Submitted by Lucas Cesar Gomes Squillante null (lucasquillante@hotmail.com) on 2018-01-19T17:39:44Z No. of bitstreams: 1 Dissertação de Mestrado Lucas Cesar Gomes Squillante.pdf: 13112928 bytes, checksum: b4a4e7a0bc1cbdc48db3b829714e912d (MD5) / Approved for entry into archive by Ana Paula Santulo Custódio de Medeiros null (asantulo@rc.unesp.br) on 2018-01-22T13:15:43Z (GMT) No. of bitstreams: 1 squillante_lcg_me_rcla.pdf: 13113103 bytes, checksum: ee63e961b931fa78df69438fc268b5f2 (MD5) / Made available in DSpace on 2018-01-22T13:15:43Z (GMT). No. of bitstreams: 1 squillante_lcg_me_rcla.pdf: 13113103 bytes, checksum: ee63e961b931fa78df69438fc268b5f2 (MD5) Previous issue date: 2017-11-24 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O fenômeno da supercondutividade atualmente um dos mais relevantes tópicos na Física da Matéria Condensada, tornando os sistemas fortemente correlacionados um tópico de grande interesse devido à possibilidade de estudar os aspectos fundamentas da interação elétron-elétron, que são o âmago da supercondutividade. Desta forma, a classe de condutores moleculares (TMTTF)2X (onde TMTTF é tetrametiltetratiafuvaleno e X é um contra-ânion) desempenha um papel sistemático e fundamental no estudo de tais aspectos de correlação. Nesta tese de mestrado, os materiais de interesse foram o (TMTTF)2PF6-H12 e o (TMTTF)2PF6-D12, onde uma anomalia na constante dielétrica diferente para os dois sais foi observada na transição ferroelétrica de Mott-Hubbard através de medidas de constante dielétrica quasi-estática no eixo c* (contribuição iônica) e o comportamento tipo relaxor da variante hidrogenada foi analisado com base na teoria de campo médio. Uma revisão de transições de fase clássicas e quânticas também foi realizada com o objetivo de estudar o chamado efeito magneto-calórico para o modelo do paramagneto de Brillouin (o parâmetro de Grüneisen magnético), que é uma grandeza Física única e poderosa para detectar experimentalmente uma transição de fase quântica induzida por campo magnético em um sistema real. Ainda, um estudo comparativo entre as fases delta (hexagonal) e delta' (tetragonal) da liga binária FeSe1-x foi realizado e monocristais foram sintetizados utilizando o método de síntese de estado sólido visando atingir a fase delta. / The phenomenon of superconductivity is currently one of the most relevant topics in Solid State Physics, making strongly correlated systems a very highattractive topic due to the possibility of studying the fundamental aspects of the electron-electron interaction that are the core of superconductivity. Thus, the class of molecular conductors (TMTTF)2X (where TMTTF is tetramethyltetrathiafuvalene and X is a counter-anion) plays a systematic and fundamental role to study such correlation aspects. In this Master Thesis, the materials of interest were the (TMTTF)2PF6-H12 and (TMTTF)2PF6-D12, where a different dielectric anomaly at the Mott-Hubbard ferroelectric transition was observed for the two salts and the relaxor behavior of the hydrogenated variant was analysed based on the mean-field theory. A review of classical and quantum phase transitions was performed aiming to study the so-called magneto-caloric effect (the magnetic Grüneisen parameter) for the Brillouin paramagnet model, which is a powerful and unique physical quantity to experimentally detect a quantum phase transition induced by magnetic field in a real system. Also, a comparative study between the (hexagonal) and (tetragonal) phases of the binary alloy FeSe1-x was performed and single-crystals were synthesized employing the solid-state reaction method in order to achieve the phase.

Energy production, storage and efficient usage are all crucial factors for environmentally sound and sustainable future technologies. One important question concerns the refrigeration industry, where the energy efficiency of the presently used technologies is at best 40% of the theoretical Carnot limit. Magnetic refrigerators offer a modern low-energy demand and environmentally friendly alternative. Iron phosphide based materials have been proposed to be amongst the most promising candidates for working body of magnetic refrigerators. Hydrogen is one of the central elements on the most promising sources of renewable energy. Considerable international research focuses on finding good solid state materials for hydrogen storage. On the other hand, hydrogen gas is obtained from hydrogen containing chemical compounds, which after breaking the chemical bounds usually yield to a mixture of different gases. Palladium-silver alloys are frequently used for hydrogen separation membranes for producing purified hydrogen gas. All these applications need a fundamental understanding of the structural, magnetic, chemical and thermophysical properties of the involved solid state materials. In the present thesis ab initio electronic structure methods are used to study the crystallographic and magnetic properties of Fe2P based magneto-caloric compounds and the thermophysical properties of Pd-Ag binary alloys. Lattice stability of pure Fe2P and the effect of Si doping on the phase stability are presented. In contrast to the observation, for the ferromagnetic state the body centered orthorhombic structure (bco, space group Imm2) is predicted to have lower energy than the hexagonal structure (hex, space group P62m). The zero-point spin fluctuation energy difference is found to be large enough to stabilize the hex phase. For the paramagnetic state, the hex structure is shown to be the stable phase and the computed total energy versus composition indicates a hex to bco crystallographic phase transition with increasing Si content. The magneto-structural effects and the mechanisms responsible for the structural phase transition are discussed in details. The magnetic properties of Fe2P can be subtly tailored by Mn doping. It has been shown experimentally that Mn atoms preferentially occupy one of the two different Fe sites of Fe2P. Theoretical results for the Mn site occupancy in MnFeP1-xSix are presented. The single crystal and polycrystalline elastic constants and the Debye temperature of Pd1-xAgx binary alloys are calculated for the whole range of concentration, 0≤x≤1. It is shown that the variation of the elastic parameters of Pd-Ag alloys with chemical composition strongly deviates from the simple expected trend. The complex electronic origin of these anomalies is demonstrated. Within the present thesis, all relaxed crystal structures are obtained using the Projector AugmentedWave full-potential method. The chemical and magnetic disorder is treated using the Exact Muffin-Tin Orbitals method in combination with the Coherent Potential Approximation. The paramagnetic phase is modeled by the Disordered Local Magnetic Moments approach. / QC 20101101