This work is a theoretical investigation on the physical properties of semiconductor-based two-dimensional photonic crystals, in particular for what concerns systems embedded in planar dielectric waveguides (GaAs/AlGaAs, GaInAsP/InP heterostructures, and self-standing membranes) or based on macro-porous silicon. The photonic-band structure of photonic crystals and photonic-crystal slabs is numerically computed and the associated light-line problem is discussed, which points to the issue of intrinsic out-of-lane diffraction losses for the photonic bands lying above the light line. The photonic states are then classified by the group theory formalism: each mode is related to an irreducible representation of the corresponding small point group. The optical properties are investigated by means of the scattering matrix method, which numerically implements a variable-angle-reflectance experiment; comparison with experiments is also provided. The analysis of surface reflectance proves the existence of selection rules for coupling an external wave to a certain photonic mode. Such rules can be directly derived from symmetry considerations. Lastly, the control of wave propagation in weak-index contrast photonic-crystal slabs is tackled in view of designing building blocks for photonic integrated circuits. The proposed designs are found to comply with the major requirements of low-loss propagation, high and single-mode transmission. These notions are then collected …

The computational part of the thesis is the investigation of titanium chloride (II) as a potential catalyst for the bis-silylation reaction of ethylene with hexaclorodisilane at different levels of theory. Bis-silylation is an important reaction for producing bis(silyl) compounds and new C-Si bonds, which can serve as monomers for silicon containing polymers and silicon carbides. Ab initio calculations on the steps involved in a proposed mechanism are presented. This choice of reactants allows them to study this reaction at reliable levels of theory without compromising accuracy. The calculations indicate that this is a highly exothermic barrierless reaction. The TiCl{sub 2} catalyst removes a 50 kcal/mol activation energy barrier required for the reaction without the catalyst. The first step is interaction of TiCl{sub 2} with ethylene to form an intermediate that is 60 kcal/mol below the energy of the reactants. This is the driving force for the entire reaction. Dynamic correlation plays a significant role because RHF calculations indicate that the net barrier for the catalyzed reaction is 50 kcal/mol. They conclude that divalent Ti has the potential to become an important industrial catalyst for silylation reactions. In the programming part of the thesis, parallelization of different quantum chemistry methods is …

The consideration of compliant mechanisms as Microelectromechanical Systems (MEMS) is the focus of this research endeavor. MEMS are micron to millimeter devices that combine electrical, mechanical, and information processing capabilities on the same device. These MEMS need some mechanical motion or parts that move relative to each other. This relative motion, using multiple parts, is not desired because of the assembly requirement and the friction introduced. Compliant devices limits or eliminates friction and the need for multi-component assembly. Compliant devices improve designs by creating single piece mechanisms. The purpose of this research is to validate surface micromachining as a viable fabrication process for compliant MEMS designs. Specifically, this research has sought to fabricate a micro-compliant gripper and a micro-compliant clamp to illustrate the process. While other researchers have created compliant MEMs, most have used comb-drive actuation methods and bulk micromachining processes. This research focused on fully-compliant devices that use device flexibility for motion and actuation. Validation of these compliant MEMS is achieved by structural optimization of device design and functional performance testing. This research contributes to the ongoing research in MEMS by evaluating the potential of using surface micromachining as a process for fabricating compliant micro-mechanisms.

Three papers are included in this dissertation. The first paper: ''Structural aspects of the fivefold quasicrystalline Al-Cu-Fe surface from STM and dynamical LEED studies'', is in press with ''Surface Science''. The second paper: ''An STM study of the atomic structure of the icosahedral Al-Cu-Fe fivefold surface'' is submitted to ''Physical Review B, Rapid Communication''. The third paper: ''Pseudomorphic starfish: arrangement of extrinsic metal atoms on a quasicrystalline substrate'' is submitted to ''Nature''. Following the third paper are general conclusions and appendices that document the published paper ''Structural aspects of the three-fold surface of icosahedral Al-Pd-Mn'' (appearing in volume 461, issue 1-3 of ''Surface Science'' on page L521-L527, 2000), the design as well as the specifications of the aluminum evaporator used in the aluminum deposition study in this dissertation, an extended discussion of the aluminum deposition on the quasicrystalline surface, and the STM database.

