Extent and limitations of density functional theory in describing magnetic systems

The performance of density-functional theory to solve the exact, nonrelativistic, many-electron problem for magnetic systems has been explored in a new implementation imposing space and spin symmetry constraints, as in ab initio wave function theory. Calculations on selected systems representative of organic diradicals, molecular magnets and antiferromagnetic solids carried out with and without these constraints lead to contradictory results, which provide numerical illustration on this usually obviated problem. It is concluded that the present exchange-correlation functionals provide reasonable numerical results although for the wrong physical reasons, thus evidencing the need for continued search for more accurate expressions.

Chaotic, memory, and cooling rate effects in spin glasses: Evaluation of the Edwards-Anderson model

We investigate chaotic, memory, and cooling rate effects in the three-dimensional Edwards-Anderson model by doing thermoremanent (TRM) and ac susceptibility numerical experiments and making a detailed comparison with laboratory experiments on spin glasses. In contrast to the experiments, the Edwards-Anderson model does not show any trace of reinitialization processes in temperature change experiments (TRM or ac). A detailed comparison with ac relaxation experiments in the presence of dc magnetic field or coupling distribution perturbations reveals that the absence of chaotic effects in the Edwards-Anderson model is a consequence of the presence of strong cooling rate effects. We discuss possible solutions to this discrepancy, in particular the smallness of the time scales reached in numerical experiments, but we also question the validity of the Edwards-Anderson model to reproduce the experimental results.

Grain boundaries in vortex matter

We explore the statistical properties of grain boundaries in the vortex polycrystalline phase of type-II superconductors. Treating grain boundaries as arrays of dislocations interacting through linear elasticity, we show that self-interaction of a deformed grain boundary is equivalent to a nonlocal long-range surface tension. This affects the pinning properties of grain boundaries, which are found to be less rough than isolated dislocations. The presence of grain boundaries has an important effect on the transport properties of type-II superconductors as we show by numerical simulations: our results indicate that the critical current is higher for a vortex polycrystal than for a regular vortex lattice. Finally, we discuss the possible role of grain boundaries in vortex lattice melting. Through a phenomenological theory we show that melting can be preceded by an intermediate polycrystalline phase.

Electronic structure of a neutral oxygen vacancy in SrTiO3

The electronic structure of an isolated oxygen vacancy in SrTiO3 has been investigated with a variety of ab initio quantum mechanical approaches. In particular we compared pure density functional theory (DFT) approaches with the Hartree-Fock method, and with hybrid methods where the exchange term is treated in a mixed way. Both local cluster models and periodic calculations with large supercells containing up to 80 atoms have been performed. Both diamagnetic (singlet state) and paramagnetic (triplet state) solutions have been considered. We found that the formation of an O vacancy is accompanied by the transfer of two electrons to the 3d(z2) orbitals of the two Ti atoms along the Ti-Vac-Ti axis. The two electrons are spin coupled and the ground state is diamagnetic. New states associated with the defect center appear in the gap just below the conduction band edge. The formation energy computed with respect to an isolated oxygen atom in the triplet state is 9.4 eV.

Coherent tunnelling in Cu2+- and Ag2+-doped MgO and CaO: Cu2+ explored through ab initio calculations

The observation of coherent tunnelling in Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ was a crucial discovery in the realm of the Jahn-Teller (JT) effect. The main reasons favoring this dynamic behavior are now clarified through ab initio calculations on Cu2+ - and Ag2+ -doped cubic oxides. Small JT distortions and an unexpected low anharmonicity of the eg JT mode are behind energy barriers smaller than 25 cm-1 derived through CASPT2 calculations for Cu2+ - and Ag2+ -doped MgO and CaO:Cu2+ . The low anharmonicity is shown to come from a strong vibrational coupling of MO610- units (M=Cu,Ag) to the host lattice. The average distance between the d9 impurity and ligands is found to vary significantly on passing from MgO to SrO following to a good extent the lattice parameter.

