First principles calculations for vacancies and antisites in PbSe and PbTe: bulk and nanowire.

The energetic stability and the electronic properties of vacancies (VX) and antisites (XY) in PbSe and PbTe are investigated. PbSe and PbTe are narrow band gap semiconductors and have the potential to be used in infrared detectors, laser, and diodes. They are also of special interest for thermoelectric devices (TE). The calculations are based in the Density Functional Theory (DFT) and the General Gradient Approximation (GGA) for the exchange-correlation term, as implemented in the VASP code. The core and valence electrons are described by the Projected Augmented Wave (PAW) and the Plane Wave (PW) methods, respectively. The defects are studied in the bulk and nanowire (NW) system. Our results show that intrinsec defects (vacancies and antisites) in PbTe have lower formation energies in the NW as compared to the bulk and present a trend in migrate to the surface of the NW. For the PbSe we obtain similar results when compare the formation energy for the bulk and NW. However, the Pb vacancy and the antisites are more stable in the core of the NW. The intrinsec defects are shallow defects for the bulk system. For both PbSe and PbTe VPb is a shallow acceptor defect and VSe and VT e are shallow donor defects for the PbSe and PbTe, respectively. Similar electronic properties are observed for the antisites. For the Pb in the anion site we obtain an n-type semiconductor for both PbSe and PbTe, SeP b is a p-type for the PbSe, and T eP b is a n-type for PbTe. Due the quantum con��nement effects present in the NW (the band gap open), these defects have different electronic properties for the NW as compared to the bulk. Now these defects give rise to electronic levels in the band gap of the PbTe NW and the VT e present a metallic character. For the PbSe NW a p-type and a n-type semiconductor is obtained for the VP b and P bSe, respectively. On the other hand, deep electronic levels are present in the band gap for the VSe and SePb. These results show that due an enhanced in the electronic density of states (DOS) near the Fermi energy, the defective PbSe and PbTe are candidates for efficient TE devices.

Contractive-like mapping principles in ordered metric spaces and application to ordinary differential equations

[EN] The purpose of this paper is to present a fixed point theorem for generalized contractions in partially ordered complete metric spaces. We also present an application to first-order ordinary differential equations.

Modeling physiological processes in plankton on enzyme kinetic principles

[EN] Many ecologically important chemical transformations in the ocean are controlled by biochemical enzyme reactions in plankton. Nitrogenase regulates the transformation of N2 to ammonium in some cyanobacteria and serves as the entryway for N2 into the ocean biosphere. Nitrate reductase controls the reduction of NO3 to NO2 and hence new production in phytoplankton. The respiratory electron transfer system in all organisms links the carbon oxidation reactions of intermediary metabolism with the reduction of oxygen in respiration. Rubisco controls the fixation of CO2 into organic matter in phytoplankton and thus is the major entry point of carbon into the oceanic biosphere. In addition to these, there are the enzymes that control CO2 production, NH4 excretion and the fluxes of phosphate. Some of these enzymes have been recognized and researched by marine scientists in the last thirty years. However, until recently the kinetic principles of enzyme control have not been exploited to formulate accurate mathematical equations of the controlling physiological expressions. Were such expressions available they would increase our power to predict the rates of chemical transformations in the extracellular environment of microbial populations whether this extracellular environment is culture media or the ocean. Here we formulate from the principles of bisubstrate enzyme kinetics, mathematical expressions for the processes of NO3 reduction, O2 consumption, N2 fixation, total nitrogen uptake.

Middleware principles and design for the integration of ubiquitos mobile services

