Conventional correlation methods suffer from the slow convergence of electron correlation energies with respect to the size of orbital expansions. This problem is due to the fact that orbital products alone cannot describe the behavior of the exact wave function at short inter-electronic distances. Explicitly correlated methods overcome this basis set problem by including the inter-electronic distances (rij) explicitly in wave function expansions. Here, the origin of the basis set problem of conventional wave function methods is reviewed, and a short history of explicitly correlated methods is presented. The F12 methods are the focus herein, as they are the most practical explicitly correlated methods to date. Moreover, some of the key developments in modern F12 technology, which have significantly improved the efficiency and accuracy of these methods, are also reviewed. In this work, the extension of the perturbative coupled-cluster F12 method, CCSD(T)F12, developed in our group for the treatment of high-spin open-shell molecules (J. Zhang and E. F. Valeev, J. Chem. Theory Comput., 2012, 8, 3175.), is also documented. Its performance is assessed for accurate prediction of chemical reactivity. The reference data include reaction barrier heights, electronic reaction energies, atomization energies, and enthalpies of formation from the following sources: (1) the DBH24/08 database of 22 reaction barriers (Truhlar et al., J. Chem. Theory Comput., 2007, 3, 569.), (2) the HJO12 set of isogyric reaction energies (Helgaker et al., Modern Electronic Structure Theory, Wiley, Chichester, first ed., 2000.), and (3) the HEAT set of atomization energies and heats of formation (Stanton et al., J. Chem. Phys., 2004, 121, 11599.). Two types of analyses were performed, which target the two distinct uses of explicitly correlated CCSD(T) models: as a replacement for the basis-set-extrapolated CCSD(T) in highly accurate composite methods like HEAT and as a distinct model chemistry for standalone applications. Hence, (1) the basis set error of each component of the CCSD(T)F12 contribution to the chemical energy difference in question and (2) the total error of the CCSD(T)F12 model chemistry relative to the benchmark values are analyzed in detail. Two basis set families were utilized in the calculations: the standard aug-cc-p(C)VXZ (X = D, T, Q) basis sets for the conventional correlation methods and the cc-p(C)VXZ-F12 (X = D, T, Q) basis sets of Peterson and co-workers that are specifically designed for explicitly correlated methods. The conclusion is that the performance of the two families for CCSD correlation contributions (which are the only components affected by the explicitly correlated terms in our formulation) are nearly identical with triple- and quadruple-ζ quality basis sets, with some differences at the double-ζ level. Chemical accuracy (~4.18 kJ/mol) for reaction barrier heights, electronic reaction energies, atomization energies, and enthalpies of formation is attained, on average, with the aug-cc-pVDZ, aug-cc-pVTZ, cc- pCVTZ-F12/aug-cc-pCVTZ, and cc-pCVDZ-F12 basis sets, respectively, at the CCSD(T)F12 level of theory. The corresponding mean unsigned errors are 1.72 kJ/ mol, 1.5 kJ/mol, ~ 2 kJ/mol, and 2.17 kJ/mol, and the corresponding maximum unsigned errors are 4.44 kJ/mol, 3.6 kJ/mol, ~ 5 kJ/mol, and 5.75 kJ/mol. In addition to accurate energy calculations, our studies were extended to the computation of molecular properties with the MP2-F12 method, and its performance was assessed for prediction of the electric dipole and quadrupole moments of the BH, CO, H2O, and HF molecules (J. Zhang and E. F. Valeev, in preparation for submission). First, various MP2- F12 contributions to the electric dipole and quadrupole moments were analyzed. It was found that the unrelaxed one-electron density contribution is much larger than the orbital response contribution in the CABS singles correction, while both contributions are important in the MP2 correlation contribution. In contrast, the majority of the F12 correction originates from orbital response effects. In the calculations, the two basis set families, the aug-cc-pVXZ (X = D, T, Q) and cc-pVXZ-F12 (X = D, T, Q) basis sets, were also employed. The two basis set series show noticeably different performances at the double-ζ level, though the difference is smaller at triple- and quadruple-ζ levels. In general, the F12 calculations with the aug-cc- pVXZ series give better results than those with the cc-pVXZ-F12 family. In addition, the contribution of the coupling from the MP2 and F12 corrections was investigated. Although the computational cost of the F12 calculations can be significantly reduced by neglecting the coupling terms, this does increase the errors in most cases. With the MP2-F12C/aug-cc-pVDZ calculations, dipole moments close to the basis set limits can be obtained; the errors are around 0.001 a.u. For quadrupole moments, the MP2-F12C/aug-cc-pVTZ calculations can accurately approximate the MP2 basis set limits (within 0.001 a.u.). / Ph. D.