This is concerned with imaging and wave propagation in nonhomogeneous media, and includes a collection of computational techniques, such as level set methods with material transport, Dijkstra-like Hamilton-Jacobi solvers for first arrival Eikonal equations and techniques for data smoothing. The theoretical components include aspects of seismic ray theory, and the results rely on careful comparison with experiment and incorporation as input into large production-style geophysical processing codes. Producing an accurate image of the Earth's interior is a challenging aspect of oil recovery and earthquake analysis. The ultimate computational goal, which is to accurately produce a detailed interior map of the Earth's makeup on the basis of external soundings and measurements, is currently out of reach for several reasons. First, although vast amounts of data have been obtained in some regions, this has not been done uniformly, and the data contain noise and artifacts. Simply sifting through the data is a massive computational job. Second, the fundamental inverse problem, namely to deduce the local sound speeds of the earth that give rise to measured reacted signals, is exceedingly difficult: shadow zones and complex structures can make for ill-posed problems, and require vast computational resources. Nonetheless, seismic imaging is a crucial part …

Lutein and zeaxanthin are the only carotenoids accumulated in the macula of the human retina and are known as the macular pigments (MP). These pigments account for the yellow color of the macula and appear to play an important role in protecting against age-related macular degeneration (AMD). The uptake of lutein and zeaxanthin in human eyes is remarkably specific. It is likely that specific transport or binding proteins are involved. The objective is to determine whether transthyretin (TTR) is a transport protein in human plasma and could thus deliver lutein from the blood to the retina. In this study, they used a biosynthetic {sup 13}C-lutein tracer and gas chromatography-combustion interfaced-isotope ratio mass spectrometry (GCC-IRMS) to gain the requisite sensitivity to detect the minute amounts of lutein expected as a physiological ligand for human transthyretin. The biosynthetic {sup 13}C-labeled lutein tracer was purified from algae. Healthy women (n = 4) each ingested 1 mg of {sup 13}C-labeled lutein daily for 3 days and a blood sample was collected 24 hours after the final dose. Plasma TTR was isolated by retinol-binding protein (RBP)-sepharose affinity chromatography and extracted with chloroform. The {sup 13}C/{sup 12}C ratio in the TTR extract was measured by GCC-IRMS. …

MP{_}Lite is a light weight message-passing library designed to deliver the maximum performance to applications in a portable and user friendly manner. The Virtual Interface (VI) architecture is a user-level communication protocol that bypasses the operating system to provide much better performance than traditional network architectures. By combining the high efficiency of MP{_}Lite and high performance of the VI architecture, they are able to implement a high performance message-passing library that has much lower latency and better throughput. The design and implementation of MP{_}Lite for M-VIA, which is a modular implementation of the VI architecture on Linux, is discussed in this thesis. By using the eager protocol for sending short messages, MP{_}Lite M-VIA has much lower latency on both Fast Ethernet and Gigabit Ethernet. The handshake protocol and RDMA mechanism provides double the throughput that MPICH can deliver for long messages. MP{_}Lite M-VIA also has the ability to channel-bonding multiple network interface cards to increase the potential bandwidth between nodes. Using multiple Fast Ethernet cards can double or even triple the maximum throughput without increasing the cost of a PC cluster greatly.

The driving force behind much of the work in this dissertation was to gain further understanding of the unique olefin to carbene isomerization observed in the thermolysis of 1,1-dimethyl-2-methylenesilacyclobutane by finding new examples of it in other silicon and germanium compounds. This lead to the examination of a novel phenylmethylenesilacyclobut-2-ene, which did not undergo olefin to carbene rearrangement. A synthetic route to methylenegermacyclobutanes was developed, but the methylenegermacyclobutane system exhibited kinetic instability, making the study of the system difficult. In any case the germanium system decomposed through a complex mechanism which may not include olefin to carbene isomerization. However, this work lead to the study of the gas phase thermochemistry of a series of dialkylgermylene precursors in order to better understand the mechanism of the thermal decomposition of dialkylgermylenes. The resulting dialkylgermylenes were found to undergo a reversible intramolecular {beta} C-H insertion mechanism.

