Raman multivariate curve resolution (Raman-MCR) spectroscopy is used to study water-mediated interactions by decomposing Raman spectra of aqueous solutions into bulk water and solute-correlated (SC) spectral components. The SC spectra are minimum-area difference spectra that reveal solute-induced perturbations of water structure, including changes in water hydrogen-bonding strength, tetrahedral structure, and formation of dangling (non-hydrogen-bonded) OH defects in a solute's hydration shell. Additionally, Raman-active intramolecular vibrational modes of the solute may be used to uncover complementary information regarding solute--solute interactions. Herein, Raman-MCR is applied to address fundamental questions related to: (1) confined cavity water and its connection to host-guest binding, (2) hydrophobic hydration of fluorinated solutes, (3) specific ion effects on nonionic micelle formation, and (4) ion pairing in aqueous solutions.

No description available.

The air transportation market has been growing steadily for the past three decades since the airline deregulation in 1978. With competition also becoming more intense, airline companies have been trying to enhance their market shares and profit margins by composing favorable flight schedules and by efficiently allocating their resources of aircraft and crews so as to reduce operational costs. In practice, this is achieved based on demand forecasts and resource availabilities through a structured airline scheduling process that is comprised of four decision stages: schedule planning, fleet assignment, aircraft routing, and crew scheduling. The outputs of this process are flight schedules along with associated assignments of aircraft and crews that maximize the total expected profit. Traditionally, airlines deal with these four operational scheduling stages in a sequential manner. However, there exist obvious interdependencies among these stages so that restrictive solutions from preceding stages are likely to limit the scope of decisions for succeeding stages, thus leading to suboptimal results and even infeasibilities. To overcome this drawback, we first study the aircraft routing problem, and develop some novel modeling foundations based on which we construct and analyze an integrated model that incorporates fleet assignment, aircraft routing, and crew pairing within a single framework. Given a set of flights to be covered by a specific fleet type, the aircraft routing problem (ARP) determines a flight sequence for each individual aircraft in this fleet, while incorporating specific considerations of minimum turn-time and maintenance checks, as well as restrictions on the total accumulated flying time, the total number of takeoffs, and the total number of days between two consecutive maintenance operations. This stage is significant to airline companies as it directly assigns routes and maintenance breaks for each aircraft in service. Most approaches for solving this problem adopt set partitioning formulations that include exponentially many variables, thus requiring the design of specialized column generation or branch-and-price algorithms. In this dissertation, however, we present a novel compact polynomially sized representation for the ARP, which is then linearized and lifted using the Reformulation-Linearization Technique (RLT). The resulting formulation remains polynomial in size, and we show that it can be solved very efficiently by commercial software without complicated algorithmic implementations. Our numerical experiments using real data obtained from United Airlines demonstrate significant savings in computational effort; for example, for a daily network involving 344 flights, our approach required only about 10 CPU seconds for deriving an optimal solution. We next extend Model ARP to incorporate its preceding and succeeding decision stages, i.e., fleet assignment and crew pairing, within an integrated framework. We formulate a suitable representation for the integrated fleeting, routing, and crew pairing problem (FRC), which accommodates a set of fleet types in a compact manner similar to that used for constructing the aforementioned aircraft routing model, and we generate eligible crew pairings on-the-fly within a set partitioning framework. Furthermore, to better represent industrial practice, we incorporate itinerary-based passenger demands for different fare-classes. The large size of the resulting model obviates a direct solution using off-the-shelf software; hence, we design a solution approach based on Benders decomposition and column generation using several acceleration techniques along with a branch-and-price heuristic for effectively deriving a solution to this model. In order to demonstrate the efficacy of the proposed model and solution approach and to provide insights for the airline industry, we generated several test instances using historical data obtained from United Airlines. Computational results reveal that the massively-sized integrated model can be effectively solved in reasonable times ranging from several minutes to about ten hours, depending on the size and structure of the instance. Moreover, our benchmark results demonstrate an average of 2.73% improvement in total profit (which translates to about 43 million dollars per year) over a partially integrated approach that combines the fleeting and routing decisions, but solves the crew pairing problem sequentially. This improvement is observed to accrue due to the fact that the fully integrated model effectively explores alternative fleet assignment decisions that better utilize available resources and yield significantly lower crew costs. / Ph. D.