Accurate correlated electronic structure methods involve a significant amount of computations and can be only employed to small molecular systems. For example, the coupled-cluster singles, doubles, and perturbative triples model (CCSD(T)), which is known as the ``gold standard" of quantum chemistry for its accuracy, usually can treat molecules with 20-30 atoms. To extend the reach of accurate correlated electronic structure methods to larger molecular systems, we work towards two directions: parallel computing and reduced-cost/scaling approaches. Parallel computing can utilize more computational resources to handle systems that demand more substantial computational efforts. Reduced-cost/scaling approaches, which introduce approximations to the existing electronic structure methods, can significantly reduce the amount of computation and storage requirements. In this work, we introduce a new distributed-memory massively parallel implementation of standard and explicitly correlated (F12) coupled-cluster singles and doubles (CCSD) with canonical bigO{N^6} computational complexity ( C. Peng, J. A. Calvin, F. Pavov{s}evi'c, J. Zhang, and E. F. Valeev, textit{J. Phys. Chem. A} 2016, textbf{120}, 10231.), based on the TiledArray tensor framework. Excellent strong scaling is demonstrated on a multi-core shared-memory computer, a commodity distributed-memory computer, and a national-scale supercomputer. We also present a distributed-memory implementation of the density-fitting (DF) based CCSD(T) method. (C. Peng, J. A. Calvin, and E. F. Valeev, textit{in preparation for submission}) An improved parallel DF-CCSD is presented utilizing lazy evaluation for tensors with more than two unoccupied indices, which makes the DF-CCSD storage requirements always smaller than those of the non-iterative triples correction (T). Excellent strong scaling is observed on both shared-memory and distributed-memory computers equipped with conventional Intel Xeon processors and the Intel Xeon Phi (Knights Landing) processors. With the new implementation, the CCSD(T) energies can be evaluated for systems containing 200 electrons and 1000 basis functions in a few days using a small size commodity cluster, with even more massive computations possible on leadership-class computing resources. The inclusion of F12 correction to the CCSD(T) method makes it converge to basis set limit much more rapidly. The large-scale parallel explicitly correlated coupled-cluster program makes the accurate estimation of the coupled-cluster basis set limit for molecules with 20 or more atoms a routine. Thus, it can be used rigorously to test the emerging reduced-scaling coupled-cluster approaches. Moreover, we extend the pair natural orbital (PNO) approach to excited states through the equation-of-motion coupled cluster singles and doubles (EOM-CCSD) method. (C. Peng, M. C. Clement, and E. F. Valeev, textit{submitted}) We simulate the PNO-EOM-CCSD method using an existing massively parallel canonical EOM-CCSD program. We propose the use of state-averaged PNOs, which are generated from the average of the pair density of excited states, to span the PNO space of all the excited states. The doubles amplitudes in the CIS(D) method are used to compute the state-averaged pair density of excited states. The issue of incorrect states in the state-averaged pair density, caused by an energy reordering of excited states between the CIS(D) and EOM-CCSD, is resolved by simply computing more states than desired. We find that with a truncation threshold of $10^{-7}$, the truncation error for the excitation energy is already below 0.02 eV for the systems tested, while the average number of PNOs is reduced to 50-70 per pair. The accuracy of the PNO-EOM-CCSD method on local, Rydberg and charge transfer states is also investigated. / Ph. D.

Thesis advisor: Geoffrey Sanzenbacher / Despite growing importance in the global economy, many of the countriees with large natural resource economies are among the poorest. In this paper, I first construct a theoretical model that provides a framework for the harm of natural resources on corruption levels and governance. Then, I construct what I call the Resource Volatility Index. This measures both a country's level of dependence on a category of resources and the price volatility of these resources themselves. Finally, I use Correlated Random Effects models to show that both average and year-varying levels of this index can explain the level of corruption and the quality of governance in a given country. The nagative impacts I find on both variables confirms previous economic theory on governments funded by natural resources. / Thesis (BA) — Boston College, 2024. / Submitted to: Boston College. Morrissey School of Arts and Sciences. / Discipline: Economics. / Discipline: Scholar of the College.