GaN is an interesting material: technologically very useful, but still having many unexplained features. Two such features are the broad defect-related luminescence bands: the YL of n-type GaN and the BL of Mg-doped p-type GaN. We have employed selective excitation to investigate these bands. In the case of the YL, most of the previous evidence has supported a recombination model between distant donors and acceptors, most likely a transition involving a shallow donor to a deep acceptor. Our selective excitation experiments have resolved finer structures within the YL. Our results indicate that the YL in bulk samples is related to the YL in film samples. We suggest that selectively excited YL involves recombination at DAP complexes, rather than between spatially distant DAPs (however other recombination channels, including that of distant DAPs may become significant under other excitation conditions). Characteristics of the DAP complexes within our YL model include (a) an electron localization energy of around 60-70 meV, (b) a localized phonon energy of around 40 meV, and (c) excited states of the complex at 200 and 370 meV above the ground state. In the case of the BL, the deep defect responsible for the BL is unknown, and there may …

Exploration of the alkali metal/alkaline-earth metal/heavy tetrel (Sn or Pb) systems has revealed a vast array of new chemistry and novel structure types. The structures and properties of these new materials have been studied in an attempt to understand the chemistry of these and other related systems. The first phase reported is Rb{sub 4}Pb{sub 9} (K{sub 4}Pb{sub 9} type). The compound contains two different types of Pb{sub 9}{sup 4-} deltahedra, a monocapped square pyramid and a distorted tricapped trigonal prism. Both cluster geometries correspond to a nido assignment even though the tricapped trigonal prism is not the classic Wade's rules nido deltahedron expected for a monocapped square antiprism. Also, a series of compounds that contain square pyramidal Tt{sub 5} polyanions of tin and lead has been obtained in alkaline-earth or rare-earth metal-tetrel systems by direct fusion of the elements to yield Sr{sub 3}Sn{sub 5}, Ba{sub 3}Pb{sub 5}, and La{sub 3}Sn{sub 5}. These phases contain square pyramidal clusters of the tetrel elements that are weakly interlinked into chains via two types of longer intercluster interactions that are mediated by bridging cations and substantially influenced by cation size and the free electron count. Attempts at incorporating another main-group element to form heteroatomic …

This report describes the development and application of a dispatch optimization algorithm for integrated energy systems (IES) comprised of on-site cogeneration of heat and electricity, energy storage devices, and demand response opportunities. This work is intended to aid commercial and industrial sites in making use of modern computing power and optimization algorithms to make informed, near-optimal decisions under significant uncertainty and complex objective functions. The optimization algorithm uses a finite set of randomly generated future scenarios to approximate the true, stochastic future; constraints are included that prevent solutions to this approximate problem from deviating from solutions to the actual problem. The algorithm is then expressed as a mixed integer linear program, to which a powerful commercial solver is applied. A case study of United States Postal Service Processing and Distribution Centers (P&DC) in four cities and under three different electricity tariff structures is conducted to (1) determine the added value of optimal control to a cogeneration system over current, heuristic control strategies; (2) determine the value of limited electric load curtailment opportunities, with and without cogeneration; and (3) determine the trade-off between least-cost and least-carbon operations of a cogeneration system. Key results for the P&DC sites studied include (1) in …

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Excitation functions for the 1n and 2n exit channels of the 208Pb(51V,xn)259-xDb reaction were measured. A maximum cross section of the 1n exit channel of 2070+1100/-760 pb was measured at an excitation energy of 16.0 +- 1.8 MeV. For the 2n exit channel, a maximum cross section of 1660+450/-370 pb was measured at 22.0 +- 1.8 MeV excitation energy. The 1n excitation function for the 209Bi(50Ti,n)258Db reaction was remeasured, resulting in a cross section of 5480+1730/1370 pb at an excitation energy of 16.0 +- 1.6 MeV. Differences in cross section maxima are discussed in terms of the fusion probability below the barrier. The extraction of niobium (Nb) and tantalum (Ta) from hydrochloric acid and mixed hydrochloric acid/lithium chloride media by bis(2-ethylhexyl) hydrogen phosphate (HDEHP) and bis(2-ethylhexyl) hydrogen phosphite (BEHP) was studied. The goal of the experiments was to find a system that demonstrates selectivity among the members of group five of the Periodic Table and is also suitable for the study of dubnium (Db, Z = 105). Experiments with niobium and tantalum were performed with carrier (10-6 M), carrier free (10-10 M) and trace (10-16 M) concentrations of metal using hydrochloric acid solution with concentrations ranging from 1 - 11 …