The American Kestrel (Falco sparverius) is the smallest and most abundant falcon in North America with a wide geographic range. Unfortunately, surveys have suggested that some kestrel populations have been in decline since the 1950s, though the nominal causes of this decline are unknown. Migratory movement patterns and connectivity have yet to be established for any population of migratory kestrels. In Chapter 2, I investigated methods for attaching migration trackers to kestrels. Specifically, I showed that leg-loop style harnesses may have negatively affected return rates whereas backpack harnesses did not. Based on these results, I recommend that backpack-style Teflon harnesses is the safest and most effective method for attaching tracking devices to small raptors. In Chapter 3, I quantified survivorship for kestrels wintering in north Texas to identify the timing of kestrel mortality. Notably, I found that juvenile kestrels had similar annual survival rates as adults (81.6% versus 79.5%). High overwintering survival in north Texas indicated that once kestrels arrived on their wintering grounds, they were highly likely to survive to spring migration. In Chapter 4, I investigated pairing behaviors previously undocumented in wintering kestrels. I found that winter pairing was relatively common, but more prevalent in urban environments than rural. My data suggested that pairing during the winter could be a coping mechanism to increase kestrel survival in stressful anthropic landscapes. Altogether, this research highlights that the documentation of migratory connectivity is essential to understanding how many processes affect kestrel population dynamics, as I found evidence of potential seasonal carryover effects.

Diese Arbeit widmet sich der Untersuchung der dynamischen und strukturellen Eigenschaften sowie des Phasenverhaltens konzentrierter flüssiger Elektrolyte und ihrer Anwendung in Energiespeichern mittels Methoden der statistischen Mechanik und mithilfe atomistischer Molekulardynamik (MD) Simulationen. Zuerst untersuchen wir die Struktur-Eigenschafts-Beziehungen in konzentrierten Elektrolytlösungen wie sie in Lithium-Schwefel (Li/S), durch wir ein MD Simulationsmodell repräsentativer state-of-the-art Elektrolyt-Systeme für Li/S-Batterien bestehend aus Polysulfiden, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) und LiNO 3 Elektrolyten mit jeweils unterschiedlichen Kettenlängen gemischt in organischen Lösungsmitteln aus 1,2-dimethoxyethane and 1,3-dioxolane erstellen. Als Zweites befassen wir uns mit der Phasenseparation, die auftritt, wenn sich die physikalisch-chemischen Eigenschaften flüssiger Gemische voneinander unterscheiden. Diese Systeme bestehen üblicherweise aus einem konzentrierten anorganischen Salz und einer ionischen Flüssigkeit. In dieser Arbeit untersuchen wir eine Vielfalt von hochkonzentrierten wässrigen Elektrolytlösungen, die aus unterschiedlichen Zusammensetzungen von LiCl und LiTFSI bestehen. Daraufhin beantworten wir die Frage, wie unterschiedlich die Komponenten in der wässrigen Lösung gemischt sein sollten, damit eine solche flüssig-flüssig-Phasentrennung stattfinden kann. Als letztes untersuchen wir die Ladungsabschirmung, die ein grundlegendes Phänomen ist, das die Struktur von Elektrolyten im Bulk und an Grenzflächen bestimmt. Wir haben in dieser Arbeit die Abschirmlängen für verschiedene Elektrolyte von niedrigen bis zu hohen Konzentrationen untersucht. / Electrolytes can be found in numerous applications in daily life as well as in scientific research. The increases in demand for energy-storage systems, such as fuel cells, supercapacitors and batteries in which liquid electrolyte properties are critical for optimal function, draw critical attention to the physical and chemical properties of electrolytes. Those energy-storage devices contain intermediate or highly concentrated electrolytes where established theories, like the Debye-Hückel (DH) theory, are not applicable. Despite the efforts to describe the physical properties of intermediate or highly concentrated electrolytes, theoretical atomistic-level studies are still lacking. This thesis is devoted to critically investigate the transport/structural properties and a phase behavior of concentrated liquid electrolytes and their application in energy-storage devices, using statistical mechanics and atomistic molecular dynamics (MD) simulations. Firstly, we investigate the structure-property relationship in concentrated electrolyte solutions in next-generation lithium-sulfur (Li/S) batteries. Secondly, phase separation may exist if the physio-chemical properties of liquid mixtures are very different. Recently, the coexistence phase of two aqueous solutions of different salts at high concentrations was found, called aqueous biphasic systems. We explore a wide range of compositions at room temperature for highly concentrated aqueous electrolytes solutions that consist of LiCl and LiTFSI. Lastly, charge screening is a fundamental phenomenon that governs the structure of liquid electrolytes in the bulk and at interfaces. From the DH theory, the screening length is expected to be extremely small in highly concentrated electrolytes. Yet, recent experiments show unexpectedly high screening lengths in those. This intriguing phenomenon has prompted a new set of theoretical works. We investigate the screening lengths for various electrolytes from low to high concentrations.

