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Contorted polycyclic aromatic hydrocarbons have found increasing utility in the application of molecular electronics due to the surpamolecular properties that result from these non-planar structures. The [n]circulene series of molecules are particularly attractive members of the contorted aromatic family due to the unique structural implications that result from their changing value of n. For example, when n ≤ 5, the structures adopt a bowl-like shape; when n = 6, a planar structure is observed; and when 7 ≤ n ≤ 16, the compounds assume a saddle-like shape. Very few molecules exhibit the structural contortions that these contorted aromatics do – primarily because aromatic molecules desire to adopt highly planar conformations. Following the model of aromaticity developed by Erich Clar, we set our sights on the synthesis of tetrabenzo[8]circulene, the stabilized form of [8]circulene established through the addition of four fused benzenoid rings around the periphery of the molecule. The initial approach towards this structure employs a Diels-Alder [4 + 2] cycloaddition reaction and a palladium catalyzed arylation reaction as the key transformation steps. The results of these studies were promising, establishing the structural characterization of this new molecule and providing access to functionalized derivatives of the saddle-shaped structure. However, access towards these functionalized derivatives proved limiting, compelling us to investigate alternative synthetic methodologies. In the course of our studies, we established a new methodology towards 2,5-diarylthiophene-1-oxides, a key precursor to the Diels-Alder cycloaddition reaction. These reactive dienes are prepared from readily available arylacetylene precursors via zirconacyclopentadiene intermediates. The isolated yields of the desired thiophene-1-oxides are comparable to those obtained from previously established oxidation strategies while avoiding the formation of over-oxidation products. Of significant importance to scope of our work, this newly established methodology offers broader versatility providing products outfitted with electron-donating or electron-withdrawing groups. These new methodologies provided access to functionalized derivatives of the saddle-shaped molecule tetrabenzo[8]circulene in improved yield when coupled with a revised Diels-Alder/oxidative cyclodehydrogenation approach. This methodology affords products containing both electron-rich and electron-poor functional groups in a more efficient manner. The optoelectronic effects that result from the introduction of this functionality and investigations into the development of larger contorted aromatic systems are also discussed.

Research towards the development of a gas-discharge fibre laser using noble gases, with target emission wavelengths in the mid-IR. Additional and separate work on gas treatment methods for managing the formation of photo-induced defects in silica glass.

Sejam M uma variedade de Hadamard com curvatura seccional KM ≤ −k2 < 0 e ∂ M sua fronteira assintótica. Dizemos que M satisfaz a condição de convexidade estrita se, dados x ∈ ∂∞M e W ⊂ ∂∞M aberto relativo contendo x, existe um aberto Ω ⊂ M de classe C2 tais que x ∈ Int (∂ Ω) ⊂ W e M \ Ω ´e convexo. Provamos que a condição de convexidade estrita implica que M éregular no infinito com relação ao operador Q[u] := div a(|∇u|) \ |∇u| ∇u definido no espa¸co de Sobolev W 1,p(M ), onde a ∈ C1([0, +∞)) satisfaz a(0) = 0, at(s) > 0 para todo s > 0, a(s) ≤ C (sp−1 + 1), ∀s ≥ 0, onde C > 0 é uma constante, e a(s) ≥ sq para algum q > 0 e para s ≈ 0 e supomos que é possível resolver problemas de Dirichlet em bolas (compactas) de M com dados contínuos no bordo. Segue disto que sob a condição de convexidade estrita, os problemas de Dirichlet para equação de hipersuperfície mínima e para o p-laplaciano, p > 1, são solúveis para qualquer dado contínuo prescrito no bordo assintótico. Também provamos que se M é rotacionalmente simétrica ou se inf BR+1 KM ≥ −e 2kR /R2+2 , R ≥ R∗, para certos R∗ e E > 0, então M satisfaz a condição de convexidade estrita. / Let M be Hadamard manifold with sectional curvature KM ≤ −k2, k > 0 and ∂∞M its asymptotic boundary. We say that M satisfies the strict convexity condition if, given x ∈ ∂∞M and a relatively open subset W ⊂ 2 ∂∞M containing x, there exists a C open subset Ω ⊂ M such that x ∈ Int (∂∞Ω) ⊂ W and M \ Ω is convex. We prove that the strict convexity condition implies that M is regular at infinity relative to the operator Q [u] := div a(|∇u|) \ |∇u| ∇u , defined on the Sobolev space W 1,p(M ), where a ∈ C 1 ([0, ∞)) satisfies a(0) = 0, at(s) > 0 for all s > 0, a(s) ≤ C (s p−1 + 1), ∀s ≥ 0, where C > 0 is a constant, and a(s) ≥ sq , for some q > 0 and for s ≈ 0 and we suppose that it is possible to solve Dirichlet problems on (compact) balls of M with continuous boundary data. It follows that under the strict convexity condition, the Dirichlet problems for the minimal hypersurface and the p-Laplacian, p > 1, equations are solvable for any prescribed continuous asymptotic boundary data. We also prove that if M is rotationally symmetric or if inf BR+1 KM ≥ −e2kR/R2+2 , R ≥ R∗, for some R∗ and E > 0, then M satisfies the SC condition.