2024 / This dissertation focuses on the development of advanced multivariate analysis methods for the analysis of genetics and genomics data with multiple sources of correlations. The dissertation describes three novel topics: (1) a method to learn partial correlation networks, also known as Gaussian Graphical Models, to analyze multi-omics data (2) a sparse network method to reduce network complexity, and (3) a Genome-Wide Association Study pipeline to analyze genome-wide genotype data in longitudinal and familial settings. In the first part of my dissertation I propose a cluster-based Bootstrap algorithm for learning Gaussian Graphical Models from correlated data. The Bootstrap algorithm is validated to effectively control Type I errors without compromising statistical power compared to alternative solutions through extensive simulations in family-based studies. Additionally the algorithm is applied to learn the partial correlation networks of 47 Polygenic Risk Scores generated from genome-wide genotype data in the Long Life Family Study to unveil the complex relationships of these Polygenic Risk Scores. The second part of the dissertation extends the Bootstrap algorithm to learn sparse Gaussian Graphical Models in correlated data. Simulation studies shows that this extended Bootstrap algorithm maintains control over the Type I errors. By varying the values of the tuning parameter, the dynamic changes of networks reveal their contraction and dissection as edges with small partial correlations are systematically removed. The application of this method in real data analysis identifies meaningful clusters in the dynamic changes of the Polygenic Risk Scores and lipids networks. In the third part, I developed a Nextflow Genome-Wide Association Study pipeline, providing a fully automated analysis tool for managing, analyzing, and visualizing genome-wide genotype data for continuous and binary traits with correlated genetics data. Applying this pipeline to investigate processing speed in the Long Life Family Study leads to the identification of 17 rare protective Single Nucleotide Polymorphisms located in/near Retinoic Acid Receptor Beta and Thyroid Hormone Receptor Beta genes on chromosome 3. These findings shed light on potential mechanisms supporting the preservation of processing speed in aging individuals. / 2026-02-11T00:00:00Z

Die vorliegende Arbeit befasst sich mit dem Dünnfilmwachstum der ternären Oxide Na2IrO3, Li2IrO3, Y2Ir2O7 und YBiO3. All diesen oxidischen Materialien ist gemein, dass sie Verwirklichungen sogenannter Topologischer Isolatoren oder Spin-Flüssigkeiten sein könnten. Diese neuartigen Materiezustände versprechen eine zukünftige Anwendung in der Quantencomputation, in magnetischen Speichern und in elektrischen Geräten mit geringer Leistungsaufnahme. Die Herstellung der hier gezeigten Dünnfilme ist daher ein erster Schritt zur Umsetzung dieser Anwendungen in der Zukunft. Alle Dünnfilme werden mittels gepulster Laserplasmaabscheidung auf verschiedenen einkristallinen Substraten hergestellt. Die strukturellen, optischen und elektrischen Eigenschaften der Filme werden mittels etablierter experimenteller Verfahren wie Röntgenbeugung, spektroskopischer Ellipsometrie und elektrischenWiderstandsmessungen untersucht. Die strukturellen Eigenschaften von erstmalig in der Masterarbeit des Authors verwirklichten Na2IrO3-Dünnfilmen können durch Abscheidung einer ZnO-Zwischenschicht deutlich verbessert werden. Einkristalline Li2IrO3-Dünnfilme mit einer definierten Kristallausrichtung werden erstmalig hergestellt. Die Messung der dielektrischen Funktion gibt Einblick in elektronische Anregungen, die gut vergleichbar mit Li2IrO3-Einkristallen und verwandten Iridaten sind. Des Weiteren wird aus den Daten eine optische Energielücke von ungefähr 300 meV bestimmt. In Y2Ir2O7-Dünnfilmen wird eine mögliche (111)-Vorzugsorientierung in Wachstumsrichtung gefunden. Im Vergleich mit der chemischen Lösungsabscheidung zeigen die hier mittels gepulster Laserplasmaabscheidung hergestellten YBiO3-Dünnfilme eine definierte, biaxiale Kristallausrichtung in der Wachstumsebene bei einer deutlich höheren Schichtdicke. Über die gemessene dielektrische Funktion können eine direkte und indirekte Bandlücke bestimmt werden. Deren Größe gibt eine notwendige experimentelle Rückmeldung an theoretische Berechnungen der elektronischen Bandstruktur von YBiO3, welche zur Vorhersage der oben erwähnten, neuartigen Materiezuständen verwendet werden. Nach einer Einleitung und Motivation dieser Arbeit gibt das zweite Kapitel einen Überblick über den gegenwärtigen Forschungsstand der hier untersuchten Materialien. Die folgenden zwei Kapitel beschreiben die Probenherstellung und die verwendeten experimentellen Untersuchungsmethoden. Anschließend werden für jedes Material einzeln die experimentellen Ergebnisse dieser Arbeit diskutiert. Die Arbeit schließt mit einer Zusammenfassung und einem Ausblick. / The present thesis reports on the thin film growth of ternary oxides Na2IrO3, Li2IrO3, Y2Ir2O7 and YBiO3. All of these oxides are candidate materials for the so-called topological insulator and spin liquid, respectively. These states of matter promise future application in quantum computation, and in magnetic memory and low-power electronic devices. The realization of the thin films presented here, thus represents a first step towards these future device applications. All thin films are prepared by means of pulsed laser deposition on various single-crystalline substrates. Their structural, optical and electronic properties are investigated with established experimental methods such as X-ray diffraction, spectroscopic ellipsometry and resistivity measurements. The structural properties of Na2IrO3 thin films, that were previously realized in the author’s M. Sc. thesis for the first time, are improved significantly by deposition of an intermediate ZnO layer. Single-crystalline Li2IrO3 thin films are grown for the first time and exhibit a defined crystal orientation. Measurement of the dielectric function gives insight into electronic excitations that compare well with single crystal samples and related iridates. From the data, an optical energy gap of about 300 meV is obtained. For Y2Ir2O7 thin films, a possible (111) out-of-plane preferential crystal orientation is obtained. Compared to chemical solution deposition, the pulsed laser-deposited YBiO3 thin films presented here exhibit a biaxial in-plane crystal orientation up to a significantly larger film thickness. From the measured dielectric function, a direct and indirect band gap energy is determined. Their magnitude provides necessary experimental feedback for theoretical calculations of the electronic structure of YBiO3, which are used in the prediction of the novel states of matter mentioned above. After the introduction and motivation of this thesis, the second chapter reviews the current state of the science of the studied thin film materials. The following two chapters introduce the sample preparation and the employed experimental methods, respectively. Subsequently, the experimental results of this thesis are discussed for each material individually. The thesis concludes with a summary and an outlook.