Les principaux objets étudiés dans cette thèse sont les équations décrivant le morphisme de groupe sur une variété abélienne, plongée dans un espace projectif, et leurs applications en cryptographie. Notons g sa dimension et k son corps de définition. Ce mémoire est composé de deux parties. La première porte sur l'étude des courbes d'Edwards, un modèle pour les courbes elliptiques possédant un sous-groupe de points k-rationnels cyclique d'ordre 4, connues en cryptographie pour l'efficacité de leur loi d'addition et la possibilité qu'elle soit définie pour toute paire de points k-rationnels (loi d'addition k-complète). Nous en donnons une interprétation géométrique et en déduisons des formules explicites pour le calcul du couplage de Tate réduit sur courbes d'Edwards tordues, dont l'efficacité rivalise avec les modèles elliptiques couramment utilisés. Cette partie se conclut par la génération, spécifique au calcul de couplages, de courbes d'Edwards dont les tailles correspondent aux standards cryptographiques actuellement en vigueur. Dans la seconde partie nous nous intéressons à la notion de complétude introduite ci-dessus. Cette propriété est cryptographiquement importante car elle permet d'éviter des attaques physiques, comme les attaques par canaux cachés, sur des cryptosystèmes basés sur les courbes elliptiques ou hyperelliptiques. Un précédent travail de Lange et Ruppert, basé sur la cohomologie des fibrés en droite, permet une approche théorique des lois d'addition. Nous présentons trois résultats importants : tout d'abord nous généralisons un résultat de Bosma et Lenstra en démontrant que le morphisme de groupe ne peut être décrit par strictement moins de g+1 lois d'addition sur la clôture algébrique de k. Ensuite nous démontrons que si le groupe de Galois absolu de k est infini, alors toute variété abélienne peut être plongée dans un espace projectif de manière à ce qu'il existe une loi d'addition k-complète. De plus, l'utilisation des variétés abéliennes nous limitant à celles de dimension un ou deux, nous démontrons qu'une telle loi existe pour leur plongement projectif usuel. Finalement, nous développons un algorithme, basé sur la théorie des fonctions thêta, calculant celle-ci dans P^15 sur la jacobienne d'une courbe de genre deux donnée par sa forme de Rosenhain. Il est désormais intégré au package AVIsogenies de Magma. / The main objects we study in this PhD thesis are the equations describing the group morphism on an abelian variety, embedded in a projective space, and their applications in cryptograhy. We denote by g its dimension and k its field of definition. This thesis is built in two parts. The first one is concerned by the study of Edwards curves, a model for elliptic curves having a cyclic subgroup of k-rational points of order 4, known in cryptography for the efficiency of their addition law and the fact that it can be defined for any couple of k-rational points (k-complete addition law). We give the corresponding geometric interpretation and deduce explicit formulae to calculate the reduced Tate pairing on twisted Edwards curves, whose efficiency compete with currently used elliptic models. The part ends with the generation, specific to pairing computation, of Edwards curves with today's cryptographic standard sizes. In the second part, we are interested in the notion of completeness introduced above. This property is cryptographically significant, indeed it permits to avoid physical attacks as side channel attacks, on elliptic -- or hyperelliptic -- curves cryptosystems. A preceeding work of Lange and Ruppert, based on cohomology of line bundles, brings a theoretic approach of addition laws. We present three important results: first of all we generalize a result of Bosma and Lenstra by proving that the group morphism can not be described by less than g+1 addition laws on the algebraic closure of k. Next, we prove that if the absolute Galois group of k is infinite, then any abelian variety can be projectively embedded together with a k-complete addition law. Moreover, a cryptographic use of abelian varieties restricting us to the dimension one and two cases, we prove that such a law exists for their classical projective embedding. Finally, we develop an algorithm, based on the theory of theta functions, computing this addition law in P^15 on the Jacobian of a genus two curve given in Rosenhain form. It is now included in AVIsogenies, a Magma package.

