Physics, Condensed Matter

Magnetic, thermodynamic, and structural properties of the manganese oxides La1-xCa xMnO3 are studied. Neutron powder diffraction reveals two distinct crystallographic phases as well as two magnetic (ferromagnetic and antiferromagnetic) phases for 0.08 < x < 0.14. Details of the compositional dependence of the phase fractions is discussed in the context of local ferromagnetism. Comparisons of magnetic and crystallographic properties are made to the analogous electron-doped Ca1- yLayMnO3 (0 < y < 0.20) system. Thermodynamic properties of La1- xCaxMnO 3 (0 < x < 0.54) are investigated for possible applications in magnetic refrigeration. A maximum magnetic entropy change of 5.5 J/kg K and a corresponding temperature change of 2 K are estimated for x = 0.28. The magnetocaloric effect in antiferromagnetic and charge-ordering compounds is found to be small.

Neutron powder diffraction, high pressure, magnetic susceptibility, and heat capacity measurements, as well as x-ray powder diffraction and iodometric titration, have been conducted on transition metal nickel oxides (TMOs), representative Ruddlesden-Popper (RP) phases Lan+1NinO3n+1 (n = 1, 2, ..., infinity) and hole-doped La2-xSr xNiO4 (0 < x < 1.2). The first complete study of La 2-xSrxNiO4 (0 < x < 1.2) and La n+1NinO3n+1 (n = 2 and 3) phases under high pressure is produced. Strong direct experimental evidence for polaron dominated electrical conduction in these charge transfer (CT) gap La2-xSr xNiO4 compounds is provided. Temperature evolution of the crystal structure of La2-xSrxNiO4 (x = 1/4 and 1/3) is revealed through neutron powder diffraction, structural relationships among n = 1, 2, and 3 phases are exhibited, and charge density wave (CDW) in multilayer Lan+1NinO3n+1 phases is strongly suggested. No superconductivity is observed at pressures up to 1.6 GPa and temperatures down to 4.2 K.

In this dissertation I have used photoluminescence (PL) spectrometric analysis to measure the temperature dependence of the spectral features of the direct band gap semiconductor CdxZn1-xSe , for two nominal concentrations x = 0.25, 0.50, in the temperature range 25--300 K. The effective concentrations were obtained from analysis of the spectra. The parameters that describe the temperature dependence of the line width broadening have been evaluated using different models. The PL broadband characteristics of Cd0.22Zn0.78Se and Cd0.41Zn0.59Se are also investigated within the energy range 1.36--2.40 eV and temperature range 25--305 K. Two broad bands are observed, the higher energy band I centered at 1.991 and 1.773 eV, the lower energy band II centered at 1.844 and 1.705 eV for the two samples, respectively. The emission bands are attributed to donor-acceptor pair transitions. The energy scheme shows two donors and two acceptor levels, the binding energies of the donors for Cd 0.22Zn0.78Se are 29 and 208 meV below the conduction band, the binding energies of the acceptors 472 and 511 meV above the valence band. The binding energies of the donors for Cd0.41Zn 0.59Se are 27 and 137 meV, the binding energies of the acceptors 393 and 423 eV. A significant blue shift in energy with increasing temperature was observed for the lower energy band. The ionization temperatures for the deep donors are 279 and 287 K for Cd0.22Zn0.78Se and Cd0.41Zn0.59Se, respectively.

Using the order-N locally-self-consistent multiple scattering (LSMS) method, we carry out first-principles studies of the displacement of atoms from their average sites in the vicinity of a vacancy and transition metal impurities in copper. Our approach is to relax the first nearest neighbor distance and to calculate total energy for a number of relaxed geometries. We then obtain the equilibrium configuration of the nuclei from minimization of the total energy.

The electronic structure of beta'-NiAl alloy and its low-index high-symmetry surfaces has been studied with a combination of photocurrent and first-principles electronic structure calculations. Bulk calculations have been performed with both the LMTO and LSMS computational codes, and the core level shifts upon alloying are discussed in detail. Defect formation and bonding mechanisms in off-stoichiometric NiAl are investigated. The electronic structure of the (110), (100) and (111) surfaces are investigated using the LMTO and LSMS, and electronic potentials for input to the photocurrent code are evaluated in the surface geometry. Photocurrent calculations for the (110), (100) and (111) surface are presented and compared with high quality experimental measurements. The (100) surface is found to have a double Ni termination. This defect layer is predicted to sustain a magnetic moment. The rippling of the (110) surface is modelled in the photocurrent calculations, and is found to effect the spectral profile in significant ways. The calculated photocurrent spectra are used to predict the surface composition for the (100), (111) and (110) surfaces, and the rippling value of the (110) surface. Agreement with experiment is good. A method for utilizing computational photoemission spectra to predict the structure and composition of metallic surfaces is presented, and its strengths and weaknesses are discussed.