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Οι ραγδαία αυξανόμενες απαιτήσεις για ασύρματες ευρείας ζώνης υπηρεσίες και τα πρόσφατα επιτεύγματα στο σχεδιασμό κι υλοποίηση κινητών τερματικών συσκευών με δυνατότητες παροχής υπηρεσιών διαδικτύου επισπεύδουν την εισαγωγή των ασυρμάτων συστημάτων επικοινωνίας τέταρτης γενεάς στην παγκόσμια αγορά. Βασικό ρόλο στην εκπλήρωση των απαιτήσεων για αυξημένο ρυθμό μετάδοσης δεδομένων και ποιότητα υπηρεσιών που έχουν τεθεί από τα συστήματα αυτά, διαδραματίζουν οι χωροχρονικές τεχνικές επεξεργασίας σήματος που εφαρμόζονται στα ασύρματα συστήματα με πολλαπλές κεραίες στον πομπό ή/και στο δέκτη. Ευρέως διαδεδομένα και συνάμα απλά στην υλοποίηση συστήματα πολλαπλών κεραιών είναι οι δέκτες χωρικού διαφορισμού (ΔΧΔ), οι οποίοι παρέχουν τη δυνατότητα αποδοτικής αντιμετώπισης του φαινομένου των διαλείψεων πολυδιόδευσης που εμφανίζονται στο ασύρματο κανάλι, συνδυάζοντας κατάλληλα τα πολλαπλά ληφθέντα αντίγραφα του εκπεμπόμενου σήματος. Η θεωρητικά αναμενόμενη βελτίωση στις επιδόσεις ασυρμάτων συστημάτων που δύνανται να προσφέρουν οι ΔΧΔ σε σύγκριση με τους συμβατικούς δέκτες μονής κεραίας, προϋποθέτει τη στατιστική ανεξαρτησία των διαλείψεων πολυδιόδευσης που εμφανίζονται στις πολλαπλές κεραίες του δέκτη. Σε πρακτικές υλοποιήσεις, όμως, ποικίλες παράμετροι, όπως για παράδειγμα η μικρή απόσταση μεταξύ των πολλαπλών κεραιών του δέκτη, συντελούν ώστε οι διαλείψεις που εμφανίζονται στους κλάδους των ΔΧΔ να είναι αυθαίρετα συσχετισμένες. Η θεωρητική μελέτη επιδόσεων ΔΧΔ που υπόκεινται σε αυθαίρετα συσχετισμένα κανάλια διαλείψεων πολυδιόδευσης, γνωστών ως διαλείψεις μικρής κλίμακας (ΔΜΙΚ), αποτελεί το αντικείμενο έρευνας της παρούσας διδακτορικής διατριβής. Αν και πολυάριθμες ερευνητικές εργασίες ασχολούνται με τη μοντελοποίηση των συσχετισμένων ΔΜΙΚ και της επίδρασής τους στις επιδόσεις ΔΧΔ, η πλειονότητά τους, χρησιμοποιώντας τις στατιστικές ιδιότητες πολυ-μεταβλητών κατανομών, περιορίζεται σε ειδικές μορφές συσχέτισης των διαλείψεων και σε συμβατικές τεχνικές ΔΧΔ. Το γεγονός αυτό οφείλεται, σε μεγάλο βαθμό, στην απουσία απλών στη χρήση και στον υπολογισμό μαθηματικών εκφράσεων για τις στατιστικές ιδιότητες πολυ-μεταβλητών κατανομών με αυθαίρετα συσχετισμένες τυχαίες μεταβλητές (ΤΜ). Στα πλαίσια της διατριβής αυτής επισκοπούνται, αρχικά, οι προταθείσες μαθηματικές εκφράσεις για τις κυριότερες στατιστικές ιδιότητες των πολυ-μεταβλητών κατανομών Rayleigh, Nakagami-m, Weibull και γενικευμένου Γάμα (ΓG) με διάφορες μορφές συσχέτισης και περιγράφονται οι δυνατότητες χρησιμοποίησής τους στη μελέτη επιδόσεων ΔΧΔ που λειτουργούν σε συσχετισμένες ΔΜΙΚ. Κατόπιν, παρουσιάζοντας μια νέα μεθοδολογία δημιουργίας αυθαίρετα συσχετισμένων και μη απαραιτήτως ταυτόσημα κατανεμημένων (ΤΚ) ΤΜ ΓG, η οποία βασίζεται σε αυθαίρετα συσχετισμένες ΤΜ Gauss και στην ειδική κατηγορία των πινάκων Householder για την τριδιαγωνιοποίηση του πίνακα συσχέτισης (ΠΣ) των ΤΜ Gauss, προέκυψαν μια κλειστής μορφής έκφραση άνω φράγματος για την από κοινού συνάρτηση πυκνότητας πιθανότητας (ΣΠΠ) και μια αναλυτική έκφραση άνω φράγματος σε αναπαράσταση απειροσειρών για την από κοινού αθροιστική συνάρτηση κατανομής (ΑΣΚ) αυθαίρετα συσχετισμένων και μη απαραιτήτως ΤΚ ΤΜ ΓG. Τα προταθέντα άνω φράγματα περιέχουν αρκετές γνωστές μαθηματικές εκφράσεις για τις από κοινού ΣΠΠ κι ΑΣΚ ως ειδικές περιπτώσεις. Στη συνέχεια, προσεγγίζοντας τον ΠΣ αυθαίρετα συσχετισμένων ΤΜ Gauss με έναν ειδικής κατηγορίας πίνακα Green, εξάγεται μια κλειστής μορφής έκφραση προσέγγισης για την από κοινού ΣΠΠ αυθαίρετα συσχετισμένων και μη απαραιτήτως ΤΚ ΤΜ ΓG καθώς και μια αναλυτική έκφραση προσέγγισης σε αναπαράσταση απειροσειρών για την από κοινού ΑΣΚ τους. Επίσης, παρουσιάζονται αναλυτικές εκφράσεις σε αναπαραστάσεις απειροσειρών για τις κυριότερες στατιστικές ιδιότητες της τρι-μεταβλητής κατανομής ΓG με αυθαίρετο ΠΣ και μη απαραιτήτως ΤΚ ΤΜ καθώς και της πολυ-μεταβλητής κατανομής ΓG με σταθερό ΠΣ και μη απαραιτήτως ΤΚ ΤΜ. Όλων των μορφών οι προταθείσες αναλυτικές μαθηματικές εκφράσεις για τις ΣΠΠ κι ΑΣΚ της πολυ-μεταβλητής κατανομής ΓG χρησιμοποιούνται για τη μελέτη