MAGNETIC FIELD INDUCED NEAR-BAND-GAP OPTICAL PROPERTIES IN EuTe LAYERS

The magnetic response of the near-band-edge optical properties is studied in EuTe layers. In several magneto-optical experiments, the absorption and emission are described as well as the related Stokes shift. Specifically, we present the first experimental report of the photoluminescence excitation (PLE) spectrum in Faraday configuration. The PLE spectra shows to be related with the absorption spectra through the observation of resonance between the excitation light and the zero-field band-gap. A new emission line appears at 1.6 eV at a moderate magnetic field in the photoluminescence (PL) spectra. Furthermore, we examine the absorption and PL red-shift induced by the magnetic field in the light of the d-f exchange interaction energy involved in these processes. Whereas the absorption red-shift shows a quadratic dependence on the field, the PL red-shift shows a linear dependence which is explained by spin relaxation of the excited state.

The effect of additional Si and SiGe layers on the confinement potential of GeMn diluted ferromagnetic semiconductor

In this work we analyze the spin-polarized charge density distribution in the GeMn diluted ferromagnetic semiconductors (DFS). The calculations are performed within a self-consistent k.p method, in which the exchange correlation effects in the local density approximation, as well as the strain effects due to the lattice mismatch, are taken into account. Our findings show that the extra confinement potential provided by the barriers and the variation of the Mn content in the DFS are responsible for a separation between the different spin charge densities, giving rise to higher mobility spin-polarized currents or high ferromagnetism transition temperatures systems. (c) 2008 Elsevier B.V. All rights reserved.

Joint Experimental and Theoretical Analysis of Order Disorder Effects in Cubic BaZrO(3) Assembled Nanoparticles under Decaoctahedral Shape

Periodic first-principles calculations based on density functional theory at the B3LYP level has been carried out to investigate the photoluminescence (PL) emission of BaZrO(3) assembled nanoparticles at room temperature. The defect created in the nanocrystals and their resultant electronic features lead to a diversification of electronic recombination within the BaZrO(3) band gap. Its optical phenomena are discussed in the light of photoluminescence emission at the green-yellow region around 570 nm. The theoretical model for displaced atoms and/or angular changes leads to the breaking of the local symmetry, which is based on the refined structure provided by Rietveld methodology. For each situation a band structure, charge mapping, and density of states were built and analyzed. X-ray diffraction (XRD) patterns, UV-vis measurements, and field emission scanning electron microscopy (FE-SEM) images are essential for a full evaluation of the crystal structure and morphology.

Satélites irregulares de Júpiter: análise da captura de asteróides binários

Pós-graduação em Física - FEG

First principles investigations on the electronic structure of anchor groups on ZnO nanowires and surfaces

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo fotodinâmico da clorofila a, azul de metileno e rosa bengala como agente inseticida contra Aedes aegypti

Photodynamic therapy, term introduced by von Tapeiner in 1900, can be defined as the administration of a non toxic drug, i.e., a dye, known as photosensitizer (FS), which subsequently will be illuminated with light of specific wavelength. PDT is based on the interaction among FS, oxygen and light, which through photochemical reactions cause cell death. The FS molecules must have a high probability to form the singlet state after the excitation, which can induce chemical changes in the neighborhood in two ways, called reactions type I and type II. The type II reaction is based on the exchange of energy to molecular oxygen, exciting it to its state of higher energy (singlet), which is highly reactive. The proposed mechanisms for cell death are linked to damage to the DNA, mitochondria and to the cytoplasmic membrane. Several pre‐clinical and clinical trials have been carried out and the PDT is already used in many countries for treatment mainly against certain types of cancer. The therapy also has been gaining strength in antimicrobial control, since the microorganisms have appeared increasingly resistant to current antibiotics. Another attempt to use the PDT is for the inactivation of macro‐organisms, such as micro‐crustaceans and mosquitoes. To this end I tested whether the photosensitizers methylene blue, rose Bengal and the chlorophyll a has insecticidal activity against the yellow fever and dengue vector mosquito, Aedes aegypti. Since these diseases have no effective treatments, its control is linked to the vector control, which has shown resistance to chemical pesticides used. Based on this, this work shows its importance, because it is a new type of mosquito control since all the photosensitizers used are low cost, do not generate toxic products at the concentrations used and showed good results in mortality. The best photosensitizer was rose Bengal... (Complete abstract click electronic access below)

Effect of hydrogen bond formation on the elastic molecular scattering: a case study with methanol

Rayleigh optical activities of small hydrogen-bonded methanol clusters containing two to five molecules are reported. For the methanol trimer, tetramer, and pentamer both cyclic and linear structures are considered. After the geometry optimizations, the dipole moments and the dipole polarizabilities (mean, interaction, and anisotropic components) are calculated using HF, MP2 and DFT (B3LYP, B3P86 and BH&HLYP) with aug-cc-pVDZ extended basis set. The polarizabilities are used to analyse the depolarization ratios and the Rayleigh scattering activities. The variations in the activity and in the depolarization for Rayleigh scattered radiation with the increase in the cluster size for both cyclic and linear structures are analysed.

