Relativistic prediction of the ground state of atomic Lawrencium

In contradiction to the prediction of the Periodic Table but in agreement with earlier suggestions by Brewer and Mann, the ground state configuration of atomic Lawrencium (Z = 103) will not be 7s^2 6d^2 D_3/2 but 7s^2 7p ^2p_1/2. The reason for this deviation from normal trends across the Periodic Table are strong relativistic effects on the outermost 7P_l/2 orbital. Multicontiguration Dirac-Fock calculations are reported for Lawrencium and analogous lighter atoms. These calculations include contributions from magnetic and retardation interactions and an estimation of quantum electrodynamic corrections.

Development of hybrid UV VCSEL with organic active material and dielectric DBR mirrors for medical, sensoric and data storage applications

Lasers play an important role for medical, sensoric and data storage devices. This thesis is focused on design, technology development, fabrication and characterization of hybrid ultraviolet Vertical-Cavity Surface-Emitting Lasers (UV VCSEL) with organic laser-active material and inorganic distributed Bragg reflectors (DBR). Multilayer structures with different layer thicknesses, refractive indices and absorption coefficients of the inorganic materials were studied using theoretical model calculations. During the simulations the structure parameters such as materials and thicknesses have been varied. This procedure was repeated several times during the design optimization process including also the feedback from technology and characterization. Two types of VCSEL devices were investigated. The first is an index coupled structure consisting of bottom and top DBR dielectric mirrors. In the space in between them is the cavity, which includes active region and defines the spectral gain profile. In this configuration the maximum electrical field is concentrated in the cavity and can destroy the chemical structure of the active material. The second type of laser is a so called complex coupled VCSEL. In this structure the active material is placed not only in the cavity but also in parts of the DBR structure. The simulations show that such a distribution of the active material reduces the required pumping power for reaching lasing threshold. High efficiency is achieved by substituting the dielectric material with high refractive index for the periods closer to the cavity. The inorganic materials for the DBR mirrors have been deposited by Plasma- Enhanced Chemical Vapor Deposition (PECVD) and Dual Ion Beam Sputtering (DIBS) machines. Extended optimizations of the technological processes have been performed. All the processes are carried out in a clean room Class 1 and Class 10000. The optical properties and the thicknesses of the layers are measured in-situ by spectroscopic ellipsometry and spectroscopic reflectometry. The surface roughness is analyzed by atomic force microscopy (AFM) and images of the devices are taken with scanning electron microscope (SEM). The silicon dioxide (SiO2) and silicon nitride (Si3N4) layers deposited by the PECVD machine show defects of the material structure and have higher absorption in the ultra violet range compared to ion beam deposition (IBD). This results in low reflectivity of the DBR mirrors and also reduces the optical properties of the VCSEL devices. However PECVD has the advantage that the stress in the layers can be tuned and compensated, in contrast to IBD at the moment. A sputtering machine Ionsys 1000 produced by Roth&Rau company, is used for the deposition of silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (Al2O3) and zirconium dioxide (ZrO2). The chamber is equipped with main (sputter) and assisted ion sources. The dielectric materials were optimized by introducing additional oxygen and nitrogen into the chamber. DBR mirrors with different material combinations were deposited. The measured optical properties of the fabricated multilayer structures show an excellent agreement with the results of theoretical model calculations. The layers deposited by puttering show high compressive stress. As an active region a novel organic material with spiro-linked molecules is used. Two different materials have been evaporated by utilizing a dye evaporation machine in the clean room of the department Makromolekulare Chemie und Molekulare Materialien (mmCmm). The Spiro-Octopus-1 organic material has a maximum emission at the wavelength λemission = 395 nm and the Spiro-Pphenal has a maximum emission at the wavelength λemission = 418 nm. Both of them have high refractive index and can be combined with low refractive index materials like silicon dioxide (SiO2). The sputtering method shows excellent optical quality of the deposited materials and high reflection of the multilayer structures. The bottom DBR mirrors for all VCSEL devices were deposited by the DIBS machine, whereas the top DBR mirror deposited either by PECVD or by combination of PECVD and DIBS. The fabricated VCSEL structures were optically pumped by nitrogen laser at wavelength λpumping = 337 nm. The emission was measured by spectrometer. A radiation of the VCSEL structure at wavelength 392 nm and 420 nm is observed.