Pauli distorted double folded potential

The enhancement in the production of even-Z nuclei observed in nuclear fission has also been observed in fragments produced from heavy ion collsions. Beams of 40Ar, 40Cl, and 40Ca at 25 MeV/nucleon were impinged on 58Fe and 58Ni targets. The resulting fragments were detected using the MSU 4pi detector array, which had additional silicon detectors for better isotopic resolution. Comparison of the ratios of yields for each element showed enhancement of even-Z fragment production. The enhancement was more pronounced for reactions with a greater difference in the N/Z of the compound system. However, this effect was less for systems that were more neutron rich. The average N/Z for fragments also displayed an odd-even effect with a lower average N/Z for the even-Z fragments. This is related to the greater availability of neutron-poor isotopes for even-Z nuclei

Magnetic moments of the Lambda(1405) and Lambda(1670) resonances

By using techniques of unitarized chiral perturbation theory, where the Lamda(1405) and Lamda(1670) resonances are dynamically generated, we evaluate the magnetic moments of these resonances and their transition magnetic moment. The results obtained here differ appreciably from those obtained with existing quark models. The width for the Lamda(1670)->Lamda(1405)gamma transition is also evaluated, leading to a branching ratio of the order of 210-6.

Superheavy nuclei in relativistic effective Lagrangian model

Isotopic and isotonic chains of superheavy nuclei are analyzed to search for spherical double shell closures beyond Z=82 and N=126 within the new effective field theory model of Furnstahl, Serot, and Tang for the relativistic nuclear many-body problem. We take into account several indicators to identify the occurrence of possible shell closures, such as two-nucleon separation energies, two-nucleon shell gaps, average pairing gaps, and the shell correction energy. The effective Lagrangian model predicts N=172 and Z=120 and N=258 and Z=120 as spherical doubly magic superheavy nuclei, whereas N=184 and Z=114 show some magic character depending on the parameter set. The magicity of a particular neutron (proton) number in the analyzed mass region is found to depend on the number of protons (neutrons) present in the nucleus.

Density matrix functional theory that includes pairing correlations

The extension of density functional theory (DFT) to include pairing correlations without formal violation of the particle-number conservation condition is described. This version of the theory can be considered as a foundation of the application of existing DFT plus pairing approaches to atoms, molecules, ultracooled and magnetically trapped atomic Fermi gases, and atomic nuclei where the number of particles is conserved exactly. The connection with Hartree-Fock-Bogoliubov (HFB) theory is discussed, and the method of quasilocal reduction of the nonlocal theory is also described. This quasilocal reduction allows equations of motion to be obtained which are much simpler for numerical solution than the equations corresponding to the nonlocal case. Our theory is applied to the study of some even Sn isotopes, and the results are compared with those obtained in the standard HFB theory and with the experimental ones.

Characterization of CNTs and CNTs/MnO2 composite for supercapacitor application

Màster en Nanociència i Nanotecnologia

Biogeochemistry of the shelf sediments of south eastern Arabian sea: Effect on benthic bacterial heterotrophs

The composition and variability of heterotrophic bacteria along the shelf sediments of south west coast of India and its relationship with the sediment biogeochemistry was investigated. The bacterial abundance ranged from 1.12 x 103 – 1.88 x 106 CFU g-1 dry wt. of sediment. The population showed significant positive correlation with silt (r = 0.529, p< 0.05), organic carbon (OC) (r = 0.679, p< 0.05), total nitrogen (TN) (r = 0.638, p< 0.05), total protein (TPRT) (r = 0.615, p< 0.05) and total carbohydrate (TCHO) (r = 0.675, p< 0.05) and significant negative correlation with sand (r = -0.488, p< 0.05). Community was mainly composed of Bacillus, Alteromonas, Vibrio, Coryneforms, Micrococcus, Planococcus, Staphylococcus, Moraxella, Alcaligenes, Enterobacteriaceae, Pseudomonas, Acinetobacter, Flavobacterium and Aeromonas. BIOENV analysis explained the best possible environmental parameters i.e., carbohydrate, total nitrogen, temperature, pH and sand at 50m depth and organic matter, BPC, protein, lipid and temperature at 200m depth controlling the distribution pattern of heterotrophic bacterial population in shelf sediments. The Principal Component Analysis (PCA) of the environmental variables showed that the first and second principal component accounted for 65% and 30.6% of the data variance respectively. Canonical Correspondence Analysis (CCA) revealed a strong correspondence between bacterial distribution and environmental variables in the study area. Moreover, non-metric MDS (Multidimensional Scaling) analysis demarcated the northern and southern latitudes of the study area based on the bioavailable organic matter

Horizontal nutrient fluxes and production efficiencies in urban and peri-urban crop and livestock husbandry of Niamey, Niger