Nowadays, in Ubiquitous computing scenarios users more and more require to exploit online contents and services by means of any device at hand, no matter their physical location, and by personalizing and tailoring content and service access to their own requirements. The coordinated provisioning of content tailored to user context and preferences, and the support for mobile multimodal and multichannel interactions are of paramount importance in providing users with a truly effective Ubiquitous support. However, so far the intrinsic heterogeneity and the lack of an integrated approach led to several either too vertical, or practically unusable proposals, thus resulting in poor and non-versatile support platforms for Ubiquitous computing. This work investigates and promotes design principles to help cope with these ever-changing and inherently dynamic scenarios. By following the outlined principles, we have designed and implemented a middleware support platform to support the provisioning of Ubiquitous mobile services and contents. To prove the viability of our approach, we have realized and stressed on top of our support platform a number of different, extremely complex and heterogeneous content and service provisioning scenarios. The encouraging results obtained are pushing our research work further, in order to provide a dynamic platform that is able to not only dynamically support novel Ubiquitous applicative scenarios by tailoring extremely diverse services and contents to heterogeneous user needs, but is also able to reconfigure and adapt itself in order to provide a truly optimized and tailored support for Ubiquitous service provisioning.

Politiche pubbliche per la stagionalit�� del turismo da una prospettiva territoriale. Casi di studio in Scozia e in Sardegna

Rita Cannas presents a PhD thesis in Economics (Geo-Economic curriculum) which is titled ���Public Policies for Seasonality in Tourism from a Territorial Perspective. Case Studies in Scotland and Sardinia���. The specific area of the research is public policies for contrasting seasonality in tourism in peripheral areas. Seasonality has seen such as a problem in terms of social and economics patterns especially for those local communities which are situated in peripheral areas. The research explores what, how and for who, public policies, that have been in place in Scotland and Sardinia over the last 10-5 years, are working and what kind of results these have produced. The research has empirical and theoretical implications for studying tourism seasonality. It aims to highlight the local supply patterns of the phenomenon investigated, and to improve knowledge about the strategies and the policies that have been adopted in the two territorial contexts (Scotland and Sardinia) for contrasting or modifying seasonality in tourism. The type of subject and the research questions have suggested the adoption of an interpretative theoretical perspective and a qualitative methodological approach, although a set of quantitative secondary data is also required for understanding main tourism's characteristics and for analyzing the specificity of seasonality. Interview with key actors of the local system in Scotland and Sardinia is the method chosen to collect primary data. In total the researcher has done 20 interviews in deep. Case studies are chosen both as unity of analysis and research strategy. The main findings of the research show a different and complex scenario about quality and quantity of public policies and strategies in tourism in the two case studies. The role of local resources is quite strategic on delivering tourism services and on counteracting seasonality. Events, festival are the main demand-side strategies. From a supply-side the principles policies are focused on quality of services, technology, high skills, sustainability. Partnership between public and private sector seems to be a fundamental way to work in order to attain changes and outcomes. The research has a strong research design, provides coherent results, and it has been done paying attention to the validation of the whole process.

Partnership fra terzo Settore e Istituzioni Locali nelle Politiche Family Friendly: Il "Distretto famiglia"

L���idea fondamentale da cui prende avvio la presente tesi di dottorato �� che sia possibile parlare di una svolta nel modo di concettualizzare e implementare le politiche sociali, il cui fuoco diviene sempre pi�� la costruzione di reti di partnership fra attori pubblici e privati, in cui una serie di soggetti sociali plurimi (stakeholders) attivano fra loro una riflessivit�� relazionale. L���ipotesi generale della ricerca �� che, dopo le politiche improntate a modelli statalisti e mercatisti, o un loro mix, nella politica sociale italiana emerga l���esigenza di una svolta riflessiva e relazionale, verso un modello societario, sussidiario e plurale, e che di fatto ��� specie a livello locale ��� stiano sorgendo molte iniziative in tal senso. Una delle idee pi�� promettenti sembra essere la creazione di distretti sociali per far collaborare tra loro attori pubblici, privati e di Terzo settore al fine di creare forme innovative di servizi per la famiglia e la persona. La presente tesi si focalizza sul tentativo della Provincia di Trento di distrettualizzare le politiche per la famiglia. Tramite l���analisi del progetto ���Trentino ��� Territorio Amico della Famiglia��� e di una sua verticalizzazione, il Distretto Famiglia, si �� studiato l���apporto delle partnership pubblico-privato nella formazione di strumenti innovativi di governance che possano determinare una svolta morfogenetica nell���elaborazione di politiche per la famiglia. Le conclusioni del lavoro, attraverso una comparazione tra esperienze territoriali, presentano la differenziazione delle partnership sociali, in base ad alcuni variabili (pluralit�� di attori, pluralit�� di risorse, shared project, capitale sociale, decision making, mutual action, logiche di lavoro relazionale, sussidiariet��). Le diverse modalit�� di gestione delle partnership (capacitante, professionale e generativa) sintetizzano i portati culturali, strutturali e personali coinvolti nelle singole costruzioni. Solo le partnership che interpretano il loro potenziale regolativo e promozionale secondo la riflessivit�� relazionale tendono a generare beni comuni nel contesto sociale.

