Undergraduate thesis on the emission of atmospheric pollutants. The pollutants focused on are NO and NO₂. The author discusses the influence of sulfur on NO emission using computational chemistry.

Undergraduate thesis examining the legalization of physician-assisted suicide in the United States and its ethics. The authors' study provides that in states where, by legislation, physicians can aid a patient by prescribing a lethal dose which the patient can choose to ingest, the benefits well surpass any risk feared by opponents of physician-assisted suicide.

This work presents explorations of the potential energy surface of clusters of atoms and of the interactions between molecules. First, structures of small aluminum clusters are examined and classified as ground states, transition states, or higher-order saddle points. Subsequently, the focus shifts to dispersion-dominated π-π interactions when the potential energy surfaces of benzene, substituted benzene, and pyridine dimers are explored. Because DNA nucleotide bases can be thought of as substituted heterocycles, a natural extension of the substituted benzene and pyridine investigations is to model paired nucleotide bases. Finally, the success of the dispersion studies inspires the development of an extension to the computational method used, which will enable the dispersion energy to be modeled – and the potential energy surface explored – in additional chemical systems. The effective fragment potential (EFP) method is described, as well as various quantum mechanical methods. An ab inito quantum mechanical study of 13-atom aluminum clusters is described. EFP studies of aromatic dimers are reported in which dispersion energy makes a significant contribution to the attraction between monomers. Theory and code development toward a means of computing dispersion energy in mixed ab inito-EFP systems are described.

This dissertation describes a measurement of the neutrino oscillation parameters #1;{Delta}m{sup 2}{sub 21}, θ{sub 12} and constraints on θ{sub 13} based on a study of reactor antineutrinos at a baseline of ∼ 180 km with the KamLAND detector. The data presented here was collected between April 2002 and November 2009, and amounts to a total exposure of 2.64 � 0.07 � 10{sup 32} proton-years. For this exposure we expect 2140 � 74(syst) antineutrino candidates from reactors, assuming standard model neutrino behavior, and 350�88(syst) candidates from background. The number observed is 1614. The ratio of background-subtracted candidates observed to expected is (N{sub Obs} − N{sub Bkg})/N{sub Exp} = 0.59 � 0.02(stat) � 0.045(syst) which confirms reactor neutrino disappearance at greater than 5σ significance. Interpreting this deficit as being due to neutrino oscillation, the best-fit oscillation parameters from a three-flavor analysis are #1;{Delta}m{sup 2}{sub 21} = 7.60{sup +0.20}{sub −0.19}�10{sup −5}eV{sup 2}, θ{sub 12} = 32.5 � 2.9 degrees and sin{sup 2} θ{sub 13} = 0.025{sup +0.035}{sub −0.035}, the 95% confidence-level upper limit on sin{sup 2} θ{sub 13} is sin{sup 2} θ{sub 13} < 0.083. Assuming CPT invariance, a combined analysis of KamLAND and solar neutrino data yields best-fit values: #1;{Delta}m{sup 2}{sub 21} …

This thesis presents first measurements of moments of the hadronic n{sub X}{sup 2} distribution measured in inclusive semileptonic decays of B mesons to final states containing a charm quark, B {yields} X{sub c}{ell}{nu}. The variable n{sub X}{sup 2} is a combination of the invariant mass of the charmed meson m{sub X}, its energy in the B-meson rest-frame E{sub X;BRF}, and a constant {tilde {Lambda}} = 0.65 GeV, n{sub X}{sup 2} = m{sub X}{sup 2}c{sup 4}-2{tilde {Lambda}}E{sub X,BRF} + {tilde {Lambda}}{sup 2}. The moments <n{sub X}{sup k}> with k = 2,4,6 are measured as proposed by theory to constrain assumptions made in the theoretical description of inclusive observables in semileptonic B-meson decays. This description uses Heavy Quark Expansion (HQE), an effective QCD combined with an Operator Product Expansion. The measurement is based on a sample of 231.6 million e{sup +}e{sup -} {yields} {Upsilon}(4S) {yields} B{bar B} events recorded with the BABAR experiment at the PEP-II e{sup +}e{sup -}-storage rings at SLAC. We reconstruct the semileptonic decay by identifying a charged lepton in events tagged by a fully reconstructed hadronic decay of the second B meson. Correction procedures are derived from Monte Carlo simulations to ensure an unbiased measurement of the moments …