Spin-polarized transport in II-VI diluted magnetic semiconductors superlattices

We studied the spin-polarized charge densities in II-VI-based diluted magnetic superlattices formed of p-doped ZnTe:Mg/ZnTe:TM/ZnTe:Mg non-magnetic/magnetic/non-magnetic layers, with TM standing for transition metal. The calculations were performed within a self-consistent k.p method, in which are also taken into account the exchange correlation effects in the local density approximation. Our results show a limit for the width of the non-magnetic layer for which the difference between the opposite spin charge densities is maximized, indicating the best conditions to obtain full polarization by varying the TM content. We also discuss these effects in the calculated photoluminescence spectra. Our findings point to the possibility of engineering the spin-polarized charge distribution by varying the widths of the magnetic and non-magnetic layers and/or varying the TM concentration in the magnetic layers, thus providing a guide for future experiments. (c) 2012 Elsevier B.V. All rights reserved.

Theoretical study of the XP3 (X = Al, B, Ga) clusters

The lowest singlet and triplet states of AlP3, GaP3 and BP3 molecules with C-s, C-2v and C-3v symmetries were characterized using the B3LYP functional and the aug-cc-pVTZ and aug-cc-pVQZ correlated consistent basis sets. Geometrical parameters and vibrational frequencies were calculated and compared to existent experimental and theoretical data. Relative energies were obtained with single point CCSD(T) calculations using the aug-cc-pVTZ, aug-cc-pVQZ and aug-cc-pV5Z basis sets, and then extrapolating to the complete basis set (CBS) limit. (C) 2011 Elsevier B.V. All rights reserved.

Characterization of geothermal reservoirs’ parameters by inverse problem resolution and geostatistical simulations

BTES (borehole thermal energy storage)systems exchange thermal energy by conduction with the surrounding ground through borehole materials. The spatial variability of the geological properties and the space-time variability of hydrogeological conditions affect the real power rate of heat exchangers and, consequently, the amount of energy extracted from / injected into the ground. For this reason, it is not an easy task to identify the underground thermal properties to use when designing. At the current state of technology, Thermal Response Test (TRT) is the in situ test for the characterization of ground thermal properties with the higher degree of accuracy, but it doesn’t fully solve the problem of characterizing the thermal properties of a shallow geothermal reservoir, simply because it characterizes only the neighborhood of the heat exchanger at hand and only for the test duration. Different analytical and numerical models exist for the characterization of shallow geothermal reservoir, but they are still inadequate and not exhaustive: more sophisticated models must be taken into account and a geostatistical approach is needed to tackle natural variability and estimates uncertainty. The approach adopted for reservoir characterization is the “inverse problem”, typical of oil&gas field analysis. Similarly, we create different realizations of thermal properties by direct sequential simulation and we find the best one fitting real production data (fluid temperature along time). The software used to develop heat production simulation is FEFLOW 5.4 (Finite Element subsurface FLOW system). A geostatistical reservoir model has been set up based on literature thermal properties data and spatial variability hypotheses, and a real TRT has been tested. Then we analyzed and used as well two other codes (SA-Geotherm and FV-Geotherm) which are two implementation of the same numerical model of FEFLOW (Al-Khoury model).

