networks that stretch relations and collaborations according to the issues being dealt with. These networks are localised but are extended beyond the geographical boundaries of clusters. One important example of this, which is in focus in this doctoral thesis, is that firms operating in clusters often interact with actors whom they have met at international trade fairs (ITFs). ITFs are those attractive events that individuals, firms and institutions attend temporarily to exhibit and trade products in foreign and national markets. This thesis is based on the work contained in a cover and five papers. Each paper contributes to the research objective and questions brought forward in the thesis cover. The empirical evidence has been mostly drawn from several case studies conducted in the Lammhult cluster in Sweden. The findings show that firms build their organising contexts in order to stretch the reach and accessibility to local and non-local actors; they jointly co-create potential opportunities. The organising contexts are mapped in networks using three proximity orders. The empirical findings report three types of situations in which there is a potential opportunity for continuous renewal. By emphasising the opportunities that can be originated when a business is not realised or when a new or improved product or process has not been generated yet, this thesis aims to stimulate a theoretical reappraisal of global spaces for local entrepreneurship. With the conceptual development of global spaces for local entrepreneurship, we put forward the idea that such spaces enhance an ability to renew firms and clusters. The underlying reason is that local entrepreneurship is centered on the social interaction between individuals, firms and/or institutions; it materialises in intended and unintended dialogical situations when there is a commitment to the continuous renewal of firms and clusters. Such dialogical situations carry with them an opportunity for co-creating new businesses, new products and new processes.

This thesis proposed solutions to some shortcomings to current eLearning architectures. The proposed DeLC architecture supports context-aware and adaptable provision of eLearning services and electronic content. The architecture is fully distributed and integrates service-oriented development with agent technology. Central to this architecture is that a node is our unit of computation (known as eLearning node) which can have purely service-oriented architecture, agent-oriented architecture or mixed architecture. Three eLeaerning Nodes have been implemented in order to demonstrate the vitality of the DeLC concept. The Mobile eLearning Node uses a three-level communication network, called InfoStations network, supporting mobile service provision. The services, displayed on this node, are to be aware of its context, gather required learning material and adapted to the learner request. This is supported trough a multi-layered hybrid (service- and agent-oriented) architecture whose kernel is implemented as middleware. For testing of the middleware a simulation environment has been developed. In addition, the DeLC development approach is proposed. The second eLearning node has been implemented as Education Portal. The architecture of this node is poorly service-oriented and it adopts a client-server architecture. In the education portal, there are incorporated education services and system services, called engines. The electronic content is kept in Digital Libraries. Furthermore, in order to facilitate content creators in DeLC, the environment Selbo2 was developed. The environment allows for creating new content, editing available content, as well as generating educational units out of preexisting standardized elements. In the last two years, the portal is used in actual education at the Faculty of Mathematics and Informatics, University of Plovdiv. The third eLearning node, known as Agent Village, exhibits a purely agent-oriented architecture. The purpose of this node is to provide intelligent assistance to the services deployed on the Education Pportal. Currently, two kinds of assistants are implemented in the node - eTesting Assistants and Refactoring eLearning Environment (ReLE). A more complex architecture, known as Education Cluster, is presented in this thesis as well. The Education Cluster incorporates two eLearning nodes, namely the Education Portal and the Agent Village. eLearning services and intelligent agents interact in the cluster.

The reactivity of group 15 Zintl ions, E₇^3– (E = P, As), towards a number of transition and post-transition metal reagents has been studied. The synthesis and characterisation of the resulting novel cluster anions are described herein. The reactions of E₇^3– with [Cu₅(mes)₅], MPh₂ (M = Zn, Cd) and InPh₃ yielded the Cu–Cu bridged species [Cu₂(E₇)₂]^4– (E = P, As), the group 12 bridged cluster anions [M(E₇)₂]^4– (M = Zn: E = P, As; M= Cd: E = P), and the In-functionalised Zintl ions [E₇InPh<sub>2<sub>]^2–, respectively. P₇^3– and As₇^3– have been found to react with a number of metal salts, namely [M(nbe)₃][SbF₆] and MCl (M = Ag, Au), InCl₃, TlCl and MI₂ (M = Sn, Pb). These reactions formed the Ag–Ag and Au–Au bridged complexes [M₂(HP₇)₂]^2– (M = Ag, Au), the In-bridged species [In(E₇)₂]^3– (E = P, As), the Tl-derivatised Zintl ions [TlE₇]^2– (E = P, As), and the sixteen vertex cluster anions [ME₁₅]^3– (M = Sn, Pb; E = P, As). The reactivity of P₇^3– towards a series of group 8 compounds has also been studied. The reactions of P₇^3– with FeCl₂ and [Ru(PPh₃)₃Cl₂] produced [M(HP₇)₂]^2- (M = Fe, Ru). NMR studies showed that these species can be deprotonated to form [M(P₇)₂]^4– (M = Fe, Ru). These Fe and Ru complexes are isoelectronic with ferrocene. In addition, P₇^3– reacts with [Ru(COD)(η³-CH₂C(CH₃)CH₂)₂] to form [(C₄H₇)P₇Ru(COD)]^2–. Both P₇^3– and As₇^3– undergo transition metal mediated activation reactions in the presence of [Co(PEt₂Ph₂)(mes)₂], yielding [Co(η⁵-P₅){η²-HP₂(mes)}]^2– and [Co([η³-As₃){η⁴-As₄(mes)₂}]^2–, respectively.