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Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interaction of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO{sub 2}{sup 2+}). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in …

Understanding chemical reactions requires the knowledge of the elementary steps of breaking and making bonds, and often a variety of experimental techniques are needed to achieve this goal. The initial steps occur on the femto- through picosecond time-scales, requiring the use of ultrafast spectroscopic methods, while the rate-limiting steps often occur more slowly, requiring alternative techniques. Ultrafast one and two-dimensional infrared and step-scan FTIR spectroscopies are used to investigate the photochemical reactions of four organometallic complexes. The analysis leads to a detailed understanding of mechanisms that are general in nature and may be applicable to a variety of reactions.

The field of spintronics offers perspectives for seamless integration of coupled and inter-tunable electrical and magnetic properties in a single device. For integration of the spin degree of freedom with current electronic technology, new semiconductors are needed that show electrically-tunable magnetic properties at room temperature and above. Dilute magnetic semiconductors derived from III-V compounds, like GaMnAs and InMnAs, show coupled and tunable magnetic, transport, and optical properties, due to the fact that their ferromagnetism is hole-mediated. These unconventional materials are ideal systems for manipulating the magnetic order by changing the carrier polarization, population density, and energy band distribution of the complementary subsystem of holes. This is the main theme we cover in this thesis. In particular, we develop a unique setup by use of ultraviolet pump, near-infrared probe femtosecond laser pulses, that allows for magneto-optical Kerr effect (MOKE) spectroscopy experiments. We photo-excite transient carriers in our samples, and measure the induced transient magnetization dynamics. One set of experiments performed allowed us to observe for the first time enhancement of the ferromagnetic order in GaMnAs, on an ultrafast time scale of hundreds of picoseconds. The corresponding transient increase of Curie temperature (Tc, the temperature above which a ferromagnetic material loses its …

(C5Me5)2LnOTf where Ln = La, Ce, Sm, Gd, and Yb have been synthesized and these derivatives are good starting materials for the synthesis of (C5Me5)2LnX derivatives. (C5Me5)2Ln(2,2'-bipyridine), where Ln = La, Ce, Sm, and Gd, along with several methylated bipyridine analogues have been synthesized and their magnetic moments have been measured as a function of temperature. In lanthanum, cerium, and gadolinium complexes the bipyridine ligand ligand is unequivocally the radical anion, and the observed magnetic moment is the result of intramolecular coupling of the unpaired electron on the lanthanide fragment with the unpaired electron on the bipyridine along with the intermolecular coupling between radicals. Comparison with the magnetic moments of the known compounds (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine) leads to an understanding of the role of the Sm(II)/Sm(III) and Yb(II)/Yb(III) couple in the magnetic properties of (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine). In addition, crystal structures of (C5Me5)2Ln(2,2'-bipyridine) and [(C5Me5)2Ln(2,2'-bipyridine)][BPh4](Ln= Ce and Gd), where the lanthanide is unequivocally in the +3 oxidation state, give the crystallographic characteristics of bipyridine as an anion and as a neutral ligand in the same coordination environment, respectively. Substituted bipyridine ligands coordinated to (C5Me5)2Yb are studied to further understand how the magnetic coupling in (C5Me5)2Yb(2,2'-bipyridine) changes with substitutions. In the …

Presented are the results of a search for direct CP violation in Cabibbo-suppressed decays of D{sup 0} to two charged daughters. The analysis described was performed on {approx}230 fb{sup -1} of the BABAR data sample, recorded at the Stanford Linear Accelerator Center and using the PEP-II electron storage rings. We measure CP asymmetries for decay to the KK and {pi}{pi} final states, as well as for the branching ratio, and develop a new technique for tagging-efficiency correction using the Cabibbo-favored K{pi} final state. We find some evidence for CP violation in decays to the KK final state and results that suggest CP violation in the {pi}{pi} final state as well.