Computational studies on the structure and stabilities of magnetic inter-metallic compounds

The purpose of this thesis is to further the understanding of the structural, electronic and magnetic properties of ternary inter-metallic compounds using density functional theory (DFT). Four main problems are addressed. First, a detailed analysis on the ternary Heusler compounds is made. It has long been known that many Heusler compounds ($X_2YZ$; $X$ and $Y$ transition elements, $Z$ main group element) exhibit interesting half-metallic and ferromagnetic properties. In order to understand these, the dependence of magnetic and electronic properties on the structural parameters, the type of exchange-correlation functional and electron-electron correlation was examined. It was found that almost all Co$_2YZ$ Heusler compounds exhibit half-metallic ferromagnetism. It is also observed that $X$ and $Y$ atoms mainly contribute to the total magnetic moment. The magnitude of the total magnetic moment is determined only indirectly by the nature of $Z$ atoms, and shows a trend consistent with Slater-Pauling behaviour in several classes of these compounds. In contrast to experiments, calculations give a non-integer value of the magnetic moment in certain Co$_2$-based Heusler compounds. To explain deviations of the calculated magnetic moment, the LDA+$U$ scheme was applied and it was found that the inclusion of electron-electron correlation beyond the LSDA and GGA is necessary to obtain theoretical description of some Heusler compounds that are half-metallic ferromagnets. The electronic structure and magnetic properties of substitutional series of the quaternary Heusler compound Co$_2$Mn$_{1-x}$Fe$_x$Si were investigated under LDA+$U$. The calculated band structure suggest that the most stable compound in a half-metallic state will occur at an intermediate Fe concentration. These calculated findings are qualitatively confirmed by experimental studies. Second, the effect of antisite disordering in the Co$_2$TiSn system was investigated theoretically as well as experimentally. Preservation of half-metallicity for Co$_2$TiSn was observed with moderate antisite disordering and experimental findings suggest that the Co and Ti antisites disorder amounts to approximately 10~% in the compound. Third, a systematic examination was carried out for band gaps and the nature (covalent or ionic) of bonding in semiconducting 8- and 18-electron or half-metallic ferromagnet half-Heusler compounds. It was found that the most appropriate description of these compounds from the viewpoint of electronic structures is one of a $YZ$ zinc blende lattice stuffed by the $X$ ion. Simple valence rules are obeyed for bonding in the 8- and 18-electron compounds. Fourth, hexagonal analogues of half-Heusler compounds have been searched. Three series of compounds were investigated: GdPdSb, GdAutextit{X} (textit{X} = Mn, Cd and In) and EuNiP. GdPdSb is suggested as a possible half-metallic weak ferromagnet at low temperature. GdAutextit{X} (textit{X} = Mn, Cd and In) and EuNiP were investigated because they exhibit interesting bonding, structural and magnetic properties. The results qualitatively confirm experimental studies on magnetic and structural behaviour in GdPdSb, GdAutextit{X} (textit{X} = Mn, Cd and In) and EuNiP compounds. ~

Quantum effects and dynamics in hydrogen-bonded systems: a first-principles approach to spectroscopic experiments

Computer simulations have become an important tool in physics. Especially systems in the solid state have been investigated extensively with the help of modern computational methods. This thesis focuses on the simulation of hydrogen-bonded systems, using quantum chemical methods combined with molecular dynamics (MD) simulations. MD simulations are carried out for investigating the energetics and structure of a system under conditions that include physical parameters such as temperature and pressure. Ab initio quantum chemical methods have proven to be capable of predicting spectroscopic quantities. The combination of these two features still represents a methodological challenge. Furthermore, conventional MD simulations consider the nuclei as classical particles. Not only motional effects, but also the quantum nature of the nuclei are expected to influence the properties of a molecular system. This work aims at a more realistic description of properties that are accessible via NMR experiments. With the help of the path integral formalism the quantum nature of the nuclei has been incorporated and its influence on the NMR parameters explored. The effect on both the NMR chemical shift and the Nuclear Quadrupole Coupling Constants (NQCC) is presented for intra- and intermolecular hydrogen bonds. The second part of this thesis presents the computation of electric field gradients within the Gaussian and Augmented Plane Waves (GAPW) framework, that allows for all-electron calculations in periodic systems. This recent development improves the accuracy of many calculations compared to the pseudopotential approximation, which treats the core electrons as part of an effective potential. In combination with MD simulations of water, the NMR longitudinal relaxation times for 17O and 2H have been obtained. The results show a considerable agreement with the experiment. Finally, an implementation of the calculation of the stress tensor into the quantum chemical program suite CP2K is presented. This enables MD simulations under constant pressure conditions, which is demonstrated with a series of liquid water simulations, that sheds light on the influence of the exchange-correlation functional used on the density of the simulated liquid.