Spectroscopic signatures from first principles calculations: from surface adsorbates to liquids and polymers

In dieser Arbeit werden drei wasserstoffverbr��ckte Systeme in der kondensierten Phase mit Hilfe von first-principles-Elektronenstruktur-Rechnungen untersucht, die auf der Dichtefunktionaltheorie (DFT) unter periodischen Randbedingungen basieren. Ihre lokalen Konformationen und Wasserstoffbr��ckenbindungen werden mittels ab-initio Molekulardynamiksimulationen berechnet und weiterhin durch die Bestimmung ihrer spektroskopischen Parameter charakterisiert. Der Schwerpunkt liegt dabei auf lokalen Strukturen und auf schnellen Fluktuationen der Wasserstoffbr��ckenbindungen, welche von zentraler Bedeutung f��r die physikalischen und chemischen Eigenschaften der betrachteten Systeme sind. Die f��r die lokalen, instantanen Konformationen berechneten Spektren werden verwendet, um die physikalischen Prozesse, die hinter den untersuchten Ph��nomenen stehen, zu erkl��ren: die Wasseradsorption auf metallischen Oberfl��chen, die Ionensolvatisierung in w��ssrigen L��sungen und der Protonentransport in protonleitenden Polymeren, welche Prototypen von Membranen f��r Brennstoffzellen sind. Die M��glichkeit der Vorhersage spektroskopischer Parameter er��ffnet vielf��ltige M��glichkeiten des Dialogs zwischen Experimenten und numerischen Simulationen. Die in dieser Arbeit vorgestellten Ergebnisse zeigen, dass die Zuverl��ssigkeit dieser theoretischen Berechnungen inzwischen f��r viele experimentell relevante Systeme ein quantitatives Niveau erreicht hat.

Quantum effects and dynamics in hydrogen-bonded systems: a first-principles approach to spectroscopic experiments

Computer simulations have become an important tool in physics. Especially systems in the solid state have been investigated extensively with the help of modern computational methods. This thesis focuses on the simulation of hydrogen-bonded systems, using quantum chemical methods combined with molecular dynamics (MD) simulations. MD simulations are carried out for investigating the energetics and structure of a system under conditions that include physical parameters such as temperature and pressure. Ab initio quantum chemical methods have proven to be capable of predicting spectroscopic quantities. The combination of these two features still represents a methodological challenge. Furthermore, conventional MD simulations consider the nuclei as classical particles. Not only motional effects, but also the quantum nature of the nuclei are expected to influence the properties of a molecular system. This work aims at a more realistic description of properties that are accessible via NMR experiments. With the help of the path integral formalism the quantum nature of the nuclei has been incorporated and its influence on the NMR parameters explored. The effect on both the NMR chemical shift and the Nuclear Quadrupole Coupling Constants (NQCC) is presented for intra- and intermolecular hydrogen bonds. The second part of this thesis presents the computation of electric field gradients within the Gaussian and Augmented Plane Waves (GAPW) framework, that allows for all-electron calculations in periodic systems. This recent development improves the accuracy of many calculations compared to the pseudopotential approximation, which treats the core electrons as part of an effective potential. In combination with MD simulations of water, the NMR longitudinal relaxation times for 17O and 2H have been obtained. The results show a considerable agreement with the experiment. Finally, an implementation of the calculation of the stress tensor into the quantum chemical program suite CP2K is presented. This enables MD simulations under constant pressure conditions, which is demonstrated with a series of liquid water simulations, that sheds light on the influence of the exchange-correlation functional used on the density of the simulated liquid.