Morphological evolution and selection of angular primary silicon is investigated in near-eutectic Al-Si alloys. Angular silicon arrays are grown directionally in a Bridgman furnace at velocities in the regime of 10{sup -3} m/sec and with a temperature gradient of 7.5 x 10{sup 3} K/m. Under these conditions, the primary Si phase grows as an array of twinned bicrystalline dendrites, where the twinning gives rise to a characteristic 8-pointed star-shaped primary morphology. While this primary Si remains largely faceted at the growth front, a complex structure of coherent symmetric twin boundaries enables various adjustment mechanisms which operate to optimize the characteristic spacings within the primary array. In the work presented here, this primary silicon growth morphology is examined in detail. In particular, this thesis describes the investigation of: (1) morphological selection of the twinned bicrystalline primary starshape morphology; (2) primary array behavior, including the lateral propagation of the starshape grains and the associated evolution of a strong <100> texture; (3) the detailed structure of the 8-pointed star-shaped primary morphology, including the twin boundary configuration within the central core; (4) the mechanisms of lateral propagation and spacing adjustment during array evolution; and (5) the thermosolutal conditions (i.e. operating state) at the primary …

Organic chemistry has served as a solid foundation for interdisciplinary research areas, such as molecular biology and medicinal chemistry. An understanding of the biological activities and structural elucidations of natural products can lead to the development of clinically valuable therapeutic options. The advancements of modern synthetic methodologies allow for more elaborate and concise natural product syntheses. The theme of this study centers on the synthesis of natural products with particularly challenging structures and interesting biological activities. The synthetic expertise developed here will be applicable to analog syntheses and to other research problems.

Arynes are among the most intensively studied systems in chemistry. However, many aspects of the chemistry of these reactive intermediates are not well understood yet and their use as reagents in synthetic organic chemistry has been somewhat limited, due to the harsh conditions needed to generate arynes and the often uncontrolled reactivity exhibited by these species. Recently, o-silylaryl triflates, which can generate the corresponding arynes under very mild reaction conditions, have been found very useful in organic synthesis. This thesis describes several novel and useful methodologies by employing arynes, which generate from o-silylaryl triflates, in organic synthesis. An efficient, reliable method for the N-arylation of amines, sulfonamides and carbamates, and the O-arylation of phenols and carboxylic acids is described in Chapter 1. Amines, sulfonamides, phenols, and carboxylic acids are good nucleophiles, which can react with arynes generated from a-silylaryl triflates to afford the corresponding N- and O-arylated products in very high yields. The regioselectivity of unsymmetrical arynes has also been studied. A lot of useful, functional groups can tolerate our reaction conditions. Carbazoles and dibenzofurans are important heteroaromatic compounds, which have a variety of biological activities. A variety of substituted carbazoles and dibenzofwans are readily prepared in good to excellent …