Highly charged ions are extracted from an electron beam ion trap and guided to Retrap, a cryogenic Penning trap, where they are merged with laser cooled Be{sup +} ions. The Be{sup +} ions act as a coolant for the hot highly charged ions and their temperature is dropped by about 8 orders of magnitude in a few seconds. Such cold highly charged ions form a strongly coupled nonneutral plasma exhibiting, under such conditions, the aggregation of clusters and crystals. Given the right mixture, these plasmas can be studied as analogues of high density plasmas like white dwarf interiors, and potentially can lead to the development of cold highly charged ion beams for applications in nanotechnology. Due to the virtually non existent Doppler broadening, spectroscopy on highly charged ions can be performed to an unprecedented precision. The density and the temperature of the Be{sup +} plasma were measured and highly charged ions were sympathetically cooled to similar temperatures. Molecular dynamics simulations confirmed the shape, temperature and density of the highly charged ions. Ordered structures were observed in the simulations.

The Jefferson Lab Hall A experiment E99-114 comprised a series of measurements to explore proton Compton scattering at high momentum transfer. For the first time, the polarisation transfer observables in the p (~ 0 ~ p) reaction were measured in the GeV energy range, where it is believed that quark-gluon degrees of freedom begin to dominate. The experiment utilised a circularly polarised photon beam incident on a liquid hydrogen target, with the scattered photon and recoil proton detected in a lead-glass calorimeter and a magnetic spectrometer, respectively.

Doping experiments on La{sub 2}CuO{sub 4}, Sr{sub 2}CuO{sub 3} and SrCu{sub 2}(BO{sub 3}){sub 2} were performed with the intent of synthesizing new metallic low-=dimensional cuprate oxide compounds. Magnetic susceptibility {chi}(T) measurements on a polycrystalline La{sub 2}CuO{sub 4} sample chemically oxidized at room temperature in aqueous NaClO showed superconductivity with a superconducting transition temperature T{sub c} of 42.6 K and a Meissner fraction of 26%. They were unable to electrochemically oxidize La{sub 2}CuO{sub 4} in a nonaqueous solution of tetramethylammonium hydroxide (TMAOH) and methanol. Sr{sub 2}CuO{sub 3} was found to decompose upon exposure to air and water. Electron paramagnetic resonance, isothermal magnetization M(H), and {chi}(T) measurements on the primary decomposition product, Sr{sub 2}Cu(OH){sub 6}, were consistent with a nearly isolated, spin S = 1/2, local moment model for the Cu{sup +2} spins. From a fit of {chi}(T) by the Curie-Weiss law and of the M(H) isotherms by a modified Brillouin function, the weakly antiferromagnetic exchange interaction between adjacent Cu{sup +2} spins in Sr{sub 2}Cu(OH){sub 6} was found to be J/k{sub B} = 1.06(4) K. Doping studies on SrCu{sub 2}(BO{sub 3}){sub 2} were inconclusive. {chi}(T) measurements on an undoped polycrystalline sample of SrCu{sub 2}(BO{sub 3}){sub 2}, a sample treated with distilled water, …

The ability to finely tune the size and shape of inorganic semiconducting nanocrystals is an area of great interest, as the more control one has, the more applications will be possible for their use. The first two basic shapes develped in nanocrystals were the sphere and the anistropic nanorod. the II_VI materials being used such as Cadmium Selenide (CdSe) and Cadmium Telluride (CdTe), exhibit polytypism, which allows them to form in either the hexagonally packed wurtzite or cubically packed zinc blende crystalline phase. The nanorods are wurtzite with the length of the rod growing along the c-axis. As this grows, stacking faults may form, which are layers of zinc blende in the otherwise wurtzite crystal. Using this polytypism, though, the first generation of branched crystals were developed in the form of the CdTe tetrapod. This is a nanocrystal that nucleates in the zincblend form, creating a tetrahedral core, on which four wurtzite arms are grown. This structure opened up the possibility of even more complex shapes and applications. This disseration investigates the advancement of branching control and further understanding the materials polytypism in the form of the stacking faults in nanorods.