Sejam M uma variedade de Hadamard com curvatura seccional KM ≤ −k2 < 0 e ∂ M sua fronteira assintótica. Dizemos que M satisfaz a condição de convexidade estrita se, dados x ∈ ∂∞M e W ⊂ ∂∞M aberto relativo contendo x, existe um aberto Ω ⊂ M de classe C2 tais que x ∈ Int (∂ Ω) ⊂ W e M \ Ω ´e convexo. Provamos que a condição de convexidade estrita implica que M éregular no infinito com relação ao operador Q[u] := div a(|∇u|) \ |∇u| ∇u definido no espa¸co de Sobolev W 1,p(M ), onde a ∈ C1([0, +∞)) satisfaz a(0) = 0, at(s) > 0 para todo s > 0, a(s) ≤ C (sp−1 + 1), ∀s ≥ 0, onde C > 0 é uma constante, e a(s) ≥ sq para algum q > 0 e para s ≈ 0 e supomos que é possível resolver problemas de Dirichlet em bolas (compactas) de M com dados contínuos no bordo. Segue disto que sob a condição de convexidade estrita, os problemas de Dirichlet para equação de hipersuperfície mínima e para o p-laplaciano, p > 1, são solúveis para qualquer dado contínuo prescrito no bordo assintótico. Também provamos que se M é rotacionalmente simétrica ou se inf BR+1 KM ≥ −e 2kR /R2+2 , R ≥ R∗, para certos R∗ e E > 0, então M satisfaz a condição de convexidade estrita. / Let M be Hadamard manifold with sectional curvature KM ≤ −k2, k > 0 and ∂∞M its asymptotic boundary. We say that M satisfies the strict convexity condition if, given x ∈ ∂∞M and a relatively open subset W ⊂ 2 ∂∞M containing x, there exists a C open subset Ω ⊂ M such that x ∈ Int (∂∞Ω) ⊂ W and M \ Ω is convex. We prove that the strict convexity condition implies that M is regular at infinity relative to the operator Q [u] := div a(|∇u|) \ |∇u| ∇u , defined on the Sobolev space W 1,p(M ), where a ∈ C 1 ([0, ∞)) satisfies a(0) = 0, at(s) > 0 for all s > 0, a(s) ≤ C (s p−1 + 1), ∀s ≥ 0, where C > 0 is a constant, and a(s) ≥ sq , for some q > 0 and for s ≈ 0 and we suppose that it is possible to solve Dirichlet problems on (compact) balls of M with continuous boundary data. It follows that under the strict convexity condition, the Dirichlet problems for the minimal hypersurface and the p-Laplacian, p > 1, equations are solvable for any prescribed continuous asymptotic boundary data. We also prove that if M is rotationally symmetric or if inf BR+1 KM ≥ −e2kR/R2+2 , R ≥ R∗, for some R∗ and E > 0, then M satisfies the SC condition.