Chapters 1 and 2 dealt with the chemistry of superoxo-, hydroperoxo-, and oxo- complexes of chromium, rhodium and cobalt. Chapter 3 dealt with the mechanism of oxygen-atom transfer catalyzed by an oxo-complex of rhenium. In Chapter 1, it was shown that hydroperoxometal complexes of cobalt and rhodium react with superoxochromium and chromyl ions, generating reduced chromium species while oxidizing the hydroperoxometal ions to their corresponding superoxometal ions. It was shown that the chromyl and superoxochromium ions are the more powerful oxidants. Evidence supports hydrogen atom transfer from the hydroperoxometal ion to the oxidizing superoxochromium or chromyl ion as the reaction mechanism. There is a significant H/D kinetic isotope effect. Comparisons to the rate constants of other known hydrogen atom transfer reactions show the expected correlation with bond dissociation energies. In Chapter 2, it was found that the superoxometal complexes Cr{sub aq}OO{sup 2+} and Rh(NH{sub 3}){sub 4}(H{sub 2}O)OO{sup 2+} oxidize stable nitroxyl radicals of the TEMPO series with rate constants that correlate with the redox potentials of both the oxidant and reductant. These reactions fit the Marcus equation for electron transfer near the theoretical value. Acid catalysis is important to the reaction, especially the thermodynamically limited cases involving Rh(NH{sub 3}){sub 4}(H{sub …

Superaustenitic stainless steels constitute a group of Fe-based alloys that are compositionally balanced to have a purely austenitic matrix and exhibit favorable pitting and crevice corrosion resistant properties and mechanical strength. However, intermetallic precipitates such as sigma and Laves can form during casting or exposure to high-temperature processing, which degrade the corrosion and mechanical properties of the material. The goal of this study was to accurately characterize the solid-solid phase transformations seen in cast superaustenitic stainless steels. Heat treatments were performed to understand the time and temperature ranges for intermetallic phase formations in alloys CN3MN and CK3MCuN. Microstructures were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy and wavelength dispersive spectroscopy (EDS, WDS). The equilibrium microstructures, composed primarily of sigma and Laves within purely austenitic matrices, showed slow transformation kinetics. Factors that determine the extent of transformation, including diffusion, nucleation, and growth, are discussed.

The potential of single molecule detection as an analysis tool in biological and medical fields is well recognized today. This fast evolving technique will provide fundamental sensitivity to pick up individual pathogen molecules, and therefore contribute to a more accurate diagnosis and a better chance for a complete cure. Many studies are being carried out to successfully apply this technique in real screening fields. In this dissertation, several attempts are shown that have been made to test and refine the application of the single molecule technique as a clinical screening method. A basic applicability was tested with a 100% target content sample, using electrophoretic mobility and multiple colors as identification tools. Both electrophoretic and spectral information of individual molecule were collected within a second, while the molecule travels along the flow in a capillary. Insertion of a transmission grating made the recording of the whole spectrum of a dye-stained molecule possible without adding complicated instrumental components. Collecting two kinds of information simultaneously and combining them allowed more thorough identification, up to 98.8% accuracy. Probing mRNA molecules with fluorescently labeled cDNA via hybridization was also carried out. The spectral differences among target, probe, and hybrid were interpreted in terms of dispersion …

This thesis consists of six sections. The first section gives the basic research background on the ionic conduction mechanism in glass, polarization in the glass, and the method of determining the mobile carrier density in glass. The proposed work is also included in this section. The second section is a paper that characterizes the structure of MI + M{sub 2}S + (0.1 Ga{sub 2}S{sub 3} + 0.9 GeS{sub 2}) (M = Li, Na, K and Cs) glasses using Raman and IR spectroscopy. Since the ionic radius plays an important role in determining the ionic conductivity in glasses, the glass forming range for the addition of different alkalis into the basic glass forming system 0.1 Ga{sub 2}S{sub 3} + 0.9 GeS{sub 2} was studied. The study found that the change of the alkali radius for the same nominal composition causes significant structure change to the glasses. The third section is a paper that investigates the ionic conductivity of MI + M{sub 2}S + (0.1Ga{sub 2}S{sub 3} + 0.9 GeS{sub 2}) (M = Li, Na, K and Cs) glasses system. Corresponding to the compositional changes in these fast ionic conducting glasses, the ionic conductivity shows changes due to the induced structural changes. …

Our research focuses on taking advantage of the ability of scanning tunneling microscopy (STM) to operate at high-temperatures and high-pressures while still providing real-time atomic resolution images. We also utilize high-pressure x-ray photoelectron spectroscopy (HPXPS) to monitor systems under identical conditions thus giving us chemical information to compare and contrast with the structural and dynamic data provided by STM.