This dissertation presents the highest four-momentum transfer, Q^2,quasielastic (x_Bj = 1) results from Experiment E01-020 which systematically explored the 2He(e,e'p)n reaction ("Electro-disintegration" of the deuteron) at three different four-momentum transfers, Q^2 = 0.8, 2.1, and 3.5 GeV^2 and missing momenta, P_miss = 0, 100, 200, 300, 400, and 500 GeV including separations of the longitudinal-transverse interference response function, R_LT, and extractoin of the longitudinal-transverse asymmetry, A_LT. This systematic approach will help to understand the reaction mechanism and the deuteron structure down to the short range part of the nucleon-nucleon interaction which is one of the fundamental missions of nuclear physics. By studying the very short distance structure of the deuteron, one may also determine whether or to what extent the description of nuclei in terms of nucleon/meson degrees of freedom must be supplemented by inclusion of explicit quark effects. The unique combination of energy, current, duty factor, and control of systematics for Hall A at Jefferson Lab made Jefferson Lab the only facility in the world where these systematic studies of the deuteron can be undertaken. This is especially true when we want to understand the short range structure of the deuteron where high energies and high luminosity/duty factor are …

The study of thermal decomposition in high explosive (HE) charges has been an ongoing process since the early 1900s. This work is specifically directed towards the analysis of PBX 9501. In the early 1970s, Dwight Jaeger of Los Alamos National Laboratory (LANL) developed a single-step, two-species kinetics system that was used in the development of one of the first finite element codes for thermal analyses known as EXPLO. Jaeger's research focused on unconfined spherical samples of HE charges to determine if varied heating ramps would cause detonation or deflagration. Tarver and McGuire of Lawrence Livermore National Laboratory (LLNL) followed soon after with a three-step, four-species kinetics system that was developed for confined spheres under relatively fast heating conditions. Peter Dickson et al. of LANL then introduced a kinetics system with four steps and five species that included bimolecular products to capture the effects of the endothermic phase change that the HE undergoes. The results of four experiments are examined to study the effectiveness of these kinetics systems. The experiments are: (1) The LLNL scaled thermal explosion (STEX) experiments on confined cylindrical charges with long heating ramps in the range of 90 hours. (2) The LLNL one-dimensional time to explosion (ODTX) …

Silver noble metal nanoparticles that are<10 nm often possess multiply twinned grains allowing them to adopt shapes and atomic structures not observed in bulk materials. The properties exhibited by particles with multiply twinned polycrystalline structures are often far different from those of single-crystalline particles and from the bulk. I will present experimental evidence that silver nanoparticles<10 nm undergo a reversible structural transformation under hydrostatic pressures up to 10 GPa. Results for nanoparticles in the intermediate size range of 5 to 10 nm suggest a reversible linear pressure-dependent rhombohedral distortion which has not been previously observed in bulk silver. I propose a mechanism for this transitiion that considers the bond-length distribution in idealized multiply twinned icosahedral particles. Results for nanoparticles of 3.9 nm suggest a reversible linear pressure-dependent orthorhombic distortion. This distortion is interpreted in the context of idealized decahedral particles. In addition, given these size-dependent measurements of silver nanoparticle compression with pressure, we have constructed a pressure calibration curve. Encapsulating these silver nanoparticles in hollow metal oxide nanospheres then allows us to measure the pressure inside a nanoshell using x-ray diffraction. We demonstrate the measurement of pressure gradients across nanoshells and show that these nanoshells have maximum resolved shear strengths …