On the difficulties of present theoretical models to predict the oxidation state of atomic Au adsorbed on regular sites of CeO2(111)

The electronic structure and oxidation state of atomic Au adsorbed on a perfect CeO2(111) surface have been investigated in detail by means of periodic density functional theory-based calculations, using the LDA+U and GGA+U potentials for a broad range of U values, complemented with calculations employing the HSE06 hybrid functional. In addition, the effects of the lattice parameter a0 and of the starting point for the geometry optimization have also been analyzed. From the present results we suggest that the oxidation state of single Au atoms on CeO2(111) predicted by LDA+U, GGA+U, and HSE06 density functional calculations is not conclusive and that the final picture strongly depends on the method chosen and on the construction of the surface model. In some cases we have been able to locate two well-defined states which are close in energy but with very different electronic structure and local geometries, one with Au fully oxidized and one with neutral Au. The energy difference between the two states is typically within the limits of the accuracy of the present exchange-correlation potentials, and therefore, a clear lowest-energy state cannot be identified. These results suggest the possibility of a dynamic distribution of Au0 and Au+ atomic species at the regular sites of the CeO2(111) surface.

Spin polarization, orbital occupation and band gap opening in vanadium dioxide: the effect of screened Hartree–Fock exchange

The metal–insulator transition of VO2 so far has evaded an accurate description by density functional theory. The screened hybrid functional of Heyd, Scuseria and Ernzerhof leads to reasonable solutions for both the low-temperature monoclinic and high-temperature rutile phases only if spin polarization is excluded from the calculations. We explore whether a satisfactory agreement with experiment can be achieved by tuning the fraction of Hartree Fock exchange (a) in the density functional. It is found that two branches of locally stable solutions exist for the rutile phase for 12:5% 6 a 6 20%. One is metallic and has the correct stability as compared to the monoclinic phase, the other is insulating with lower energy than the metallic branch. We discuss these observations based on the V 3d orbital occupations and conclude that a ¼ 10% is the best possible choice for spin-polarized VO2 calculations.

Synthesis, mechanism of formation, and molecular orbital calculations of arylamidoximes

A simple and easy synthesis of ten arylamidoximes from arylnitriles and hydroxylamine is described. The formation of the arylamides has been observed to a much lesser extent in the present work. A new mechanism for the formation of arylamidoximes, as well as arylamides, from arylnitriles and hydroxylamine is suggested. Quantum mechanical calculations have been carried out to support this mechanism. The enthalpy of formation in conjunction with atomic charges of the reactants and intermediates helped to understand more about the generation of the products.

Dependence of Response Functions and Orbital Functionals on Occupation Numbers

Explicitly orbital-dependent approximations to the exchange-correlation energy functional of density functional theory typically not only depend on the single-particle Kohn-Sham orbitals but also on their occupation numbers in the ground-state Slater determinant. The variational calculation of the corresponding exchange-correlation potentials with the optimized effective potential (OEP) method therefore also requires a variation of the occupation numbers with respect to a variation in the effective single-particle potential, which is usually not taken into account. Here it is shown under which circumstances this procedure is justified.

Orbital-polarization terms: From a phenomenological to a first-principles description of orbital magnetism in density-functional theory

Phenomenological orbital-polarizition (OP) terms have been repeatedly introduced in the single-particle equations of spin-density-functional theory, in order to improve the description of orbital magnetic moments in systems containing transition metal ions. Here we show that these ad hoc corrections can be interpreted as approximations to the exchange-correlation vector potential A(xc) of current-density functional theory (CDFT). This connection provides additional information on both approaches: phenomenological OP terms are connected to first-principles theory, leading to a rationale for their empirical success and a reassessment of their limitations and the approximations made in their derivation. Conversely, the connection of OP terms with CDFT leads to a set of simple approximations to the CDFT potential A(xc), with a number of desirable features that are absent from electron-gas-based functionals. (C) 2008 Wiley Periodicals, Inc.