The overall aim of this thesis is to investigate the environments of AGN, in particular, the density of galaxies in the environments of radio-loud and radio-quiet AGN. This determines whether AGN trace dense environments at high redshifts and whether the environments are important in addressing the problem of radio-loud dichotomy. I extend my research by investigating whether star-formation evolves differently in high-redshift AGN environments compared to the field. I begin by investigating the environments of 169 AGN using Spitzer data at z ∼ 1. I investigate the source density of star-forming galaxies in the environments of radio galaxies, radio-loud quasars and radio- quiet quasars. I do not find any significant overdensity of star-forming galaxies in these environments, although I find tentative evidence for a diff erence in the colours of galaxies in the radio galaxy environments compared to the quasar and field environments. I next use VIDEO data to investigate the environments of the quasars out to z ∼ 3. Firstly, I use a training sample of QSOs and galaxies, which trains a neural network to detect QSOs in the VIDEO data. I detect 274 possible QSOs in the VIDEO data using this method. I am able to determine that the efficiency of the neural network clas- sification is 95 per cent using the training sample. I compare these results to a colour selection method, which detects 88 QSOs in the VIDEO data, and find that the neural network is able to detect ∼ 80 per cent of the colour selected QSOs at Ks = 21. I then investigate the source overdensity using a radial analysis on the environments of the VIDEO QSOs. I find a significant overdensity of galaxies in the environments of the whole QSO sample and in the environments of the radio-loud quasars compared to the radio-quiet quasars. I extend the density analysis by using a second density measure, called the spatial clustering amplitude technique, to compare the environments of the quasars with their radio luminosities, absolute magnitudes and redshifts. I do not fi any significant correlations between environmental density and radio luminosity, absolute magnitude or redshift for the QSOs. I extend this research to investigate the type of galaxies found in the AGN environments. However, I do not find any significant differences between the type of galaxies found in the QSO environments and the background field.