We developed code in MasPar Fortran (an extension of Fortran 90) to conduct molecular dynamics simulations on a MasPar MP-1 massively parallel computer. The code is portable to other Single-Instruction Multiple-Data (SIMD) platforms with minor modifications. We used a two dimensional grid containing over 220,000 atoms to simulate a high strain-rate fracture growth in Cu-Ni alloys. The atoms are arranged in a triangular lattice corresponding to an fcc (111) surface and a Lennard-Jones (LJ) potential with a spline cutoff is used for the inter-atomic potential. The location of the spline cutoff can be adjusted to simulate either brittle or ductile fracture. The atomic positions are spatially decomposed on each Processor Element, the data are shared with adjacent PEs, and atoms are transferred as they move. Free boundary conditions are used, and the appropriate techniques for applying strain and damping unwanted reflections are developed. We report variations in the critical applied strain with increasing temperature, and propose a novel method for characterizing the location of a crack tip. This method lends itself to algorithmic calculation and reporting by the fracture code. Our results represent the first microscopic analysis of fracture in an alloy system and extend recent work on pure metals. During the investigation, we introduced a Sigma 5 grain boundary (36.9) into the sample, with appropriate grain-boundary segregation. We developed a technique for rapidly quenching the high-energy particles at an artificially constructed grain boundary. We demonstrate crack blunting at the grain boundary. We also report on flyer/target impact simulations in an alloy with an LJ inter-atomic potential.

The electronic structure of equi-atomic CuAu has been investigated by a combination of photoelectron spectroscopy and first-principles band structure calculations. The study includes the first ever ARUPS and ARAES measurements from a single crystal of CuAu I. We have studied in detail the energy dispersion and shifts of a Tamm state on the (001) and (100) surfaces and we determined the surface lattice constants and the dependencies of the energy shifts on atomic concentration and geometry. Two new surface states were found on the two surfaces and their properties have been investigated. Comparisons between the valence band spectra from the two samples of CuAu I have been carried out and the results show that the different atomic arrangements in the crystal do not have a significant effect on the band structure. We also compared spectra from the alloy with those from the parent metals. A series of calculations of the electronic structure of CuAu I has been carried out by the SCF-LMTO-ASA and RKKR methods. We found that the superzone boundaries that are created when the CuAu II phase is formed destroy appreciable regions of Fermi surface, thus, favoring the latter phase. The positions of the new boundaries are related directly to the period of the long period superlattice and we have investigated their dependence on the e/a ratio and pressure. The results are in very good agreement with previous experimental measurements. We also calculated the Fermi surfaces of three disordered Cu-Au alloys near the equi-atomic composition using the KKR-CPA scheme. The results have shown strong evidence that the Fermi surface topology may play an important role in stabilizing and determining the modulation of the LPS in CuAu II.

Zinc tungstate (ZnWO4) is promising as a scintillator and laser host material. However, the presence of color centers limit its applications. It has been found that special annealing techniques or doping with metallic elements such as Nb or Sb can bleach the samples (Zhou et al. 1986a, 1986b, 1989). A group-theoretical analysis of the characteristic lattice vibrational modes for ZnWO4 single crystals is given. The mode assignments have been made. The temperature dependence of the Raman spectra has been obtained experimentally in various polarization geometries. Anharmonic contributions and interactions between phonons are discussed. Photoluminescence studies of ZnWO4 (colored, color-free), ZnWO4: Nb and ZnWO4:Sb have been carried out in the temperature range from 11 to 430 K. All samples show the blue emission band. An IR emission band with a zero-phonon line (ZPL) has been found in ZnWO4 colored samples only. The lineshape function of the emission bands has been theoretically studied and compared with the experimental results. Radiative, non-radiative and multiphonon transitions have been investigated in the thermal quenching model. The temperature dependences of the intensity, the frequency and the linewidth of the ZPL have been studied. Using the Single Configurational Coordinate model, the linear coupling between electrons and phonons has been analyzed. The quadratic coupling of electrons and phonons has been studied in the Debye approximation. The coupling of electronic transitions to normal vibrational modes, pseudo-localized vibrational modes and localized modes is also discussed.

In this dissertation, multiple scattering theory (MST) plays a fundamental role. It is applied to develop the electronic structure calculation techniques for ordered solids, single impurities and binary alloys. The most accurate fast-band-theory technique based on the MST is the quadratic Korringa-Kohn-Rostoker (QKKR) method. A method for carrying out the self-consistent QKKR calculation for ordered compounds is derived and applied to palladium hydride. The application of the QKKR method to single impurity problems is also examined. In order to study phase diagrams of binary alloys, a new approach, called the embedded cluster Monte Carlo (ECMC) method, is developed. It is used to calculate the miscibility gap in the Pd-Rh alloy phase diagram to an accuracy that has never before been achieved. A non-magnetic calculation for Cu-Ni alloys is also provided. These calculations required the mastery of Korringa-Kohn-Rostoker coherent-potential-approximation methods and the development of embedded cluster codes.

The electronic structures of beta'-AgMg and Ag3Mg alloys have been investigated by a combination of photoelectron spectroscopy and first-principles band structure and photocurrent calculations. The study includes the first ever XPS and UPS measurements from the ordered and disordered phases of Ag3Mg. We concentrated mainly on measurements of the valence bands and the core level binding energies for these alloys and their parent metals. The band structures of the ordered alloys and pure metals have been calculated by the SCF-LMTO-ASA method, and the KKR and KKRCPA calculational schemes have been used in order to determine the electronic structures of both ordered and disordered phases of Ag3Mg on an equal footing. For the purpose of interpreting the core level shifts due to alloying, a modified LMTO scheme has been applied, in a supercell geometry, to allow for relaxation effects. In addition, we have shown that the Fermi surface topology may well be an important factor in determining the relative stability of the long period superlattice structure in Ag3Mg. In general, the calculations are in very good agreement with the experimental results. We conclude that the combination of theoretical calculations and photoemission measurements provides a detailed understanding of the electronic structures and the properties of Ag-Mg alloys.