Electronic structure calculations constitute a valuable tool to predict the properties of materials. In this study we propose an efficient scheme to study correlated electron systems with essentially only one free parameter, the screening length of the Coulomb potential. A general reformulation of the exchange energy of the correlated electron shell is combined with this method in order to analyze the calculations. The results are interpreted in terms of different polarization channels, due to different multipoles. The method is applied to various actinide compounds, in order to increase the understanding of the complicate behaviour of 5f electrons in these systems. We studied the non-magnetic phase of δ-Pu, where the spin polarization is taken over by a spin-orbit-like term that does not break the time reversal symmetry. We also find that a non-trivial high multipole of the magnetization density, the triakontadipole, constitutes the ordering parameter in the mysterious hidden order phase of the heavy-fermion superconductor URu2Si2. This type of multipolar ordering is also found to play an essential role in the hexagonal-based superconductors UPd2Al3,  UNi2Al3 and UPt3 and in the dioxide insulators UO2, NpO2 and PuO2. The triakontadipole moments are also present in all magnetic actinides we considered, except for Cm. These results led us to formulate a new set of rules for the ground state of a system, that are valid in presence of strong spin-orbit coupling interaction instead of those of Hund; the Katt's rules. Finally, we applied our method to a new class of high-Tc superconductors, the Fe-pnictides, where the Fe 3d electrons are moderately correlated. In these materials we obtain the stabilization of a low spin moment solution, in agreement with experiment, over a large moment solution, due to the gain in exchange energy in the formation of large multipoles of the spin magnetization density. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 705

Ce manuscrit présente la synthèse et la caractérisation de deux nouvelles familles de complexes mononucléaires, [Fe(L)2(NCS)2] et [Fe(L)(H2B(pz)2)2], montrant des propriétés bistables. L'étude des structures cristallographiques a permis de discuter l'influence de l'élongation des ligands L sur le réseau cristallin et sur les contacts intermoléculaires ainsi que l'existence de corrélations structures / propriétés. Enfin, la dernière partie de ce travail est consacrée à l'élaboration de façon contrôlée d'objets à transition de spin à l'échelle nanométrique, sous la forme de films déposés par sublimation et de nanoclusters synthétisés en milieu confiné.

Femtosecond electron diffraction experiments were performed on solid state iron(II) tris(2,2'-bipyridine) bis(hexafluorophosphate). The cation is known to undergo a spin crossover process when solvated in water and irradiated with 400 nm coherent light which results in a transition from a low spin to high spin state within a picosecond which is accompanied by a uniform 0.2 Å Fe-N bond elongation. A femtosecond diffraction experiment was performed on the solid sample and was unable to find evidence of a fast spin crossover transition. Suspecting this may be due to limitations of the apparatus, an ultrafast transient absorption experiment was performed. Emulating the liquid study by Gawelda et al, the pump probe experiment found evidence of spin crossover in the solid state sample. This result awaits verification by an improved transient absorption apparatus and has inspired efforts to perform an improved femtosecond electron diffraction experiment.

Femtosecond electron diffraction experiments were performed on solid state iron(II) tris(2,2'-bipyridine) bis(hexafluorophosphate). The cation is known to undergo a spin crossover process when solvated in water and irradiated with 400 nm coherent light which results in a transition from a low spin to high spin state within a picosecond which is accompanied by a uniform 0.2 Å Fe-N bond elongation. A femtosecond diffraction experiment was performed on the solid sample and was unable to find evidence of a fast spin crossover transition. Suspecting this may be due to limitations of the apparatus, an ultrafast transient absorption experiment was performed. Emulating the liquid study by Gawelda et al, the pump probe experiment found evidence of spin crossover in the solid state sample. This result awaits verification by an improved transient absorption apparatus and has inspired efforts to perform an improved femtosecond electron diffraction experiment.

Au cours de la dernière décennie, le procédé de fabrication additive par fusion sélective d'un lit de poudre SLM a attiré une grande attention dans le domaine de l'industrie, car il permet de produire rapidement des pièces de formes complexes. Le but de ce travail est d'étendre les performances des procédés SLM en étudiant la possibilité d'élaborer des pièces en atmosphère raréfiée. Pour atteindre cet objectif, une approche théorique et expérimentale a été développée, avec la mise en place d'une machine de fusion sélective par laser capable de travailler dans le domaine de pression de 1 à 10-2 mbar.Le travail sous vide permet d'éviter la formation du "bouclier" de plasma généré à partir de l'atmosphère de gaz ionisé par l'énergie du laser. Ceci permet d'une part d'éviter la contamination chimique du matériau (oxydation, nitruration,...) au cours des processus de fusion et d'autre part de réduire le taux de porosité. L'effet des paramètres du laser et des variables d'environnement sur la qualité de pièces a été étudié en considérant le cas du fer pur, de l'acier Inox 316L et du titane.Par ailleurs nous avons étudié la possibilité d'obtenir des alliages in-situ au cours de la fabrication par la technique SLM à partir de mélanges de poudres.Des essais ont été conduits à partir de mélanges Mg/Al, Fe/Ni et Ti/Ni. Dans tous les cas nous avons pu obtenir des alliages in-situ pour les domaines de composition visés qui correspondent à des applications pratiques (structures légères, alliage magnétique à faible coercivité, alliage à mémoire de forme). Les propriétés des matériaux obtenus, d'après les premières caractérisations effectuées, se comparent de façon favorable par rapport aux techniques classiques d'élaboration et de mise en œuvre.