Contour integration and principles of perceptual grouping

Ziel der Arbeit ist die Analyse von Prinzipien der Konturintegration im menschlichen visuellen System. Die perzeptuelle Verbindung benachbarter Teile in einer visuellen Szene zu einem Ganzen wird durch zwei gestalttheoretisch begr��ndete Propositionen gekennzeichnet, die komplement��re lokale Mechanismen der Konturintegration beschreiben. Das erste Prinzip der Konturintegration fordert, dass lokale ��hnlichkeit von Elementen in einem anderen Merkmal als Orientierung nicht hinreicht f��r die Entdeckung von Konturen, sondern ein zus��tzlicher statistischer Merkmalsunterschied von Konturelementen und Umgebung vorliegen muss, um Konturentdeckung zu erm��glichen. Das zweite Prinzip der Konturintegration behauptet, dass eine kollineare Ausrichtung von Konturelementen f��r Konturintegration hinreicht, und es bei deren Vorliegen zu robuster Konturintegrationsleistung kommt, auch wenn die lokalen merkmalstragenden Elemente in anderen Merkmalen in hohem Ma��e zuf��llig variieren und damit keine nachbarschaftliche ��hnlichkeitsbeziehung entlang der Kontur aufweisen. Als empirische Grundlage f��r die beiden vorgeschlagenen Prinzipien der Konturintegration werden drei Experimente berichtet, die zun��chst die untergeordnete Rolle globaler Konturmerkmale wie Geschlossenheit bei der Konturentdeckung aufweisen und daraufhin die Bedeutung lokaler Mechanismen f��r die Konturintegration anhand der Merkmale Kollinearit��t, Ortsfrequenz sowie der spezifischen Art der Interaktion zwischen beiden Merkmalen beleuchten. Im ersten Experiment wird das globale Merkmal der Geschlossenheit untersucht und gezeigt, dass geschlossene Konturen nicht effektiver entdeckt werden als offene Konturen. Das zweite Experiment zeigt die Robustheit von ��ber Kollinearit��t definierten Konturen ��ber die zuf��llige Variation im Merkmal Ortsfrequenz entlang der Kontur und im Hintergrund, sowie die Unm��glichkeit der Konturintegration bei nachbarschaftlicher ��hnlichkeit der Konturelemente, wenn ��hnlichkeit statt ��ber kollineare Orientierung ��ber gleiche Ortsfrequenzen realisiert ist. Im dritten Experiment wird gezeigt, dass eine redundante Kombination von kollinearer Orientierung mit einem statistischen Unterschied im Merkmal Ortsfrequenz zu erheblichen Sichtbarkeitsgewinnen bei der Konturentdeckung f��hrt. Aufgrund der St��rke der Summationswirkung wird vorgeschlagen, dass durch die Kombination mehrerer Hinweisreize neue kortikale Mechanismen angesprochen werden, die die Konturentdeckung unterst��tzen. Die Resultate der drei Experimente werden in den Kontext aktueller Forschung zur Objektwahrnehmung gestellt und ihre Bedeutung f��r die postulierten allgemeinen Prinzipien visueller Gruppierung in der Konturintegration diskutiert. Anhand ph��nomenologischer Beispiele mit anderen Merkmalen als Orientierung und Ortsfrequenz wird gezeigt, dass die gefundenen Prinzipien Generalisierbarkeit f��r die Verarbeitung von Konturen im visuellen System beanspruchen k��nnen.