Ce travail de recherche s’inscrit dans le champ théorique de la didactique des langues et du bilinguisme. Il a pour objet l’étude et la réflexion sur l’harmonisation des pratiques d’enseignement dans deux écoles primaires du réseau de l’Agence de l’Enseignement Français à l’Étranger (AEFE) en Amérique latine : l’école de Santiago du Chili et celle de La Paz (Bolivie). À partir d’un certain stade de son développement, cette étude s’étend à d’autres écoles du réseau AEFE implantées sur le continent latino-américain. L’interlangue des jeunes apprenants constitue la matrice à partir de laquelle se fonde ce travail de théorisation. Une grande partie de la thèse est consacrée à l’analyse des interactions linguistiques en classe de français, d’espagnol et en classe bilingue afin d’appréhender les moyens pédagogiques déployés par les enseignants pour traiter de faits de langue et en particulier des interférences linguistiques qui leur sont inhérentes. Cette analyse s’attache donc à la dynamique d’articulation entre la langue nationale et la langue française dans les pratiques quotidiennes de classe. À partir de réflexions théoriques et d’expériences menées sur le terrain, cette recherche s’interroge, d’une part, sur la prise en compte de certains paramètres didactiques nécessaires à la construction d’un curriculum d’enseignement convergent, et, d’autre part, sur la conceptualisation et la mise en œuvre d’un curriculum de formation des enseignants en didactique convergente. / This investigative work is part of the theoretical field of language instruction and bilingualism. Its purpose is the study of, and the reflection upon the harmonization of teaching practices in two primary schools belonging to the network of the Agency for French Instruction Abroad (AEFE) in Latin America: one in Santiago, Chili, and the other in La Paz, Bolivia. After a certain point in its development, this study extends to other schools in the AEFE network located in Latin America. The interlanguage of young learners is the matrix for this theorization work. A large part of the dissertation is dedicated to analyzing linguistic interactions in French class, Spanish class and bilingual class in order to grasp the pedagogical means used by instructors to deal with language features and in particular, inherent linguistic interferences. This analysis deals closely with the dynamics of articulation between the national language and the french language in daily classroom practices. This investigation uses theoretical reflections and field experiments to examine the taking into account of certain didactic parameters needed to implement a convergent instruction curriculum, on the one hand, and the conceptualization and implementation of an instructor training curriculum in convergent didactics, on the other hand. / Este trabajo de investigación se enmarca en el ámbito teórico de la didáctica lingüística y del bilingüismo. Contempla el estudio y la reflexión sobre la armonización de prácticas de enseñanza y de aprendizaje en dos escuelas primarias asociadas a la red educativa de los centros de la Agencia para la Enseñanza Francesa en el Extranjero (A.E.F.E): la escuela de Santiago de Chile (Centro de la Alianza Saint-Exupéry) y la de La Paz en Bolivia (Centro del Colegio Franco Boliviano Alcide d’Orbigny). A partir de cierto grado de su desarrollo, este estudio abarca otras escuelas de la red de centros A.E.F.E ubicadas en el continente suramericano.La interlengua de los alumnos que en este contexto inician su aprendizaje a una edad temprana constituye la matriz en la que se fundamenta este trabajo de teorización.Gran parte de la tesis se centra en el análisis de las interacciones lingüísticas en las clases de francés, de español y en la clase bilingüe, a fin de potenciar la comprensión de los recursos pedagógicos utilizados por los docentes para plantear fenómenos lingüísticos y, en particular, las interferencias lingüísticas que los caracterizan. Siendo así, este análisis se fija en la dinámica de articulación entre la lengua nacional y la lengua francesa en las prácticas educativas cotidianas.A partir de reflexiones teóricas y de experiencias directas, esta investigación cuestiona, por una parte, el tener presentes ciertas consideraciones didácticas necesarias en el planteamiento convergente de una enseñanza curricular, y, por otra, la conceptualización y la aplicación de un currículo de capacitación docente en didáctica convergente.