Sejam M uma variedade de Hadamard com curvatura seccional KM ≤ −k2 < 0 e ∂ M sua fronteira assintótica. Dizemos que M satisfaz a condição de convexidade estrita se, dados x ∈ ∂∞M e W ⊂ ∂∞M aberto relativo contendo x, existe um aberto Ω ⊂ M de classe C2 tais que x ∈ Int (∂ Ω) ⊂ W e M \ Ω ´e convexo. Provamos que a condição de convexidade estrita implica que M éregular no infinito com relação ao operador Q[u] := div a(|∇u|) \ |∇u| ∇u definido no espa¸co de Sobolev W 1,p(M ), onde a ∈ C1([0, +∞)) satisfaz a(0) = 0, at(s) > 0 para todo s > 0, a(s) ≤ C (sp−1 + 1), ∀s ≥ 0, onde C > 0 é uma constante, e a(s) ≥ sq para algum q > 0 e para s ≈ 0 e supomos que é possível resolver problemas de Dirichlet em bolas (compactas) de M com dados contínuos no bordo. Segue disto que sob a condição de convexidade estrita, os problemas de Dirichlet para equação de hipersuperfície mínima e para o p-laplaciano, p > 1, são solúveis para qualquer dado contínuo prescrito no bordo assintótico. Também provamos que se M é rotacionalmente simétrica ou se inf BR+1 KM ≥ −e 2kR /R2+2 , R ≥ R∗, para certos R∗ e E > 0, então M satisfaz a condição de convexidade estrita. / Let M be Hadamard manifold with sectional curvature KM ≤ −k2, k > 0 and ∂∞M its asymptotic boundary. We say that M satisfies the strict convexity condition if, given x ∈ ∂∞M and a relatively open subset W ⊂ 2 ∂∞M containing x, there exists a C open subset Ω ⊂ M such that x ∈ Int (∂∞Ω) ⊂ W and M \ Ω is convex. We prove that the strict convexity condition implies that M is regular at infinity relative to the operator Q [u] := div a(|∇u|) \ |∇u| ∇u , defined on the Sobolev space W 1,p(M ), where a ∈ C 1 ([0, ∞)) satisfies a(0) = 0, at(s) > 0 for all s > 0, a(s) ≤ C (s p−1 + 1), ∀s ≥ 0, where C > 0 is a constant, and a(s) ≥ sq , for some q > 0 and for s ≈ 0 and we suppose that it is possible to solve Dirichlet problems on (compact) balls of M with continuous boundary data. It follows that under the strict convexity condition, the Dirichlet problems for the minimal hypersurface and the p-Laplacian, p > 1, equations are solvable for any prescribed continuous asymptotic boundary data. We also prove that if M is rotationally symmetric or if inf BR+1 KM ≥ −e2kR/R2+2 , R ≥ R∗, for some R∗ and E > 0, then M satisfies the SC condition.

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Cette thèse à pour objet l’étude des résonances du laplacien sur les variétés à pointes. Ce sont des variétés dont les bouts sont des pointes hyperboliques réelles. Ces objets ont été introduits par Selberg pour les surfaces à pointes de courbure constante dans les années 50. Leur définition a ensuite été étendue en courbure variable par Lax et Phillips. Les résonances sont les poles d’une famille méromorphe de fonctions propres généralisées du laplacien. Elles sont associées au spectre continu du laplacien. Pour analyser ce spectre continu, plusieurs directions de recherche sont explorées ici. D’une part, on obtient des résultats sur la localisation de ces résonances. En particulier, si la courbure est négative, on montre que pour un ensemble générique de métriques, les résonances se séparent en deux ensembles. Le premier est contenu dans une bande près du spectre continu. L’autre partie est composé de résonances qui s’éloignent du spectre. Ceci laisse une zone de taille log sans résonance.D’autre part, on étudie les mesures microlocales associées à certaines suites de paramètre spectraux. En particulier, on montre que pour des suites de paramètres spectraux qui s’approche du spectre, mais pas trop vite, la mesure microlocale associée est nécessairement la mesure de Liouville. Cette propriété est valable quand la courbure de la variété est négative. / In this thesis, we study the resonances of the Laplace operator on cusp manifolds. They are manifolds whose ends are real hyperbolic cusps. The resonances were introduced by Selberg in the 50's for the constant curvature cusp surfaces. Their definition was later extended to the case of variable curvature by Lax and Phillips. The resonances are the poles of a meromorphic family of generalized eigenfunctions of the Laplace operator. They are associated to the continuous spectrum of the Laplace operator. To analyze this continuous spectrum, different directions of research are investigated.On the one hand, we obtain results on the localization of resonances. In particular, if the curvature is negative, for a generic set of metrics, they split into two sets. The first one is included in a band near the spectrum. The other is composed of resonances that are far from the spectrum. This leaves a log zone without resonances. On the other hand, we study the microlocal measures associated to certain sequences of spectral parameters. In particular we show that for some sequences of parameters that converge to the spectrum, but not too fast, the associated microlocal measure has to be the Liouville measure. This property holds when the curvature is negative.