No description available.

Les complexes à transition de spin sont des molécules qui peuvent être commutées entre deux états, l'un diamagnétique et l'autre paramagnétique. Cette commutation peut s'effectuer, entre autre, à l'aide d'une excitation lumineuse, ouvrant la voie vers un possible stockage de l'information au niveau d'une molécule unique. Toutefois, l'information photo-inscrite n'est stable qu'au-dessous d'une certaine température appelée T(LIESST). L'objectif principal de cette thèse a constitué en des modifications chimiques (modification du ligand organique, désolvatation, modifications d'anion,...) d'un complexe macrocyclique de Fe(II) qui présente à l'heure actuelle l'un des T(LIESST) les plus élevés (134 K), et ce afin d'augmenter encore cette valeur. Parmi les divers résultats expérimentaux, un T(LIESST) de 160 K a été obtenu.

Demands for new, energy-efficient appliances have greatly increased in response to our growing need for a more environmentally friendly society. Magnetic refrigeration is a technique that utilizes the magnetocaloric effect, with possible energy savings of up to 30% compared to commercial gas compression refrigerators. A material appropriate for commercial magnetocaloric devices should be both cheap and non-toxic; it should also exhibit a first-order magnetic transitions close to room temperature. The magnetic properties of Fe2P-related materials can be relevant in this context, since their magnetic properties can be finely tuned through the substitution of Fe by Mn and P by Si, As, Ge or B to meet the general requirements for a magnetocaloric device. An in-depth study has therefore here been made of the structural and magnetic properties of the (Fe,Mn)2(P,Si)-system. The phase diagram of the FeMnP1-xSix-system has been carefully re-examined. It is found to contain two single-phase regions: an orthorhombic Co2P-type structure (x < 0.15) and a hexagonal Fe2P-type structure (0.24 ≤ x < 0.50). Selected compounds within the Fe2P-type region of the phase diagram have been shown to exhibit potential for use in magnetic refrigeration applications. Neutron powder diffraction has here been used to determine the magnetic structures of selected crystalline compositions within the FeMnP1-xSix-system to gain a better understanding of its magnetic properties. The Fe2P-type region is mainly ferromagnetic, but an incommensurate antiferromagnetic structure has also been identified close to the Co2P/Fe2P-type phase border for x ≈ 0.25. The so-called ''virgin effect'' in the Fe2P-type region of the FeMn(P,Si) phase diagram is found to be accompanied by an irreversible structural phase transition induced by magnetostriction. This new phase is found to be preserved during successive cooling-heating cycles. Furthermore, the magnetic properties of the substituted Fe2P-type structure changes significantly for metal:non-metal ratios away from 2:1. Such deviations could well explain the apparently conflicting structure-property relationships described in earlier literature for the FeMnP1-xSix-system.

No description available.

Fours sets of PM10 samples were collected in three sites in SEQ from December 2002 to August 2004. Three of these sets of samples were collected by QLD EPA as a part of their regular air monitoring program at Woolloongabba, Rocklea and Eagle Farm. Half of the samples were used in this study for the analysis of water-soluble ions, which are Na+, K+, Mg2+, Ca2+, NH4 +, Cl-, NO3 -, SO4 2-, F-, Br-, NO2 -, PO4 -3 and the other half was retained by QLD EPA. The fourth set of samples was collected at Rocklea, specifically for this study. A quarter of the samples obtained from this set of samples were used to analyse water-soluble ions; a quarter of the sample was used to analyse Pb, Cu, Al, Fe, Mn and Zn; and the rests were used to analyse US EPA 16 priority PAHs. The water-soluble ions were extracted ultrasonically with water and the major watersoluble anions as well as NH4 + were analysed using IC. Na+, K+, Mg2+, Ca2+ Pb, Cu, Al, Fe, Mn and Zn were analysed using ICP-AES while PAHs were extracted by acetonitrile and analysed using HPLC. Of the analysed water-soluble ions, Cl-, NO3 -, SO4 2-, Na+, K+, Mg2+ and Ca2+ were high in concentration and determined in all the samples. F-, Br-, NO2 -, PO4 -3 and NH4 + ions were lower in concentration and determined only in some samples. Na+ and Cl- were high in all samples indicating the importance of a marine source. Principal Component Analysis (PCA) was used to examine the temporal variations of the water-soluble ions at the three sites. The results indicated that there was no major difference between the three sites. However, comparing the average concentrations of ions and Cl-/Na+ it was concluded that Woolloongabba had more marine influence than the other sites. Al, Fe and Zn were detected in all samples. Al and Fe were high in all samples indicating the significance of a source of crustal matter. Cu, Mn and Pb were in low concentrations and were determined only in some samples. The lower Pb concentrations observed in the study than in previous studies indicate that the phasing-out of leaded petrol had an appreciable impact on Pb levels in SEQ. This study reports for the first time, simultaneous data on the water-soluble, metal ion and PAH levels of PM10 aerosols in Brisbane, and provides information on the most likely sources of these chemical species. Such information can be used alongside those that already exist to formulate PM10 pollution reduction strategies for SEQ in order to protect the community from the adverse effects of PM pollution.