Physical Sciences and Mathematics Commons^™

Optimization Of Useful Hard X-Ray Photochemistry, David Lewis Goldberger

UNLV Theses, Dissertations, Professional Papers, and Capstones

X-ray induced damage is generally considered a nuisance, but in the field of Useful Hard X-ray Photochemistry we harness the highly ionizing and penetrating properties of hard X-rays (> 7 keV) to initiate novel photochemical decomposition and synthesis at ambient and extreme conditions. Preliminary experiments suggest that the energy of irradiating photons and the sample pressure play roles in determining the nature of X-ray induced damage. Here, we present the X-ray energy dependence of damage induced in strontium oxalate, strontium nitrate, and barium nitrate, as well as the pressure dependence of X-ray induced damage of strontium oxalate. Our results indicate …

A Case For Chiral Contributions To Nondipole Effects In Photoionization Using Linearly Polarized Soft X-Rays, Kyle Patrick Bowen

UNLV Theses, Dissertations, Professional Papers, and Capstones

Modelling angular distributions of photoelectrons requires making accurate approximations of both the incoming light and the behavior of bound electrons. The experimental determination of photoelectron angular distributions is crucial to the development of accurate theoretical models governing the light-matter interaction. To date, many models have relied upon the dipole approximation, which assumes a constant electric field as the source of ionization. Despite knowing that the dipole approximation would break down as photon energy increased, the precise limit was unclear. Over the past two decades, a strong case has been made that corrections to the dipole approximation are necessary for accurately …

Li+ Ion Transport In Select Lithium-Rich Antiperovskites, John William Howard

UNLV Theses, Dissertations, Professional Papers, and Capstones

Lithium-Rich Antiperovskites (LiRAPs) have been shown to possess relatively high ionic conductivity at room temperature, and become superionic conductors at elevated temperatures. These materials generally have a stoichiometry Li3BX, where B is a doubly deficient anion, and X is a monovalent anion. Ideally they belong to the high symmetry space group Pm-3m where lithium atoms occupy octahedral corners, B anions occupy octahedral centers, and X anions occupy the interstitial centers between the octahedra. LiRAPs were synthesized using several different methods and characterized by XRD, EIS, DSC, TGA, FTIR, and INS techniques. Chemical analyses were performed to determine the stoichiometries of …

A Gauge Theoretic Treatment Of Rovibrational Motion In Diatoms, Gregory Colarch

UNLV Theses, Dissertations, Professional Papers, and Capstones

The Born-Oppenheimer approximation has long been the standard approach to solving the Schrödinger equation for diatomic molecules. In it, nuclear and electronic motions are separated into "slow" and "fast" degrees of freedom and couplings between the two are ignored. The neglect of non-adiabatic couplings leads to an incomplete description of diatomic motion, and in a more refined approach, non-adiabatic couplings are uncoupled by transforming the angular momentum of the molecule and electrons into the body-fixed frame.

In this thesis we examine a "modern" form of the Born-Oppenheimer approximation by exploiting a gauge theoretic approach in a description of molecular motion. …

Hybrid Plasmonic Nanoantennas: Fabrication, Characterization, And Application, Shengjie Zhai

UNLV Theses, Dissertations, Professional Papers, and Capstones

As optical counterpart of microwave antennas, plasmonic nanoantennas are important nanoscale devices for converting propagating optical radiation into confined/enhanced electromagnetic fields. Presently, nanoantennas, with a typical size of 200-500 nm, have found their applications in bio-sensing, bio-imaging, energy harvesting, and disease cure and prevention. With the device feature size of next generation IC goes down to 22 nm or smaller, and biological/chemical sensing reaches the Gene’s level, the sizes of the corresponding nanoantennas have to be scaled down to sub-100nm level. In the literature, these sub-100nm nanoantennas are referred as deep subwavelength nanoantennas as size of such miniaturized nanoantennas is …

Measured Rates Of D2 Abstraction In H2o+ , D2 Substitution In H2do+ And Charge Transfer Of He2+ With Noble And Other Gases At <1ev, Chrysanthos Kyriakides

UNLV Theses, Dissertations, Professional Papers, and Capstones

Experimental determination of the rate coefficient values of deuterium abstraction in water ions and deuterium substitution in hydronium ions can improve the understanding of D/H in water at planetary atmospheres, cometary atmospheres, and interstellar medium. Using a cylindrical ion trap, (CIT) and time of flight (TOF) mass spectrometry, a number of measurements at energies below 1 eV have been performed. The deuterium abstraction rate coefficient in water ions, H₂O⁺, and an upper limit for the hydrogen-deuterium substitution rate coefficient in monodeuterated hydronium ion, H₂DO⁺, have been measured. Both the abstraction and substitution …

New Cross Sections For H On H2 Collisional Transitions, Qianxia Zou

UNLV Theses, Dissertations, Professional Papers, and Capstones

The cross section for H on H₂ collisions is important for astrophysics as well as our understanding of the simple chemical systems. This is the simplest atom-molecule cross section. With a new H₃ potential surface by Mielke et al., we have modified the ABC code by Skouteris, Castillo and Manolopoulos to calculate new cross sections. These cross sections are compared to previous cross section calculations.