επιδόσεων δεκτών διαφορισμού επιλογής (ΔΕ), διαφορισμού μέγιστου λόγου (ΔΜΛ) και διαφορισμού μεταγωγής κι εξέτασης (ΔΜκΕ) που υπόκεινται σε ποικίλα περιβάλλοντα αυθαίρετα συσχετισμένων ΔΜΙΚ. Αρχικά, εξάγονται αναλυτικές εκφράσεις άνω φραγμάτων για την πιθανότητα διακοπής επικοινωνίας (ΠΔΕ), τη μέση πιθανότητα σφάλματος συμβόλου (ΜΠΣΣ) διαφόρων σχημάτων διαμόρφωσης και τη μέση χωρητικότητα καναλιού (ΜΧΚ) κατά Shannon δεκτών ΔΕ που λειτουργούν σε περιβάλλον αυθαίρετα συσχετισμένων και μη απαραιτήτως ΤΚ διαλείψεων ΓG. Επίσης, παρουσιάζονται αναλυτικές εκφράσεις για τα ίδια κριτήρια επίδοσης δεκτών ΔΕ με τρεις κεραίες καθώς κι αναλυτικές εκφράσεις προσεγγίσεων για τα κριτήρια επίδοσης δεκτών ΔΕ οποιουδήποτε πλήθους κεραιών. Κατόπιν, εξάγοντας νέες αναλυτικές μαθηματικές εκφράσεις σε αναπαραστάσεις απειροσειρών για τις κυριότερες στατιστικές ιδιότητες του αθροίσματος οποιουδήποτε αριθμού αυθαίρετα συσχετισμένων και ΤΚ ΤΜ Γάμα, προκύπτουν αναλυτικές εκφράσεις για την ΠΔΕ, τη ΜΠΣΣ διαφόρων σχημάτων διαμόρφωσης και τη ΜΧΚ κατά Shannon δεκτών ΔΜΛ που λειτουργούν σε αυθαίρετα συσχετισμένες και ΤΚ διαλείψεις Nakagami-m. Για το ίδιο περιβάλλον διαλείψεων, παρουσιάζονται αναλυτικές εκφράσεις σε αναπαραστάσεις απειροσειρών για την ΠΔΕ και τη ΜΠΣΣ διαφόρων σχημάτων διαμόρφωσης δεκτών ΔΜκΕ οποιουδήποτε πλήθους κεραιών. Η στενότητα των προταθέντων άνω φραγμάτων για τα κριτήρια επίδοσης των δεκτών ΔΕ, ΔΜΛ και ΔΜκΕ που υπόκεινται σε περιβάλλοντα αυθαίρετα συσχετισμένων ΔΜΙΚ, η ορθότητα των αναλυτικών εκφράσεων για τα ίδια κριτήρια κι η ακρίβεια των προταθέντων προσεγγίσεών τους μελετήθηκαν εκτενώς συγκρίνοντας πολυάριθμα αριθμητικά αποτελέσματα των εκφράσεων αυτών με αντίστοιχα αποτελέσματα που προέκυψαν από προσομοιώσεις σε Η/Υ, οι οποίες υλοποιήθηκαν για το σκοπό αυτό. / The rapidly increasing demands for wireless wideband services and the recent advances in the design and implementation of mobile terminal devices with Internet-based service providing capabilities expedite the introduction of fourth generation (4G) wireless communications systems in the international wireless market. These systems are expected to ensure increased data rates and quality of service in an anytime anywhere basis. Wireless systems that utilize multiple antennas at the transmitter and/or receiver as well as space-time signal processing techniques play a fundamental role in accomplishing the demands imposed by 4G wireless communications systems. Well-known multiple-antenna systems that enable simple implementations are space diversity receivers (SDRs). By properly combining the multiple received replicas of the transmitted signal, SDRs are capable of effectively mitigating the detrimental effects of multipath fading, known as small-scale fading (SSF), that is inherent in wireless channels. SDRs are theoretically known to improve wireless system’s performance compared with conventional single-antenna receivers. This improvement requires that the SSF channels among multiple receiver’s antennas are statistically independent. However, in practical implementations, due to several parameters such as for example the small distance among the receiver’s multiple branches, SSF channels are arbitrarily correlated. This doctoral dissertation presents a theoretical performance study of SDRs operating over arbitrarily correlated SSF channels. Although numerous scientific papers deal with correlated SSF channel modeling and the impact of correlated SSF on the performance of SDRs, their vast majority, which utilizes the statistical properties of multivariate distributions for studying SDRs’ performance, is restricted to special forms of fading correlation and conventional SDR techniques. This happens mainly due the fact that there is a lack of simple mathematical expressions for the statistical properties of multivariate distributions with arbitrarily correlated random variables (RVs) in the literature. Within the framework of this dissertation, firstly, the previously proposed mathematical expressions for the most prevalent statistical properties of the multivariate