Στην παρούσα διατριβή μελετάμε το πρόβλημα της βελτιστοποίησης μη γραμμικών συναρτήσεων πολλών μεταβλητών, όπου η αντικειμενική συνάρτηση είναι συνεχώς διαφορίσιμη σε ένα ανοιχτό υποσύνολο του Rn. Αναπτύσσουμε μαθηματικές μεθόδους βελτιστοποίησης αποσκοπώντας στην επίλυση προβλημάτων μεγάλης κλίμακας, δηλαδή προβλημάτων των οποίων οι μεταβλητές είναι πολλές χιλιάδες, ακόμα και εκατομμύρια. Η βασική ιδέα των μεθόδων που αναπτύσσουμε έγκειται στη θεωρητική μελέτη των χαρακτηριστικών μεγεθών των Quasi-Newton ενημερώσεων ελάχιστης και μικρής μνήμης. Διατυπώνουμε θεωρήματα αναφορικά με το χαρακτηριστικό πολυώνυμο, τον αριθμό των διακριτών ιδιοτιμών και των αντίστοιχων ιδιοδιανυσμάτων. Εξάγουμε κλειστούς τύπους για τον υπολογισμό των ανωτέρω ποσοτήτων, αποφεύγοντας τόσο την αποθήκευση όσο και την παραγοντοποίηση πινάκων. Τα νέα θεωρητικά απoτελέσματα εφαρμόζονται αφενός μεν στην επίλυση μεγάλης κλίμακας υποπροβλημάτων περιοχής εμπιστοσύνης, χρησιμοποιώντας τη μέθοδο της σχεδόν ακριβούς λύσης, αφετέρου δε, στην καμπυλόγραμμη αναζήτηση, η οποία χρησιμοποιεί ένα ζεύγος κατευθύνσεων μείωσης, την Quasi-Newton κατεύθυνση και την κατεύθυνση αρνητικής καμπυλότητας. Η νέα μέθοδος μειώνει δραστικά τη χωρική πολυπλοκότητα των γνωστών αλγορίθμων του μη γραμμικού προγραμματισμού, διατηρώντας παράλληλα τις καλές ιδιότητες σύγκλισής τους. Ως αποτέλεσμα, οι προκύπτοντες νέοι αλγόριθμοι έχουν χωρική πολυπλοκότητα Θ(n). Τα αριθμητικά αποτελέσματα δείχνουν ότι οι νέοι αλγόριθμοι είναι αποδοτικοί, γρήγοροι και πολύ αποτελεσματικοί όταν χρησιμοποιούνται στην επίλυση προβλημάτων με πολλές μεταβλητές. / In this thesis we study the problem of minimizing nonlinear functions of several variables, where the objective function is continuously differentiable on an open subset of Rn. We develop mathematical optimization methods for solving large scale problems, i.e., problems whose variables are many thousands, even millions. The proposed method is based on the theoretical study of the properties of minimal and low memory Quasi-Newton updates. We establish theorems concerning the characteristic polynomial, the number of distinct eigenvalues and corresponding eigenvectors. We derive closed formulas for calculating these quantities, avoiding both the storage and factorization of matrices. The new theoretical results are applied in the large scale trust region subproblem for calculating nearly exact solutions as well as in a curvilinear search that uses a Quasi-Newton and a negative curvature direction. The new method is drastically reducing the spatial complexity of known algorithms of nonlinear programming. As a result, the new algorithms have spatial complexity Θ(n), while they are maintaining good convergence properties. The numerical results show that the proposed algorithms are efficient, fast and very effective when used in solving large scale problems.