<p>The overall aim of this thesis is to compare different methods for calculation of Core-Level shifts in metallic alloys. The methods compared are the Initial State model, the Complete screening and the Transition state model. Core-level shifts can give information of chemical bonding and about the electronic structure in solids.</p><p>The basic theory used is the so-called Density-Functional-Theory, in conjunction with the Local-Density Approximation and the Coherent-Potential- Approximation. The metallic alloys used are Silver-Palladium, Copper-Palladium, Copper-Gold and Copper-Platinum, all inface-centered-cubic configuration.</p><p>The complete screening- and the transition-state model are found to be in better agreement with experimental results than those calculated with the initial state model. This is mainly due to the fact that the two former models includes final-state effects, whereas the last one do not. The screening parameters within the Coherent-Potential approximation are also investigated. It is found that the Screened-Impurity Model can extend the validity of the Coherent-Potential-Approximation and increase it's accuracy.</p>

The overall aim of this thesis is to compare different methods for calculation of Core-Level shifts in metallic alloys. The methods compared are the Initial State model, the Complete screening and the Transition state model. Core-level shifts can give information of chemical bonding and about the electronic structure in solids. The basic theory used is the so-called Density-Functional-Theory, in conjunction with the Local-Density Approximation and the Coherent-Potential- Approximation. The metallic alloys used are Silver-Palladium, Copper-Palladium, Copper-Gold and Copper-Platinum, all inface-centered-cubic configuration. The complete screening- and the transition-state model are found to be in better agreement with experimental results than those calculated with the initial state model. This is mainly due to the fact that the two former models includes final-state effects, whereas the last one do not. The screening parameters within the Coherent-Potential approximation are also investigated. It is found that the Screened-Impurity Model can extend the validity of the Coherent-Potential-Approximation and increase it's accuracy.

<p>A screened GPM approach in an EMTO-CPA framework was investigated in order to study its ability of describing transition temperatures in phase separating systems, i. e. systems giving either a random or a cluster structure depending on the temperature and the relative concentration of the ingoing atoms of the binary alloy used for the study. A motivation for the study is that the method works well for ordering systems, i. e. systems giving either a random or ordered structure dependent on the temperature and the relative concentration of the components in the binary alloy. Thereby is it of interest to find out the methods capacity in phase separating systems. The so called GPM potentials derived in the approach were applied in statistical Monte Carlo simulations for this purpose. The systems chosen for the investigation were the RhPd and the AlZn binary alloy systems. For both systems the method showed acceptable accuracy when properties as lattice parameter and mixing enthalpy were calculated. The quality of the derived GPM potentials has also been checked by calculating ordering energy for different ordered structures; directly from first principles calculations and from the GPM approach. The results were in acceptable agreement and thereby indicating that the GPM potentials were reliable. The transition temperatures in the RhPd phase diagram, derived by the statistical Monte Carlo simulations showed anyway deviation from experimental results. The error in the predictions might be due to the existing concentration dependencies in the GPM potentials.The conclusion from this study is that the Monte Carlo scheme might be inconvenient in order to handle the concentration dependencies seen in the GPM potentials.</p>

<p>Ab-initio results of the core-level shift and the distribution about the average for the 3<i>d</i>_5/2 electrons of Ag, Pd and 2<i>p</i>_3/2 of Cu are presented for the face-centered-cubic AgPd and CuPd random alloys. The complete screening model, which includes both initial and final states effects in the same scheme, has been used in the investigations. </p><p>The alloys have been modeled with a supercell containing 256 atoms. Density-functional theory calculations are carried out using the locally self consistent Green's function approach. </p><p>Results from the calculations clearly shows that the core-level shift distributions characteristic is Gaussian, but the components reveals a substantial difference in the FWHM (Full-Width at Half-Maximum). Comparison between the experimental and the calculated broadening shows a remarkable agreement.</p>

A screened GPM approach in an EMTO-CPA framework was investigated in order to study its ability of describing transition temperatures in phase separating systems, i. e. systems giving either a random or a cluster structure depending on the temperature and the relative concentration of the ingoing atoms of the binary alloy used for the study. A motivation for the study is that the method works well for ordering systems, i. e. systems giving either a random or ordered structure dependent on the temperature and the relative concentration of the components in the binary alloy. Thereby is it of interest to find out the methods capacity in phase separating systems. The so called GPM potentials derived in the approach were applied in statistical Monte Carlo simulations for this purpose. The systems chosen for the investigation were the RhPd and the AlZn binary alloy systems. For both systems the method showed acceptable accuracy when properties as lattice parameter and mixing enthalpy were calculated. The quality of the derived GPM potentials has also been checked by calculating ordering energy for different ordered structures; directly from first principles calculations and from the GPM approach. The results were in acceptable agreement and thereby indicating that the GPM potentials were reliable. The transition temperatures in the RhPd phase diagram, derived by the statistical Monte Carlo simulations showed anyway deviation from experimental results. The error in the predictions might be due to the existing concentration dependencies in the GPM potentials.The conclusion from this study is that the Monte Carlo scheme might be inconvenient in order to handle the concentration dependencies seen in the GPM potentials.

