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This thesis covers different problems that arise due to crystal and pseudospin anisotropy present in 3d and 5d transition metal oxides. We demonstrate that the methods of computational quantum chemistry can be fruitfully used for quantitative studies of such problems. In Chapter 2, Chapter 3, and Chapter 7 we show that it is possible to reliably calculate local multiplet splittings fully ab initio, and therefore help to assign peaks in experimental spectra to corresponding electronic states. In a situation of large number of peaks due to low local symmetry such assignment using semi-empirical methods can be very tedious and non-unique. Moreover, in Chapter 4 we present a computational scheme for calculating intensities as observed in the resonant inelastic X-ray scattering and X-ray absorption experiments. In our scheme highly-excited core-hole states are calculated explicitly taking into account corresponding orbital relaxation and electron polarization. Computed Cu L-edge spectra for the Li2CuO2 compound reproduce all features present in experiment. Unbiased ab initio calculations allow us to unravel a delicate interplay between the distortion of the local ligand cage around the transition metal ions and the anisotropic electrostatic interactions due to second and farther coordination shells. As shown in Chapter 5 and Chapter 6 this interplay can lead to the counter intuitive multiplet structure, single-ion anisotropy, and magnetic g factors. The effect is quite general and may occur in compounds with large difference between charges of metal ions that form anisotropic environment around the transition metal, like Ir 4+ in plane versus Sr 2+ out of plane in the case of Sr2IrO4. An important aspect of the presented study is the mapping of the quantum chemistry results onto simpler physical models, namely extended Heisenberg model, providing an ab initio parametrization. In Chapter 5 we employ the effective Hamiltonian technique for extracting parameters of the anisotropic Heisenberg model with single-ion anisotropy in the case of quenched orbital moment and second-order spin-orbit coupling. Calculated strong easy-axis anisotropy of the same order of magnitude as the symmetric exchange is consistent with experimentally-observer all-in/all-out magnetic order. In Chapter 6 we introduce new flavour of the mapping procedure applicable to systems with first-order spin-orbit coupling, such as 5d 5 iridates based on analysis of the wavefunction and interaction with magnetic field. In Chapter 6 and Chapter 7 we use this new procedure to obtain parameters of the pseudospin anisotropic Heisenberg model. We find large antisymmetric exchange leading to the canted antiferromagnetic state in Sr2IrO4 and nearly ideal one-dimensional Heisenberg behaviour of the CaIrO3, both agree very well with experimental findings.

This thesis covers different problems that arise due to crystal and pseudospin anisotropy present in 3d and 5d transition metal oxides. We demonstrate that the methods of computational quantum chemistry can be fruitfully used for quantitative studies of such problems. In Chapter 2, Chapter 3, and Chapter 7 we show that it is possible to reliably calculate local multiplet splittings fully ab initio, and therefore help to assign peaks in experimental spectra to corresponding electronic states. In a situation of large number of peaks due to low local symmetry such assignment using semi-empirical methods can be very tedious and non-unique. Moreover, in Chapter 4 we present a computational scheme for calculating intensities as observed in the resonant inelastic X-ray scattering and X-ray absorption experiments. In our scheme highly-excited core-hole states are calculated explicitly taking into account corresponding orbital relaxation and electron polarization. Computed Cu L-edge spectra for the Li2CuO2 compound reproduce all features present in experiment. Unbiased ab initio calculations allow us to unravel a delicate interplay between the distortion of the local ligand cage around the transition metal ions and the anisotropic electrostatic interactions due to second and farther coordination shells. As shown in Chapter 5 and Chapter 6 this interplay can lead to the counter intuitive multiplet structure, single-ion anisotropy, and magnetic g factors. The effect is quite general and may occur in compounds with large difference between charges of metal ions that form anisotropic environment around the transition metal, like Ir 4+ in plane versus Sr 2+ out of plane in the case of Sr2IrO4. An important aspect of the presented study is the mapping of the quantum chemistry results onto simpler physical models, namely extended Heisenberg model, providing an ab initio parametrization. In Chapter 5 we employ the effective Hamiltonian technique for extracting parameters of the anisotropic Heisenberg model with single-ion anisotropy in the case of quenched orbital moment and second-order spin-orbit coupling. Calculated strong easy-axis anisotropy of the same order of magnitude as the symmetric exchange is consistent with experimentally-observer all-in/all-out magnetic order. In Chapter 6 we introduce new flavour of the mapping procedure applicable to systems with first-order spin-orbit coupling, such as 5d 5 iridates based on analysis of the wavefunction and interaction with magnetic field. In Chapter 6 and Chapter 7 we use this new procedure to obtain parameters of the pseudospin anisotropic Heisenberg model. We find large antisymmetric exchange leading to the canted antiferromagnetic state in Sr2IrO4 and nearly ideal one-dimensional Heisenberg behaviour of the CaIrO3, both agree very well with experimental findings.