La dimensione esterna della politica migratoria dell'UE

Conformemente ai trattati, l'UE sviluppa una politica comune in materia di asilo, immigrazione e controllo delle frontiere esterne, fondata sulla solidariet�� e sul rispetto dei diritti fondamentali e, a tal fine, avvia relazioni strategiche con i Paesi terzi e le Organizzazioni internazionali. Un fenomeno ���senza frontiere���, quale quello migratorio, esige del resto un'azione coerente e coordinata sia sul piano interno sia su quello esterno. La messa in atto di quest'ultima, tuttavia, si scontra con difficolt�� di rilievo. Innanzitutto, l'UE e i suoi Stati membri devono creare i presupposti per l'avvio della collaborazione internazionale, vale a dire stimolare la fiducia reciproca con i Paesi terzi, rafforzando la propria credibilit�� internazionale. A tal fine, le istituzioni, gli organi e gli organismi dell'UE e gli Stati membri devono impegnarsi a fornire un modello coerente di promozione dei valori fondanti, quali la solidariet�� e il rispetto dei diritti fondamentali, nonch�� a coordinare le proprie iniziative, per individuare, insieme ai Paesi terzi e alle Organizzazioni internazionali, una strategia d'azione comune. In secondo luogo, l'UE e gli Stati membri devono adottare soluzioni volte a promuovere l'efficacia della collaborazione internazionale e, pi�� precisamente, assicurare che la competenza esterna sia esercitata dal livello di governo in grado di apportare il valore aggiunto e utilizzare la forma collaborativa di volta in volta pi�� adeguata alla realizzazione degli obiettivi previsti. In definitiva, l'azione esterna dell'UE in materia di politica migratoria necessita di una strategia coerente e flessibile. Se oggi la coerenza �� garantita dalla giustiziabilit�� dei principi di solidariet��, di rispetto dei diritti fondamentali e, giustappunto, di coerenza, la flessibilit�� si traduce nel criterio del valore aggiunto che, letto in combinato disposto con il principio di leale cooperazione, si pone al centro del nuovo modello partenariale proposto dall'approccio globale, potenzialmente idoneo a garantire la gestione efficace del fenomeno migratorio.

EPR spectroscopy as a tool for the elucidation of non-covalent structuring principles in complex soft matter

This thesis aims at connecting structural and functional changes of complex soft matter systems due to external stimuli with non-covalent molecular interaction profiles. It addresses the problem of elucidating non-covalent forces as structuring principle of mainly polymer-based systems in solution. The structuring principles of a wide variety of complex soft matter types are analyzed. In many cases this is done by exploring conformational changes upon the exertion of external stimuli. The central question throughout this thesis is how a certain non-covalent interaction profile leads to solution condition-dependent structuring of a polymeric system.rnTo answer this question, electron paramagnetic resonance (EPR) spectroscopy is chosen as the main experimental method for the investigation of the structure principles of polymers. With EPR one detects only the local surroundings or environments of molecules that carry an unpaired electron. Non-covalent forces are normally effective on length scales of a few nanometers and below. Thus, EPR is excellently suited for their investigations. It allows for detection of interactions on length scales ranging from approx. 0.1 nm up to 10 nm. However, restriction to only one experimental technique likely leads to only incomplete pictures of complex systems. Therefore, the presented studies are frequently augmented with further experimental and computational methods in order to yield more comprehensive descriptions of the systems chosen for investigation.rnElectrostatic correlation effects in non-covalent interaction profiles as structuring principles in colloid-like ionic clusters and DNA condensation are investigated first. Building on this it is shown how electrostatic structuring principles can be combined with hydrophobic ones, at the example of host-guest interactions in so-called dendronized polymers (denpols).rnSubsequently, the focus is shifted from electrostatics in dendronized polymers to thermoresponsive alkylene oxide-based materials, whose structuring principles are based on hydrogen bonds and counteracting hydrophobic interactions. The collapse mechanism in dependence of hydrophilic-hydrophobic balance and topology of these polymers is elucidated. Complementarily the temperature-dependent phase behavior of elastin-like polypeptides (ELPs) is investigated. ELPs are the first (and so far only) class of compounds that is shown to feature a first-order inverse phase transition on nanoscopic length scales.rnFinally, this thesis addresses complex biological systems, namely intrinsically disordered proteins (IDPs). It is shown that the conformational space of the IDPs Osteopontin (OPN), a cytokine involved in metastasis of several kinds of cancer, and BASP1 (brain acid soluble protein one), a protein associated with neurite outgrowth, is governed by a subtle interplay between electrostatic forces, hydrophobic interaction, system entropy and hydrogen bonds. Such, IDPs can even sample cooperatively folded structures, which have so far only been associated with globular proteins.