High pressure high temperature CO adsorption and coadsorption with ethylene and propylene on Pt(111) was monitored in situ with infrared-visible sum frequency generation (SFG). At high pressures and high temperatures, CO dissociates on a Pt(111) surface to form carbon. At 400 torr CO pressure and 673K, CO modifies the Pt(111) surface through a carbonyl intermediate, and dissociates to leave carbon on the surface. SFG was used to follow the CO peak evolution from monolayer adsorption in ultra high vacuum (UHV) to 400 torr CO pressure. At this high pressure, a temperature dependence study from room temperature to 823K was carried out. Auger electron spectroscopy was used to identify carbon on the surface CO coadsorption with ethylene and CO coadsorption with propylene studies were carried out with 2-IR 1-visible SFG. With this setup, two spectral ranges covering the C-H stretch range and the CO stretch range can be monitored simultaneously. The coadsorption study with ethylene reveals that after 5L ethylene exposure on a Pt(111) surface to form ethylidyne , CO at high pressures cannot completely displace the ethylidyne from the surface. Instead, CO first adsorbs on defect sites at low pressures and then competes with ethylidyne for terrace sites at high …

Magnetic particle inspection (MPI) is a widely used nondestructive inspection method for aerospace applications essentially limited to experiment-based approaches. The analysis of MPI characteristics that affect sensitivity and reliability contributes not only reductions in inspection design cost and time but also improvement of analysis of experimental data. Magnetic particles are easily attracted toward a high magnetic field gradient. Selection of a magnetic field source, which produces a magnetic field gradient large enough to detect a defect in a test sample or component, is an important factor in magnetic particle inspection. In this work a finite element method (FEM) has been employed for numerical calculation of the MPI simulation technique. The FEM method is known to be suitable for complicated geometries such as defects in samples. This thesis describes the research that is aimed at providing a quantitative scientific basis for magnetic particle inspection. A new FEM solver for MPI simulation has been developed in this research for not only nonlinear reversible permeability materials but also irreversible hysteresis materials that are described by the Jiles-Atherton model. The material is assumed to have isotropic ferromagnetic properties in this research (i.e., the magnetic properties of the material are identical in all directions in …

Correlation between length scales in the field of magnetism has long been a topic of intensive study. The long-term desire is simple: to determine one theory that completely describes the magnetic behavior of matter from an individual atomic particle all the way up to large masses of material. One key piece to this puzzle is connecting the behavior of a material's domains on the nanometer scale with the magnetic properties of an entire large sample or device on the centimeter scale. In the first case study involving the FeSiAl thin films, contrast and spacing of domain patterns are clearly related to microstructure and stress. Case study 2 most clearly demonstrates localized, incoherent domain wall motion switching with field applied along an easy axis for a square hysteresis loop. In case study 3, axis-specific images of the complex Gd-Si-Ge material clearly show the influence of uniaxial anisotropy. Case study 4, the only study with the sole intent of creating domain structures for imaging, also demonstrated in fairly simple terms the effects of increasing stress on domain patterns. In case study 5, it was proven that the width of magnetoresistance loops could be quantitatively predicted using only MFM. When all of the …

Eu(Ba{sub 1-x}Nd{sub x}){sub 2}Cu{sub 3}O{sub 7+{delta}} were systematically studied in order to understand how the valence of the rear earth elements, ionic sizes and magnetic moment affect the crystal structure and magnetic and electrical properties. Differential thermal analyses were carried out to check the phase purity, X-ray data were least-squares fitted to determine the lattice parameters, and DC-SQUID magnetometry was used to characterize the superconducting properties. These results showed that the crystallography is consistent with other EuLR123ss series, LR = La, Pr, Eu. The lattice parameters vary with the ionic radii of the rare earth ions. Unlike the uniform change in lattice parameter, the superconducting transition did not vary systematically with the ionic size of the dopants. Although the general trend was for T{sub c} to decrease with decreasing ionic size of the dopant, for the same doping level, Pr was anomalous, depressing T{sub c} faster. Although the exact mechanism is not clear, this result is consistent with the depression of T{sub c} for Pr substitution for the rare earth in R123. The critical current J{sub c} was determined using the Bean model from magnetization versus field measurements as a function of temperature and field. The effect of the dopants …