A criptografia de chave pública sem certificado (certificateless) é uma alternativa ao modelo convencional de criptografia assimétrica, pois a autenticação da chave pública ocorre implicitamente durante a execução dos protocolos, sem a necessidade de gerenciamento e distribuição de certificados digitais. Potencialmente reduz custos computacionais e o nível de segurança alcançado é maior quando comparado ao modelo baseado em identidade. Nesta tese de doutorado, modelos formais de segurança para acordo de chave com autenticação sem certificado são aprimorados visando dois objetivos paralelos: (1) aumentar o nível de confiança que usuários podem depositar na autoridade geradora de chaves secretas parciais e (2) viabilizar protocolos que sejam eficientes computacionalmente e com propriedades de segurança relevantes, dentre as quais se inclui resistência a ataques de adversários que têm total controle do canal de comunicação e que podem substituir chaves públicas de usuários por valores arbitrários. Para atestar que as melhorias efetuadas são praticáveis e possibilitam que os objetivos sejam alcançados, novos protocolos são propostos para o caso que envolve dois participantes na comunicação. Os protocolos são provados seguros, usando-se técnica de redução de problemas computacionais. / Certificateless public key cryptography is an alternative model to traditional asymmetric key cryptography, because the public key authentication occurs implicitly during a protocol run, with no need of digital certificates management and distribution. It has the potential to reduce computing costs, and it allows a higher security level than the one in the identity-based model. In this PhD thesis, formal security models for certificateless authenticated key agreement are improved with two independent objectives: (1) to increase the trust level for the partial secret key generating authority on which users rely, and (2) to enable computationally efficient protocols, with significant security properties, such as resistance against attacks from adversaries with full control of the communication channel, and from adversaries who are able to replace users\' public keys by any chosen value. In order to demonstrate that these improvements made are feasible and achieve the objectives, new protocols are proposed in the two-party case. These protocols are proved secure by using reduction techniques for provable security.

A criptografia de chave pública sem certificado (certificateless) é uma alternativa ao modelo convencional de criptografia assimétrica, pois a autenticação da chave pública ocorre implicitamente durante a execução dos protocolos, sem a necessidade de gerenciamento e distribuição de certificados digitais. Potencialmente reduz custos computacionais e o nível de segurança alcançado é maior quando comparado ao modelo baseado em identidade. Nesta tese de doutorado, modelos formais de segurança para acordo de chave com autenticação sem certificado são aprimorados visando dois objetivos paralelos: (1) aumentar o nível de confiança que usuários podem depositar na autoridade geradora de chaves secretas parciais e (2) viabilizar protocolos que sejam eficientes computacionalmente e com propriedades de segurança relevantes, dentre as quais se inclui resistência a ataques de adversários que têm total controle do canal de comunicação e que podem substituir chaves públicas de usuários por valores arbitrários. Para atestar que as melhorias efetuadas são praticáveis e possibilitam que os objetivos sejam alcançados, novos protocolos são propostos para o caso que envolve dois participantes na comunicação. Os protocolos são provados seguros, usando-se técnica de redução de problemas computacionais. / Certificateless public key cryptography is an alternative model to traditional asymmetric key cryptography, because the public key authentication occurs implicitly during a protocol run, with no need of digital certificates management and distribution. It has the potential to reduce computing costs, and it allows a higher security level than the one in the identity-based model. In this PhD thesis, formal security models for certificateless authenticated key agreement are improved with two independent objectives: (1) to increase the trust level for the partial secret key generating authority on which users rely, and (2) to enable computationally efficient protocols, with significant security properties, such as resistance against attacks from adversaries with full control of the communication channel, and from adversaries who are able to replace users\' public keys by any chosen value. In order to demonstrate that these improvements made are feasible and achieve the objectives, new protocols are proposed in the two-party case. These protocols are proved secure by using reduction techniques for provable security.