Adiabatic and local approximations for the kohn-sham potential in the hubbard model

We obtain the exact time-dependent Kohn-Sham potentials Vks for 1D Hubbard chains, driven by a d.c. external field, using the time-dependent electron density and current density obtained from exact many-body time-evolution. The exact Vxc is compared to the adiabatically-exact Vad-xc and the “instantaneous ground state” Vigs-xc. The effectiveness of these two approximations is analyzed. Approximations for the exchange-correlation potential Vxc and its gradient, based on the local density and on the local current density, are also considered and both physical quantities are observed to be far outside the reach of any possible local approximation. Insight into the respective roles of ground-state and excited-state correlation in the time-dependent system, as reflected in the potentials, is provided by the pair correlation function.

Accurate computations of the structures and binding energies of the imidazole ... benzene and pyrrole ... benzene complexes

Using explicitly-correlated coupled-cluster theory with single and double excitations, the intermolecular distances and interaction energies of the T-shaped imidazole⋯⋯benzene and pyrrole⋯⋯benzene complexes have been computed in a large augmented correlation-consistent quadruple-zeta basis set, adding also corrections for connected triple excitations and remaining basis-set-superposition errors. The results of these computations are used to assess other methods such as Møller–Plesset perturbation theory (MP2), spin-component-scaled MP2 theory, dispersion-weighted MP2 theory, interference-corrected explicitly-correlated MP2 theory, dispersion-corrected double-hybrid density-functional theory (DFT), DFT-based symmetry-adapted perturbation theory, the random-phase approximation, explicitly-correlated ring-coupled-cluster-doubles theory, and double-hybrid DFT with a correlation energy computed in the random-phase approximation.

Evaluación geoecológica de los paisajes del Departamento Minas (Provincia de Neuquén), para el estudio de la degradación de la tierra

Las sociedades en su afán de aprovechar los recursos naturales que la tierra le provee, han ido transformando permanentemente el medio que habitamos, generando una crisis ambiental que es tema de preocupación y permanente discusión en organismos, foros y conferencias relacionados con el cuidado y protección del medio ambiente. En las regiones áridas y semiáridas uno de los problemas ambientales más comunes es la degradación de tierras por efecto del sobrepastoreo. La tercera parte de la superficie terrestre del planeta es árida y semiárida y en ella los procesos de desertización se han intensificado en los últimos decenios. Según la Convención de las Naciones Unidas de lucha contra la Desertificación (CNULD), este problema amenaza al 40 por ciento aproximadamente, de la masa terrestre de nuestro planeta. Más de 1000 millones de personas en alrededor de 100 países están afectadas directamente por la desertificación o corren peligro de estarlo (CNULD, 2003), estimándose que "la pérdida de ingresos en las áreas afectadas alcanza a unos 42.000 millones de dólares". Argentina en general y la Patagonia en particular, no son ajenas a esta situación. La Secretaría de Recursos Naturales y Medio Ambiente Humano (1996), calcula que aproximadamente el 75 por ciento de nuestro territorio nacional se encuentra afectado por crecientes condiciones de aridez y en la Patagonia, el 90 por ciento de la superficie (unos 780.000 km2) presenta signos de degradación. De esta superficie, un 30 por ciento, está bajo procesos erosivos eólicos e hídricos severos o graves con tendencia a agravarse. Teniendo en cuenta esta situación, esta tesis tiene como propósito aplicar las concepciones metodológicas de la geoecología de los paisajes en el Departamento Minas (Provincia de Neuquén), con vistas a estudiar la estructura y funcionamiento de los paisajes, herramienta fundamental para comprender el fenómeno de la degradación de la tierra. El objetivo central de este trabajo consiste en estudiar la degradación de los paisajes de este lugar a partir de los preceptos de la geoecología, con apoyo de los Sistemas de Información Geográfica y la teledetección, estableciendo índices diagnósticos que reflejen la interacción e interdependencia entre los componentes naturales y sociales del paisaje. El estudio de los paisajes brinda la posibilidad de integrar transdisciplinariamente los conocimientos y percepciones de la diversidad geoecológica y socioeconómica desde una perspectiva dinámica. Mediante este análisis se puede arribar al conocimiento de las formas de ocupación y conservación de los recursos naturales procurando la protección de la oferta ecológica a largo plazo. El paisaje geográfico o geosistema se concibe como "un sistema espacio-temporal, complejo y abierto, que se origina y evoluciona justamente en la interfase naturaleza-sociedad, en un constante estado de intercambio de energía, materia e información, donde su estructura, funcionamiento, dinámica y evolución reflejan la interacción entre los componentes naturales (abióticos y bióticos), técnico-económicos y socio-culturales (Mateo, J. 1991; Salinas. E. 1991y 1997). Se trata de una formación socio-natural que constituye una categoría científica y como tal, será adoptada en este trabajo.