Ab-initio results of the core-level shift and the distribution about the average for the 3d5/2 electrons of Ag, Pd and 2p3/2 of Cu are presented for the face-centered-cubic AgPd and CuPd random alloys. The complete screening model, which includes both initial and final states effects in the same scheme, has been used in the investigations. The alloys have been modeled with a supercell containing 256 atoms. Density-functional theory calculations are carried out using the locally self consistent Green's function approach. Results from the calculations clearly shows that the core-level shift distributions characteristic is Gaussian, but the components reveals a substantial difference in the FWHM (Full-Width at Half-Maximum). Comparison between the experimental and the calculated broadening shows a remarkable agreement.

Orientadores: Roberto Eugenio Lagos Monaco, Guillermo Gerardo Cabrera Oyarzun / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-04T08:16:12Z (GMT). No. of bitstreams: 1 ChavesNeto_AntonioMaiadeJesus_D.pdf: 1164069 bytes, checksum: a0ef564c6eb492fa671d7430fad4221a (MD5) Previous issue date: 2004 / Resumo: O Hamiltoniano do modelo de Anderson para duas impurezas é estudado via um desacoplamento das funções de Green. Neste caso resulta ser equivalente a aproximação de potencial coerente (CPA) que também, neste caso, coincide com a aproximação Hubbard-I. Consideram-se todos os termos de interação impureza-impureza, tanto os denominados termos de um corpo como os de dois corpos. Os parâmetros associados às interações mencionadas acima incluem: repulsão coulombiana intra e intersítio, hopping direto, hopping correlacionado e o termo de troca (exchange). Todos estes são modelados via orbitais atômicos de Slater, e neste caso se considera o modelo mais simples, o caso não degenerado, ou seja, um nível por impureza. Nesta modelagem, incluindo o metal hospedeiro, os parâmetros independentes resultam ser: a constante de hibridização eletrônica impureza-metal, o número de portadores do metal hospedeiro, o vetor de onda de Fermi associado ao mesmo, a largura dos orbitais atômicos das impurezas e a distância impureza-impureza. Para o caso particular de temperatura nula e no regime denominado de banda semicheia (a metade dos níveis das impurezas são preenchidos considerando os valores esperados) são calculadas as densidades espectrais (densidade de estados) associadas às impurezas, as funções de correlações de spin e carga, suscetibilidades magnéticas e de carga, e a energia de correlação associada as impurezas. Os resultados são discutidos no contexto dos modelos já a existentes na literatura, assim como os casos limites para os quais existem resultados exatos. Os resultados encontrados estão de acordo com os casos limites conhecidos e são interessantes. Mostram também a importância de se considerar todas as interações impureza-impureza, fato negligenciado até agora na literatura / Abstract: We study the two impurity Anderson Model Hamiltonian via a Greens function decoupling scheme. This case turns out to be equivalent to the Coherent Potential Approximation (CPA) and furthermore equivalent to the Hubbard-I approximation. We consider all one and two body impurity-impurity interactions. The parameters associated to the latter include: the intra and intersite Coulomb repulsion, direct (band) hopping, correlated hopping and the exchange term. All of the above are modeled via Slater atomic orbitals, and here we consider the simplest model, non degenerate single impurity level. Including the host metal the resulting independent parameters are: The impurity-metal hybridization constant, the metal host carrier density, the associated Fermi wavevector, the atomic orbital width and the impurity-impurity distance. For the zero temperature case and in the so called band half called regime (impurities levels half called, in the mean) we compute the impurities spectral densities (density of states), spin and charge correlation functions, their respective susceptibilities and the correlation energy. We discuss our results considering the existing literature as well as the exact results for particular limiting cases. Our results agree with the latter and also yield interesting consequences, among others: the importance of including all impurity-impurity interactions, hitherto not considered. / Doutorado / Física da Matéria Condensada / Mestre em Física