Les nouvelles technologies mises en œuvre actuellement suscitent des demandes croissantes auprès de l’industrie électronique dont la capacité des circuits électroniques et de leurs microprocesseurs croît de façon explosive en suivant la loi de Moore. Le nombre croissant de transistors par unité de surface entraîne des échauffements considérables qui sont nuisibles au bon fonctionnement des systèmes et posent des problèmes d’évacuation de la chaleur générée, de façon très localisée, dans les composants électroniques. Afin de maîtriser les flux de chaleur créés, il est indispensable d’utiliser des matériaux nouveaux capables de conduire très rapidement et efficacement, c’est à dire de façon unidirectionnelle, la chaleur vers un puits thermique. Les travaux présentés dans cette thèse s’inscrivent dans cette problématique et proposent l’étude de matériaux, isolants électriques, afin d’éviter des courts circuits dans la fabrication de composants électroniques, mais aussi présentant une conductivité thermique fortement anisotrope afin d’évacuer la chaleur dans une seule direction. Pour cela des matériaux très conducteurs, à l’état monocristallin, sont nécessaires. Pour réaliser des mesures de conductivité thermique dans les meilleures conditions, de tels échantillons, d’excellente qualité et parfaitement homogènes ont été synthétisés. Pour obtenir une telle qualité d’échantillons, la méthode de la zone solvante (TSZM : Travelling Solvent Zone Method) a été utilisée. Cette méthode de croissance cristalline, n’utilisant pas de creuset, permet l’obtention de monocristaux exempts d’impuretés, de plusieurs centimètres de longueur. Les matériaux étudiés dans ce travail sont les cuprates de basse dimensionnalité Sr2CuO3, SrCuO2 et La5Ca9Cu24O41 présentant dans leur structure un arrangement d’ions cuivre Cu2+, de spin ½, sous forme de chaînes linéaires ou d’échelles, présentant un caractère 1D marqué. Leur conductivité thermique, dans la direction 1D, est décrite par la somme de deux contributions, l’une, phononique et, l’autre, d’origine magnétique, liée aux spins des ions cuivre. Pour obtenir une meilleure compréhension des différents mécanismes d’interaction en compétition, l’influence de la pureté de ces composés ainsi que celle du dopage sur le site des ions Cu2+ sur la conduction thermique d’origine magnétique, a été étudiée. La pureté des échantillons joue un grand rôle, à basse température, sur la conductivité thermique magnétique du fait d’une diminution des interactions spinons-défauts. Par ailleurs, une étude structurale par diffraction des rayons X et de neutrons sur chacun des composés a été réalisée et a mis en évidence la présence de distorsions dans la structure du composé La5Ca9Cu24O41. / Today’s new technologies bring increasing demands to the electronics industry whose capacity of electronic circuits and related microprocessors increases very rapidly, following Moore’s law. The increasing number of transistors per unit area brings about significant heating which may be harmful to the good functioning of the systems and creates problems in the evacuation of the very localized heat generated in the electronic components. In order to control the heat flow which is produced, it is essential to use new materials able to conduct rapidly and efficiently, i. e. unidirectionally, the heat toward a heat sink. The present thesis work deals with the above described issues and presents the study of materials which have to be insulating in order to avoid short circuits in the electronic components and also exhibit a strong anisotropy of the thermal conductivity in order to evacuate the heat exclusively in one direction. Single crystals are therefore required. In order to realize thermal conductivity measurements in the best conditions, perfect homogeneous single crystals of excellent quality were synthesized by the Travelling Solvent Zone Method. This no-crucible crystal growth method allows the synthesis of impurity-free single crystals several cm long. The investigated materials are the low dimensional cuprates Sr2CuO3, SrCuO2 and La5Ca9Cu24O41 exhibiting in their structures an alignment of Cu2+ ions of spin ½ as linear chains or ladders, showing thus a distinct 1D character. Their thermal conductivity in the 1D direction is described as the sum of two contributions, one phononic and the other of magnetic origin. In order to obtain a better understanding of the different competitive interaction mechanisms, the influence on thermal conductivity, of the purity of the compounds and also of doping on the copper site has been investigated. Furthermore, structural refinement was done (X-ray and neutron diffraction) and has permitted to highlight distortions in the La5Ca9Cu24O41 samples