Urban and peri-urban agriculture (UPA) increasingly supplies food and non-food values to the rapidly growing West African cities. However, little is known about the resource use efficiencies in West African small-scale UPA crop and livestock production systems, and about the benefits that urban producers and retailers obtain from the cultivation and sale of UPA products. To contribute to filling this gap of knowledge, the studies comprising this doctoral thesis determined nutrient use efficiencies in representative urban crop and livestock production system in Niamey, Niger, and investigated potential health risks for consumers. Also assessed was the economic efficiency of urban farming activities. The field study, which was conducted during November 2005 to January 2008, quantified management-related horizontal nutrient flows in 10 vegetable gardens, 9 millet fields and 13 cattle and small ruminant production units. These farms, selected on the basis of a preceding study, represented the diversity of UPA crop and livestock production systems in Niamey. Based on the management intensity, the market orientation and especially the nutrient input to individual gardens and fields, these were categorized as high or low input systems. In the livestock study, high and low input cattle and small ruminant units were differentiated based on the amounts of total feed dry matter offered daily to the animals at the homestead. Additionally, economic returns to gardeners and market retailers cultivating and selling amaranth, lettuce, cabbage and tomato - four highly appreciated vegetables in Niamey were determined during a 6-months survey in forty gardens and five markets. For vegetable gardens and millet fields, significant differences in partial horizontal nutrient balances were determined for both management intensities. Per hectare, average annual partial balances for carbon (C), nitrogen (N), phosphorus (P) and potassium (K) amounted to 9936 kg C, 1133 kg N, 223 kg P and 312 kg K in high input vegetable gardens as opposed to 9580 kg C, 290 kg N, 125 kg P and 351 kg K in low input gardens. These surpluses were mainly explained by heavy use of mineral fertilizers and animal manure to which irrigation with nutrient rich wastewater added. In high input millet fields, annual surpluses of 259 kg C ha-1, 126 kg N ha-1, 20 kg P ha-1 and 0.4 kg K ha-1 were determined. Surpluses of 12 kg C ha-1, 17 kg N ha-1, and deficits of -3 kg P ha-1 and -3 kg K ha-1 were determined for low input millet fields. Here, carbon and nutrient inputs predominantly originated from livestock manure application through corralling of sheep, goats and cattle. In the livestock enterprises, N, P and K supplied by forages offered at the farm exceeded the animals’ requirements for maintenance and growth in high and low input sheep/goat as well as cattle units. The highest average growth rate determined in high input sheep/goat units was 104 g d-1 during the cool dry season, while a maximum average gain of 70 g d-1 was determined for low input sheep/goat units during the hot dry season. In low as well as in high input cattle units, animals lost weight during the hot dry season, and gained weight during the cool dry season. In all livestock units, conversion efficiencies for feeds offered at the homestead were rather poor, ranging from 13 to 42 kg dry matter (DM) per kg live weight gain (LWG) in cattle and from 16 to 43 kg DM kg-1 LWG in sheep/goats, pointing to a substantial waste of feeds and nutrients. The economic assessment of the production of four high value vegetables pointed to a low efficiency of N and P use in amaranth and lettuce production, causing low economic returns for these crops compared to tomato and cabbage to which inexpensive animal manure was applied. The net profit of market retailers depended on the type of vegetable marketed. In addition it depended on marketplace for amaranth and lettuce, and on season and marketplace for cabbage and tomato. Analysis of faecal pathogens in lettuce irrigated with river water and fertilized with animal manure indicated a substantial contamination by Salmonella spp. with 7.2 x 104 colony forming units (CFU) per 25 g of produce fresh matter, while counts of Escherichia coli averaged 3.9 x 104 CFU g-1. In lettuce irrigated with wastewater, Salmonella counts averaged 9.8 x 104 CFU 25 g-1 and E. coli counts were 0.6 x 104 CFU g-1; these values exceeded the tolerable contamination levels in vegetables of 10 CFU g-1 for E. coli and of 0 CFU 25 g-1 for Salmonella. Taken together, the results of this study indicate that Niamey’s UPA enterprises put environmental safety at risk since excess inputs of N, P and K to crop and livestock production units favour N volatilisation and groundwater pollution by nutrient leaching. However, more detailed studies are needed to corroborate these indications. Farmers’ revenues could be significantly increased if nutrient use efficiency in the different production (sub)systems was improved by better matching nutrient supply through fertilizers and feeds with the actual nutrient demands of plants and animals.