Rayleigh, Nakagami-m, Weibull and generalized Gamma (ΓG) distributions with various forms of correlation are summarized. Moreover, their capabilities of being utilized for the performance study of SDRs operating over correlated SSF are described. Next, by presenting a new methodology for generating arbitrarily correlated and not necessarily identically distributed (ID) ΓG RVs that is based on arbitrarily correlated Gaussian RVs and the special class of Householder matrices for tridiagonalizing the correlation matrix (CM) of Gaussian RVs, a closed-form upper bound expression for the joint probability density function (PDF) and an analytical upper bound expression in infinite series form for the joint cumulative distribution function (CDF) of arbitrarily correlated and not necessarily ID ΓG RVs are derived. The proposed upper bounds contain several known mathematical expressions for the joint PDF and CDF as special cases. In addition, by approximating the CM of arbitrarily correlated Gaussian RVs with the special class of Green’s matrices, a closed-form approximate expression for the joint PDF and an analytical approximate expression in infinite series form for the joint CDF of arbitrarily correlated and not necessarily ID ΓG RVs are obtained. Furthermore, analytical expressions in infinite series form for the most prevalent statistical properties of the trivariate ΓG distribution with an arbitrary CM and not necessarily ID RVs as well as of the multivariate ΓG distribution with a constant CM and not necessarily ID RVs are presented. The proposed analytic mathematical expressions of all forms for the PDF and CDF of the multivariate ΓG distribution are used for the performance study of selection diversity (SD), maximal-ratio diversity (MRD), and switch-and-examine diversity (SED) receivers over various arbitrarily correlated SSF channels. Firstly, analytical upper bound expressions for the outage probability (OP), average symbol error probability (ASEP) for several modulation formats, and average channel capacity (ACC) in Shannon’s sense of SD receivers operating over arbitrarily correlated and not necessarily ID ΓG fading are derived. Moreover, analytical expressions for the same performance criteria of triple-branch SD receivers as well as analytical approximate expressions for the performance criteria of multibranch SD receivers are presented. Next, by obtaining new analytic mathematical expressions in infinite series form for the most prevalent statistical properties of the sum of any number of arbitrarily correlated and ID Gamma RVs, analytical expressions for the OP, ASEP for several modulation formats, and ACC in Shannon’s sense of multibranch MRD receivers operating over arbitrarily correlated and ID Nakagami-m fading are derived. For the same fading conditions, analytical expressions in infinite series form for the OP and ASEP for several modulation formats of multibranch SED receivers are presented. The tightness of the proposed upper bounds for the performance criteria of multibranch SD, MRD, and SED receivers in various arbitrarily correlated SSF environments, the correctness of the analytical expressions for the same criteria, and the accuracy of the proposed approximations for them are studied in depth through comparisons between numerically evaluated results for the expressions and equivalent results obtained by means of computer simulations that were implemented for this purpose.

Die vorliegende Arbeit befasst sich mit dem Dünnfilmwachstum der ternären Oxide Na2IrO3, Li2IrO3, Y2Ir2O7 und YBiO3. All diesen oxidischen Materialien ist gemein, dass sie Verwirklichungen sogenannter Topologischer Isolatoren oder Spin-Flüssigkeiten sein könnten. Diese neuartigen Materiezustände versprechen eine zukünftige Anwendung in der Quantencomputation, in magnetischen Speichern und in elektrischen Geräten mit geringer Leistungsaufnahme. Die Herstellung der hier gezeigten Dünnfilme ist daher ein erster Schritt zur Umsetzung dieser Anwendungen in der Zukunft. Alle Dünnfilme werden mittels gepulster Laserplasmaabscheidung auf verschiedenen