Das Forschungsgebiet der Kuprat- oder Hochtemperatursupraleiter (HTSL) ist bis heute einer der lebendigsten Bereiche der Physik kondensierter Materie. Ein besonderer Stellenwert kommt dem normalleitenden Zustand oberhalb TC zu, dessen Verständnis wesentlich zu einer Theorie der Hochtemperatur-Supraleitung beitragen könnte. Gegenstand dieser Arbeit ist die Untersuchung der Elektronenstruktur von HTSLn der Bi2Sr2CaCu2O8+[delta](Bi2212)-Familie nahe der Fermifläche im normalleitenden Zustand. Die Experimente wurden mittels winkelaufgelöster Photoemissionsspektroskopie (ARPES) durchgeführt, wobei die hohe Auflösung in Energie und Impuls recht genaue Rückschlüsse auf die Spektralfunktion und die Übergangs-Matrixelemente erlaubt. Die wichtigsten experimentellen Ergebnisse sind: 1) Hochaufgelöste ARPES-Fermiflächenkarten von Bi2212 und (Pb,Bi)2212 zeigen folgendes Bild: Die Hauptfermifläche ist lochartig und um die Ecken der Brillouinzone zentriert. Weiterer Bestandteil der Elektronenstruktur ist die Schattenfermifläche. Bei reinem Bi2212 treten außerdem extrinsische Beugungskopien der Fermifläche auf. 2) ARPES-Messungen entlang der -M-Richtung von Bi2212 zeigen eine starke Abhängigkeit von der Anregungsenergie, die auf starken Matrixelement-Effekten beruht. Verschiedene Methoden zur Bestimmung von kF zeigen, dass die Daten konsistent mit einer lochartigen Topologie der Hauptfermifläche sind. Des Weiteren wird die Qualität verschiedener Methoden zur Bestimmung von kF bei starken Matrixelement-Effekten bewertet. 3) Die Hauptfermifläche von (Pb,Bi)2212 behält ihre lochartige Topologie über einen großen Dotierungsbereich nahe optimaler Dotierung. 4) Erste hochaufgelöste ARPES-Messungen des Zirkulardichroismus wurden an (Pb,Bi)2212 durchgeführt. In der verwendeten nicht-chiralen Messanordnung wird ein CDAD (Circular Dichroism in the Angular Distribution of Photoelectrons)-Effekt beobachtet, dessen Asymmetrie antisymmetrisch bezüglich der Zweischicht-aufgespaltenen Zustände ist.

Nous présentons ici une étude par diffusion Raman électronique de la dynamique des charges dans l'état supraconducteur des cuprates. L'utilisation de règles de sélection nous permet de sonder différentes régions de la surface de Fermi, plus particulièrement les régions nodales, où le gap supraconducteur de symétrie d des cuprates s'annule, et les régions anti-nodales, où il atteint sa valeur maximale. Des mesures systématiques de l'évolution avec le dopage des réponses nodales et anti-nodales ont permis de montrer qu'une simple description de type BCS du condensât superfluide était satisfaisante pour les régions optimalement et légèrement sur-dopées du diagramme de phase des cuprates, mais parfaitement inadaptée en ce qui concerne l'état supraconducteur des cuprates sous-dopés. Dans ce dernier en effet, nos mesures ont permis de révéler l'existence de deux échelles d'énergie distinctes, se comportant de manière antagoniste lorsque le dopage diminue. Des expériences menées en fonction de la température et de substitutions d'impuretés indiquent que l'échelle d'énergie associée aux régions anti-nodales est une signature du pseudogap, plutôt que du gap supraconducteur comme cela est généralement admis. Ce gap supraconducteur est en revanche visible dans les régions nodales,<br />et son amplitude suit, comme on s'y attendrait, la température critique de transition supraconductrice Tc. Enfin, l'effet d'impuretés magnétiques et non-magnétiques sur la réponse A1g qui sonde l'ensemble de la surface de Fermi, confirme la présence dans le canal de charge d'un mode lié à une excitation collective de spins, la résonance neutrons.