Dispersion Of The Hyperpolarizability Of The Carbon Tetrachloride Molecule, Scott Wilde

UNLV Theses, Dissertations, Professional Papers, and Capstones

The second hyperpolarizability of a molecule is the microscopic version of the third order susceptibility. Direct measurements of the ratio of the second hyperpolarizability of carbon tetrachloride to diatomic nitrogen are made possible through electric field induced second harmonic generation. Whenever the dispersion of the second hyperpolarizability is not negligible, there should be deviations from Kleinman symmetry. Previous experimental data for second hyperpolarizability of this molecule have only been at two frequencies and theory predicts the zero frequency value. In order to provide for a better extrapolation to zero frequency, additional gas phase measurements of this ratio at optical frequencies …

Speciation And Spectroscopy Of The Uranyl And Tetravalent Plutonium Nitrate Systems: Fundamental Studies And Applications To Used Fuel Reprocessing, Nicholas A. Smith

UNLV Theses, Dissertations, Professional Papers, and Capstones

This dissertation explores the use of UV-Visible spectroscopy and Time Resolved Laser Induced Fluorescence spectroscopy as near real time process monitors of uranium and plutonium concentrations in aqueous reprocessing trains. The molar absorptivities and linear ranges of these metals were investigated under total nitrate and acid concentrations similar to those found in current reprocessing systems. Concurrent to this, a new multiple wavelength monitor was derived that is capable of determining the total nitrate concentration spectroscopically. This method uses the uranium absorbance spectrum to calculate the nitrate concentration in solution. When used as part of an Advanced Safeguard suite, this technique …

Vibrational Spectroscopic Study Of The 1,3,5,7-Cyclooctatetraene At High Static Pressures, Edward Romano

UNLV Theses, Dissertations, Professional Papers, and Capstones

1,3,5,7-cyclooctatetraene (COT) is a single-ringed hydrocarbon that has not been studied extensively under high static pressures. It was the intent of this study to reveal its high-pressure behavior through its vibrational spectra. To this end, its infrared spectra as a function of pressure were collected at the National Synchrotron Light Source (NSLS) U2A beamline, as well as its Raman spectra over pressure using a micro-Raman spectrometer.

The spectra show the typical stiffening of force constants with increasing pressure for most peaks, particularly those which would theoretically exhibit a mode-softening behavior under hypotheses of molecular planarization and aromatization. Additionally, the data …

Partial Phonon Density Of States Of 57-Iron And 161-Dysprosium In Dyfe3 By Nuclear Resonant Inelastic X-Ray Scattering Under High Pressure, Elizabeth Anne Tanis

UNLV Theses, Dissertations, Professional Papers, and Capstones

The dual partial phonon density of states (DOS) from two different Mossbauer isotopes (161Dy and 57Fe) in the same material (DyFe3) was successfully measured using the nuclear resonant inelastic x-ray scattering (NRIXS) technique at high pressure. Nuclear inelastic scattering measurements yield an in-depth understanding of the element-specific dynamic properties. The Debye temperatures , the Lamb-Mossbauer factor, and the vibrational contributions to the Helmholtz free energy, specific heat , entropy and internal energy are calculated directly from the phonon density of states.

Investigation Of The Corrosion Of Steel By Lead-Bismuth Eutectic (Lbe) Using Scanning Electron Microscopy And X-Ray Photoelectron Spectroscopy, Daniel Koury

UNLV Theses, Dissertations, Professional Papers, and Capstones

Lead Bismuth Eutectic (LBE) has been proposed for use in programs for accelerator transmutation of waste. LBE is the leading candidate material as a spallation target and an option for the sub-critical blanket coolant. The corrosion of 316 and 316L stainless steels by LBE has been studied using UNLV's facilities for Scanning Electron Microscopy (SEM) and X-ray Photoelectron Spectroscopy (XPS). We have compared exposed and unexposed samples and studied the differences. Some amount of surface contamination is present on the samples and has been removed by ionbeam etching. The unexposed samples reveal typical stainless steel characteristics: a chromium oxide passivation …