einkristallinen Substraten hergestellt. Die strukturellen, optischen und elektrischen Eigenschaften der Filme werden mittels etablierter experimenteller Verfahren wie Röntgenbeugung, spektroskopischer Ellipsometrie und elektrischenWiderstandsmessungen untersucht. Die strukturellen Eigenschaften von erstmalig in der Masterarbeit des Authors verwirklichten Na2IrO3-Dünnfilmen können durch Abscheidung einer ZnO-Zwischenschicht deutlich verbessert werden. Einkristalline Li2IrO3-Dünnfilme mit einer definierten Kristallausrichtung werden erstmalig hergestellt. Die Messung der dielektrischen Funktion gibt Einblick in elektronische Anregungen, die gut vergleichbar mit Li2IrO3-Einkristallen und verwandten Iridaten sind. Des Weiteren wird aus den Daten eine optische Energielücke von ungefähr 300 meV bestimmt. In Y2Ir2O7-Dünnfilmen wird eine mögliche (111)-Vorzugsorientierung in Wachstumsrichtung gefunden. Im Vergleich mit der chemischen Lösungsabscheidung zeigen die hier mittels gepulster Laserplasmaabscheidung hergestellten YBiO3-Dünnfilme eine definierte, biaxiale Kristallausrichtung in der Wachstumsebene bei einer deutlich höheren Schichtdicke. Über die gemessene dielektrische Funktion können eine direkte und indirekte Bandlücke bestimmt werden. Deren Größe gibt eine notwendige experimentelle Rückmeldung an theoretische Berechnungen der elektronischen Bandstruktur von YBiO3, welche zur Vorhersage der oben erwähnten, neuartigen Materiezuständen verwendet werden. Nach einer Einleitung und Motivation dieser Arbeit gibt das zweite Kapitel einen Überblick über den gegenwärtigen Forschungsstand der hier untersuchten Materialien. Die folgenden zwei Kapitel beschreiben die Probenherstellung und die verwendeten experimentellen Untersuchungsmethoden. Anschließend werden für jedes Material einzeln die experimentellen Ergebnisse dieser Arbeit diskutiert. Die Arbeit schließt mit einer Zusammenfassung und einem Ausblick. / The present thesis reports on the thin film growth of ternary oxides Na2IrO3, Li2IrO3, Y2Ir2O7 and YBiO3. All of these oxides are candidate materials for the so-called topological insulator and spin liquid, respectively. These states of matter promise future application in quantum computation, and in magnetic memory and low-power electronic devices. The realization of the thin films presented here, thus represents a first step towards these future device applications. All thin films are prepared by means of pulsed laser deposition on various single-crystalline substrates. Their structural, optical and electronic properties are investigated with established experimental methods such as X-ray diffraction, spectroscopic ellipsometry and resistivity measurements. The structural properties of Na2IrO3 thin films, that were previously realized in the author’s M. Sc. thesis for the first time, are improved significantly by deposition of an intermediate ZnO layer. Single-crystalline Li2IrO3 thin films are grown for the first time and exhibit a defined crystal orientation. Measurement of the dielectric function gives insight into electronic excitations that compare well with single crystal samples and related iridates. From the data, an optical energy gap of about 300 meV is obtained. For Y2Ir2O7 thin films, a possible (111) out-of-plane preferential crystal orientation is obtained. Compared to chemical solution deposition, the pulsed laser-deposited YBiO3 thin films presented here exhibit a biaxial in-plane crystal orientation up to a significantly larger film thickness. From the measured dielectric function, a direct and indirect band gap energy is determined. Their magnitude provides necessary experimental feedback for theoretical calculations of the electronic structure of YBiO3, which are used in the prediction of the novel states of matter mentioned above. After the introduction and motivation of this thesis, the second chapter reviews the current state of the science of the studied thin film materials. The following two chapters introduce the sample preparation and the employed experimental methods, respectively. Subsequently, the experimental results of this thesis are discussed for each material individually. The thesis concludes with a summary and an outlook.