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Left unprotected, both transmissive and reflective final optics in a laser-driven inertial fusion power plant would quickly fail from melting, pulsed thermal stress, or degradation of optical properties as a result of ion implantation. One potential option for mitigating this threat is to magnetically deflect the ions such that they are directed to a robust energy dump. In this paper we detail integrated studies that have been carried out to assess the viability of this approach for protecting final optics.

The standard non-photochemical hole burning (NPHB) mechanism, which involves phonon-assisted tunneling in the electronically excited state, was originally proposed to explain the light-induced frequency change of chemically stable molecules in glassy solids at liquid helium temperatures by this research group more than two decades ago. The NPHB mechanism was then further elucidated and the concept of intrinsic to glass configurational relaxation processes as pre-mediating step to the hole burning process was introduced. The latter provided the theoretical basis for NPHB to evolve into a powerful tool probing the dynamics and nature of amorphous media, which aside from ''simple'' inorganic glasses may include also ''complex'' biological systems such as living cells and cancerous/normal tissues. Presented in this dissertation are the experimental and theoretical results of hole burning properties of aluminum phthalocyanine tetrasulphonate (APT) in several different matrices: (1) hyperquenched glassy water (HGW); (2) cubic ice (I{sub c}); and (3) water confined into poly(2-hydroxyethylmethacrylate) (poly-HEMA). In addition, results of photochemical hole burning (PHB) studies obtained for phthalocyanine tetrasulphonate (PcT) in HGW and free base phthalocyanine (Pc) in ortho-dichlorobenzene (DCB) glass are reported. The goal of this dissertation was to provide further evidence supporting the NPHB mechanism and to provide more insight that …

A study has been made of the generation of particles during laser ablation and has included size distribution measurements and observation of the formation processes. The particle size distribution with respect to different laser parameters was obtained in-line using a differential mobility analyzer (DMA) and a particle counter. The experimental results show that the particle size varies with laser energy, laser pulsewidth, ambient gas flow rate and sample properties. The results serve as a basis for controlling the size of nanoparticles generated by laser ablation. Laser shadowgraph imaging was used to study mass ejection processes and mechanisms. At higher laser irradiance, some particles were ejected in the liquid and even in the solid phase. Time-resolved images show the propagation of the shockwaves: external shockwaves propagate outward and decelerate, and internal shockwaves reflect back and forth between the gas contact surface and the sample surface. The internal shockwave is proposed to cause the ejection of liquid particles when the internal shockwave strikes the liquid molten layer. A simulation based on vapor plume expansion was carried out and provides satisfactory agreement with experimental results. Different material properties result in different particle ejection behavior:particle ejection for most materials including metals result in a …

A collocation method using cubic splines is developed and applied to simulate steady and time-dependent, including turbulent, thermally convecting flows for two-dimensional compressible fluids. The state variables and the fluxes of the conserved quantities are approximated by cubic splines in both space direction. This method is shown to be numerically conservative and to have a local truncation error proportional to the fourth power of the grid spacing. A ''dual-staggered'' Cartesian grid, where energy and momentum are updated on one grid and mass density on the other, is used to discretize the flux form of the compressible Navier-Stokes equations. Each grid-line is staggered so that the fluxes, in each direction, are calculated at the grid midpoints. This numerical method is validated by simulating thermally convecting flows, from steady to turbulent, reproducing known results. Once validated, the method is used to investigate many aspects of thermal convection with high numerical accuracy. Simulations demonstrate that multiple steady solutions can coexist at the same Rayleigh number for compressible convection. As a system is driven further from equilibrium, a drop in the time-averaged dimensionless heat flux (and the dimensionless internal entropy production rate) occurs at the transition from laminar-periodic to chaotic flow. This observation is …