Hybrid materials from intermolecular associations between cationic lipid and polymers

Intermolecular associations between a cationic lipid and two model polymers were evaluated from preparation and characterization of hybrid thin films cast on silicon wafers. The novel materials were prepared by spin-coating of a chloroformic solution of lipid and polymer on silicon wafer. Polymers tested for miscibility with the cationic lipid dioctadecyldimethylammonium bromide (DODAB) were polystyrene (PS) and poly(methyl methacrylate) (PMMA). The films thus obtained were characterized by ellipsometry, wettability, optical and atomic force microscopy, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and activity against Escherichia coli. Whereas intermolecular ion-dipole interactions were available for the PMMA-DODAB interacting pair producing smooth PMMA-DODAB films, the absence of such interactions for PS-DODAB films caused lipid segregation, poor film stability (detachment from the silicon wafer) and large rugosity. In addition, the well-established but still remarkable antimicrobial DODAB properties were transferred to the novel hybrid PMMA/DODAB coating, which is demonstrated to be highly effective against E. coli.

Structure and microstructure of PbTiO3 thin films obtained from hybrid chemical method

PbTiO3 thin films were deposited on Si(100) via hybrid chemical method and crystallized between 400 and 700 degreesC to study the effect of the crystallization kinetics on structure and microstructure of these materials. X-ray diffraction (XRD) technique was used to study the structure of the crystallized films. In the temperature range investigated, the lattice strain (c/a) presented a maximum value (c/a = 1.056) for film crystallized at 600 degreesC for I h. Atomic force microscopy (AFM) was used in investigation of the microstructure of the films. The rms roughness of the films linearly increases with temperature and ranged from 1.25 to 9.04 nm while the grain sizes ranged from 130.6 to 213.6 nm. Greater grain size was observed for film crystallized at 600 degreesC for 1 h. (C) 2002 Elsevier B.V. S.A. All rights reserved.

Momentum-space non-hydrogenic wavefunction of quantum defect theory

We derive a closed-form analytic expression in momentum space for the asymptotic non-hydrogenic wavefunction of the quantum defect theory (QDT) due to Seaton and compare it with a widely used QDT-approximate wavefunction for the Rydberg states Li-3(2s), Mg-24(6s) and Rb-37(5s).

Vibrational-rotational analysis of the Hulthen potential using hydrogenic eigenfunction bases

Hulthen's potential admits analytical solutions for its energy eigenvalues and eigenfunctions corresponding to zero orbital angular momentum stales, but its non zero angular momentum states are not equally known. This work presents a vibrational-rotational analy sis of Hulthen's potential using hydrogenic eigenfunction bases, which may be of interest and useful to students of quantum mechanics at different stages.

Stability and collapse of a hybrid Bose-Einstein condensate of atoms and molecules

The dynamics of stability and collapse of a trapped atomic Bose-Einstein condensate (BEC) coupled to a molecular one is studied using the time-dependent Gross-Pitaevskii (GP) equation including a nonlinear interaction term which can transform two atoms into a molecule and vice versa. We find an interesting oscillation of the number of atoms and molecules for a BEC of fixed mass. This oscillation is a consequence of continuous transformation in the condensate of two atoms into a molecule and vice versa. For the study of collapse an absorptive contact interaction and an imaginary quartic three-body recombination term are included in the GP equation. It is possible to have a collapse of one or both components when one or more of the nonlinear terms in the GP equation are attractive in nature, respectively.

Charge injection in an LED with a hybrid composite as the emissive layer

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Microstructure and corrosion resistance of inorganic-organic (ZrO2-PMMA) hybrid coating on stainless steel

Zirconia-polymethylmetacrylate hybrids prepared by a sol-gel method were deposited by dip-coating on stainless steel to improve the resistance against wet corrosion. The effect of the concentration of polymethylmetacrylate and the number of coating applications on the microstructure and corrosion performance of coated samples was investigated. The microstructural properties of samples was analyzed by scanning electron and atomic force microscopy, adhesion tests and profilemeter measurements. The electrochemical corrosion was evaluated through potentiodynamic polarization curves at room temperature. Results show that the sample prepared with 17 vol.% of polymethylmethacrylate has a maximum corrosion resistance, smaller roughness, are hermetic and adherent to the substrate. This film increases the life time of the stainless steel by a factor 30. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Structural deformation monitored by vibrational properties and orbital modeling in (Pb,Sm)TiO3 systems

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)