This thesis represents a systematic study of electronic structure of the modulation-free Pb-doped Bi2212 superconducting cuprates with respect to interlayer coupling done by using the angle-resolved photoemission spectroscopy (ARPES), which is a leading technique in the experimental investigation of the single particle excitations in solids. The results presented in this work indicate a very different origin for the observed complex spectra lineshape. Specifically, the peak-dip-hump lineshape can be easily understood in terms of the superposition of spectral features due to bilayer band splitting, namely the splitting of the CuO2 plane derived electronic structure in bonding and antibonding bands due to the interlayer coupling of CuO2 bilayer blocks within the unit cell of Bi2212. By performing experiments at synchrotron beamlines where the energy of the incoming photons can be tuned over a very broad range, the detailed matrix elements energy dependence for both bonding and antibonding bands was determined. This gave the opportunity to study the electronic properties these two bands separately. For the first time, it was proved that the superconducting gap has the same value and symmetry for both bands. Furthermore, having recognized and sorted out the bilayer splitting effects, it became possible to identify more subtle effects hidden in the details of the ARPES lineshapes. On underdoped samples an &amp;quot;intrinsic&amp;quot; peak-dip-hump structure due to the interaction between electrons and a bosonic mode was observed. Studying the doping, temperature, and momentum dependence of the photoemission spectra it was established that: the mode has a characteristic energy of 38-40 meV and causes strong renormalization of the electronic structure only in the superconducting state; the electron-mode coupling is maximal around the (?à,0) point in momentum space and is strongly doping dependent (being greatly enhanced in the underdoped regime). From the above, it was concluded that the bosonic mode must correspond to the sharp magnetic resonance mode observed in inelastic neutron scattering experiments, and that this coupling is relevant to superconductivity and the pairing mechanism in the cuprates.

Since the middle of the 20th century, significant interest has evolved from the scientific community towards the polypropionate family of marine natural products. A number of these compounds have been shown to possess significant biological activity, and this property, as well as their structural complexity, has driven numerous efforts towards their synthesis. The first chapter provides an introduction into the world of polypropionates, with a discussion on synthetic studies into a number of members of the tridachiapyrone family. Fundamental synthetic concepts utilised in this thesis towards the preparation of polyketides are also described, with a focus on their application towards the synthesis of 9,10-deoxytridachione, anti tridachiahydropyrone and syn tridachiahydropyrone. Chapter 2 describes the work undertaken towards the total synthesis of 9,10-deoxytridachione. The novel tandem conjugate addition-Dieckmann condensation of complex enones developed previously in the Perkins group was used to generate anti methylated cyclohexenones as key synthetic intermediates. The conversion of the cyclohexenones into the corresponding cyclohexadienes via allylic alcohols was attempted, utilising a Grignard-mediated reaction to achieve the selective 1,2-reduction. Studies into the Grignard-mediated reduction were also undertaken on seven additional cyclohexenones, in order to investigate the utility and scope of the reaction. The extension of the methodology previously developed for the synthesis of cyclohexenones is the subject of Chapter 3. This section describes investigations into the synthesis of stereochemically-diverse cyclohexenones from complex enones. The conjugate addition-Dieckmann condensation strategy was extended successfully towards the synthesis of a syn methylated cyclohexenone, which allowed the synthesis of the proposed true structure of tridachiahydropyrone to be pursued. The methodology developed in Chapter 3 was utilised in Chapter 4 to synthesise a model system of syn tridachiahydropyrone. A comparative analysis of the NMR data of the syn model, an anti model and anti tridachiahydropyrone with the natural product indicated that the true structure of tridachiahydropyrone may indeed have syn stereochemistry. The synthesis of syn tridachiahydropyrone was attempted, and to this end a suitable cyclohexanone was successfully synthesised. However, the subsequent methylation-elimination cascade failed to furnish the desired syn methylated cyclohexenone, producing only an anti methylated cyclohexanone. The stereochemistry of the methylation was deduced using high and low variable temperature NMR coupled with selective irradiation NOESY.