Alors qu’il existe de nombreux calculs microscopiques de barrières de fission pour des noyaux composés pair-pairs, il n’y a cependant que relativement peu de tels calculs pour des noyaux de masse impaire. Ceci est dû aux complications induites par la brisure de la symétric de reversement du sens du temps au niveau du champ moyen qui est engendrée par la présence d’un nucleon non apparié. Pour éviter cette difficulté, des calculs existants pour des noyaux de masse impaire ont tout simplement négligé ces effets de brisure de la symétrie de reversement du sens du temps.Dans ce travail, on se donne pour but d’améliorer la description des barrières de fission, aussi bien que des propriétés spectroscopiques du niveau fondamental et de l’état isomérique de fission,pour quelques isotopes de masse impaire dans la région des actinides en prenant en compte de tels effets. Ceci a été réalisé dans le cadre du formalisme de Skyrme–Hartree–Fock plus BCS avec blocking en adaptant ce formalisme à la brisure de la symétrie considérée. L’interaction résiduelle d’appariement a été approchée par une force de séniorité dont les paramètres ont été ajustés pour reproduire les différences de masse pair-impair de quelques noyaux de la région des actinides.Les énergies des têtes de bande rotationnelle de basse énergie ont été calculées dans le cadre du modèle unifié de Bohr-Mottelson pour quatre noyaux bien déformés (235U, 239Pu, 237Np, 241Am)produisant un bon accord qualitatif avec les données pour les noyaux impairs en neutrons. L’accord significativement moins bon obtenu pour les noyaux impairs en protons pourrait résulter de l’usage de l’approximation de Slater pour l’interaction d’échange de Coulomb. Les énergies de déformation de deux noyaux impairs en neutrons (235U, 239Pu) ont été calculées pour quelques configurations de particule individuelle, jusqu’après la barrières de fission externe. La symétrie axiale a été imposée tandis que la brisure de la symétrie droite-gauche (ou de parité intrinsèque) a été permise dans la région de la seconde barrière. Les hauteurs des barrières de fission pour ces noyaux impairs dépendent significativement des configurations de particule individuelle. Un accord qualitatif avec les données disponibles pour les hauteurs de barrières des noyaux impairs considérés et leurs voisins pair-pairs a été généralement obtenu. / While there have been numerous microscopic calculations on fission barriers of even-even compoundnuclei, there are however, relatively few such work dedicated to odd-mass nuclei. This is dueto the complications posed by the breaking of the time-reversal symmetry at the mean-field leveldue to the presence of an unpaired nucleon. In order to circumvent this difficulty, previous fission barriercalculations of odd-mass nuclei have been performed by neglecting the effect of time-reversalsymmetry breaking. This work aims to improve on the description of fission barriers as well asthe spectroscopic properties of ground and fission-isomeric state, of some odd-mass actinide nucleiby taking the effect of time-reversal symmetry breaking into account. This has been perfomedwithin a Skyrme-Hartree-Fock-plus-BCS framework with blocking, where the BCS formalism hasbeen adapted to accomodate this symmetry breaking. The Skyrme nucleon-nucleon effective forcehas been used with various sets of parameters (SIII, SkM*, SLy5*). The residual pairing interactionhas been approximated by seniority forces whose neutron and proton parameters have beenfitted to reproduce the odd-even mass differences of some actinide nuclei. The low-lying rotationalband-head energies evaluated within the Bohr-Mottelson unified model have been determined forfour well-deformed odd-nuclei (235U, 239Pu, 237Np, 241Am) yielding a good qualitative agreementto the data for odd-neutron nuclei. The agreement was significantly less good for the odd-protonnuclei, possibly due to the use of the Slater approximation for the exchange Coulomb interaction.The deformation energies of two odd-neutron nuclei (235U and 239Pu) have been calculated forsome single-particle configurations up to a point beyond the outer fission-barrier. Axial symmetrynuclear shape has been assumed while a breaking of the left-right (or intrinsic parity) symmetryhas been allowed around the outer fission-barrier. The fission-barrier heights of such odd-neutronnuclei depend significantly on the particle configurations. A special attention has been paid tothe very important rotational correction to deformation energies. In particular, the correction ofthe moment of inertia calculated from the usual Belyaev expression was considered. Overall, aqualitative agreement with available data on fission-barrier heights for the considered odd-neutronnuclei and their even neighbours has been obtained.