Quasi-one-dimensional quantum models are ideal for theoretically exploring the physical phenomena associated with strong correlations. In this thesis we study three examples where strong correlations play an important role in the static or dynamic properties of the system. Firstly, we examine the behaviour of a doped fermionic two-leg ladder in which umklapp interactions are present. Such interactions arise at special band fillings and can be induced by the formation of charge density wave order in an array of two-leg ladders with long-range (three-dimensional) interactions. For the umklapp which arises from the half-filling of one of the bands, we show that the low-energy theory has a number of phases, including a strong coupling regime in which the dominant fluctuations are superconducting in nature. These superconducting fluctuations carry a finite wave vector – they are the one-dimensional analogue of Fulde-Ferrell-Larkin-Ovchinnikov superconductivity. In a second example, we consider a quantum spin model which captures the essential one-dimensional physics of CoNb₂O₆, a quasi-one-dimensional Ising ferromagnet. Motivated by high-resolution inelastic neutron scattering experiments, we calculate the dynamical structure in the paramagnetic phase and show that a small misalignment of the transverse field can lead to quasi-particle breakdown – a surprising broadening in the single particle mode observed in experiment. Finally, we study the out-of-equilibrium dynamics of a model with tuneable integrability breaking. When integrability is broken by the presence of weak interactions, we show that the system relaxes to a non-thermal state on intermediate time scales, the so-called “prethermalization plateau”. We describe the approximately stationary behaviour in this regime by constructing a generalised Gibbs ensemble with charges deformed to leading order in perturbation theory. Expectation values of these charges are time-independent, but interestingly the charges do not commute with the Hamiltonian to leading order in perturbation theory. Increasing the strength of the integrability breaking interactions leads to behaviour compatible with thermalisation. In each case we use a combination of perturbative analytical calculations and non-perturbative numerical computations to study the problem at hand.

This paper uses data for 255 NUTS-2 European regions over the period 1995-2003 to test the relative explanatory performance of two important rival theories seeking to explain variations in the level of economic development across regions, namely the neoclassical model originating from the work of Solow (1956) and the so-called Wage Equation, which is one of a set of simultaneous equations consistent with the short-run equilibrium of new economic geography (NEG) theory, as described by Fujita, Krugman and Venables (1999). The rivals are non-nested, so that testing is accomplished both by fitting the reduced form models individually and by simply combining the two rivals to create a composite model in an attempt to identify the dominant theory. We use different estimators for the resulting panel data model to account variously for interregional heterogeneity, endogeneity, and temporal and spatial dependence, including maximum likelihood with and without fixed effects, two stage least squares and feasible generalised spatial two stage least squares plus GMM; also most of these models embody a spatial autoregressive error process. These show that the estimated NEG model parameters correspond to theoretical expectation, whereas the parameter estimates derived from the neoclassical model reduced form are sometimes insignificant or take on counterintuitive signs. This casts doubt on the appropriateness of neoclassical theory as a basis for explaining cross-regional variation in economic development in Europe, whereas NEG theory seems to hold in the face of competition from its rival. (authors' abstract)