Throughout the 1960s and the early 1970s, almost all developing countries pursued an import substitution policy that sought to develop a domestic manufacturing sector. At the same time, these governments carried out nationalisation programmes based on the view that foreign ownership of industry and assets was a drain on their wealth and hindered the economic development of the nation. Some developing countries saw foreign investment as a continuation of their colonial past and wanted to move away from it. As a result, there was a natural dislike and distrust of foreign investment. However, in the last three decades there has been a sea change in government opinions regarding foreign investment, and now many countries are actively encouraging it. In fact, some governments have paid financial incentives reaching as much as US$150,000 per employee to foreign companies to attract them to their country. These financial incentives are paid on the basis that governments believe that inward investment has positive effects on the economy, the most important of which is transfer of technology. Through improved technology a country can significantly enhance its competitiveness in the global marketplace leading to increased economic growth. With economic growth countries can also improve their social indicators such as education, health etc. Therefore, technology transfer from inward investment is viewed as the catalyst to change within a country. Despite the widespread popularity of governments seeking to attract inward investment there is no conclusive evidence that it leads to positive spillover effects in the form of technology transfer. This study seeks to fill this gap in the current body of academic knowledge, using the case of a small resource abundant country with a low population, such as the UAE, using both qualitative and quantitative research methods. The primary data was obtained through a detailed questionnaire, and provides an in depth approach to understanding the issue of technology transfer for the UAE; while the secondary data, obtained from UNCTAD and the World Bank, is more macro level in nature. The macro level data indicate that certain factors in the UAE are conducive to technology transfer taking place. The primary data seek to interrogate this for the case study presented in this study. In doing so, the primary and secondary data sets are connected in so far as to provide cross reliability through the identification of commonalities and differences of results. This study aims to provide understanding on whether FDI does indeed lead to a transfer of technology from the overseas firm into the host country economy. Understanding such a link within an academic framework allows this study to arrive at relevant policy recommendations that can be taken up by policy makers in similar contexts. The prior literature has shown that FDI both flows into countries that have proven economic growth and that FDI leads to economic growth, and therefore these factors are interrelated. This study has found that FDI can play an important role in filling domestic gaps in investment and also spur economic growth. This study develops a simultaneous regression to test the existence of a joint relationship between economic growth, which is a proxy for technology transfer, and FDI. In the case of host country factors a linear regression model is developed and tested. At a more micro level this study examined the case of Tawazun Economic Council, a high technology organisation that operates within the aerospace and defence industry cluster, in order to understand whether its investments have led to any real impact as far as technology transfer is concerned. The Tawazun Economic Council is a project with a total investment of US$60 billion, and as such allows this research to capture the impact of technology transfer in an enhanced cluster that has aerospace and defence as its core theme. The aerospace and defence sectors have leading edge technology, and therefore a high probability of technology transfer taking place. Through a survey of senior managers within the organisation responsible for strategy development, this study also found that technology transfer has taken place due to the very sophisticated off-take contracts that have been negotiated with buyers and technology suppliers. However, none of these technologies have been applied outside their narrow aerospace and defence usage. In addition, if capital abundant countries wish to capitalise on the technology transfer benefits from FDI then, future government policies should seek to protect intellectual property rights. The novel contribution of this study is that it has identified factors that are important for technology transfer from FDI to take place in capital abundant countries that have a small population. As such, the research has not only increased the current body of knowledge in this area, but has sought to provide policy recommendations that could help in increasing the level of FDI-based technology transfer in developing countries, with a particular emphasis on capital abundant and low population countries.

published_or_final_version / Urban Planning / Doctoral / Doctor of Philosophy

Uganda’s economy is agro-based; although the country is land locked it has great potential for industrial development. It is well endowed with natural resources and salubrious climate, but with little success in transforming its agricultural and mineral wealth into processed commodities for local, regional and international markets. The Uganda’s National Development Plan 2010- 2014 and Uganda Vision 2040 call for a transformed Ugandan society from a peasant to a modern and prosperous country within 30 years. To achieve this goal, Ugandan economy needs to be industrialized. This need is one of the identified strategic bottlenecks. Various strategies and action plans have been developed to steer the country’s economy towards sustainable development and increased competitiveness but with little success. It has been recognized globally that economic development depends heavily on small and medium sized enterprises (SMEs). SMEs are the prime source of new jobs and play a crucial role in income generation as well as in industrialization processes. However, most small businesses fail within their early stages of operation mainly due to under-capitalization and / or lack of proper management and business skills. Globally, through business incubators, start-ups and SMEs have been significantly enhanced to overcome their initial and critical stages of development. Business incubators have been tried in Uganda but not in a successful way. An Open Innovation Business Incubator is a physical or virtual environment that combines the attributes of open innovation and business incubation concepts in creating and supporting new start-ups. This research aimed at understanding more of the situation in Uganda, how the innovation systems and incubators are managed in other countries and to design a model for how to create better conditions for incubators in Uganda and similar low-income countries and stimulate industrial development. The proposed model has adopted an open innovation approach and a list of suggestions and recommendations has been made. Different methodological tools and participatory approaches were utilized in the process of undertaking the study to achieve the objectives. Data were collected through literature review, analysis of relevant theories such as industrialization, entrepreneurship, science, technology and innovation, business incubation, triple helix and clusters theory, open innovation, and public private partnerships. Review of Government reports and policy documents, discussions with industrial and incubation experts, surveys, focus group discussions and case studies were done. Useful ideas were obtained from seminars and conferences. Research findings indicated that: • There are hardly any graduate incubatees in Uganda, thus there is a need to foster partnerships and synergies between government, private sector/non-government organizations and academia for open incubation, • All incubators in Uganda focus on incubatees developing technologies and products but not on business models , • Open innovation incubators combined with entrepreneurial oriented strategies can effectively support start-ups and SMEs but requires strong mutual trust amongst actors, • Through public-private partnerships and open innovation incubators, industrial transformation can be stimulated.