Physics Commons^™

Photophysical And Photochemical Processes In Small Molecules And Materials For Solar Energy Conversion, Ethan Lambert

Honors Theses

The work covered in this thesis all falls under the theme of photophysical processes after light and matter interact. Those of primary interest are Raman scattering induced vibrations and excited state dynamics probed by transient absorption spectroscopy. Small molecules are studied with Raman spectroscopy and computational chemistry. These studies unearth the shifts in vibrational frequency as a function of charge transfer or receipt and how a quantitative assay of natural orbital populations and delocalization can offer both the nature and magnitude of this charge transfer. Further, a method is presented that builds upon previous work within the academic family tree; …

Influence Of Platinum Nanoparticles On Ionic Transport And Hydrogen Reactivity Of Yttria-Stabilized Zirconia Thin Films, Firas Mahyob

Electronic Theses and Dissertations

Yttria-stabilized zirconia (YSZ) is a widely used ceramic material in solid oxide fuel cells, oxygen sensors, and sensing applications due to its high ionic conductivity, chemical inertness, and thermal stability. YSZ is promising active coating for use in miniaturized harsh environment wireless surface acoustic sensors to monitor gases such as H₂. Adding catalytic Pt nanoparticles can enhance gas reactivity and lead to associated film conductivity changes.

In this work, thin films with an (8% Y₂O₃ - 92% ZrO₂) composition were deposited onto piezoelectric langasite substrates using RF magnetron sputtering in Ar:O₂ - …

Hierarchically Structured Photoelectrodes Via Atomic Layer Deposition, Justin Rowan Reed Demoulpied

Graduate Theses and Dissertations

In the search for a sustainable method to meet increasing energy needs, solar energy emerges as an underutilized, plentiful resource. Solar intermittency and requirements for transportation necessitate storing solar energy in the form of chemical bonds via artificial photosynthesis. Photoelectrochemical (PEC) water splitting generates hydrogen fuel from solar energy and water. A semiconducting material that successfully meets the complex requirements for building an industrially scalable PEC device has yet to emerge. This is leading to a reevaluation of materials previously overlooked within PEC research, mainly materials with limitations such as minimal charge carrier mobility and propensity to corrosion under illumination …

Using Powder Diffraction To Give Insight Into Structures Of Ir2(Diisocyanomenthane)4x2 [Dimen] (X = Cl; Pf6; Bph4), Mairead Brownell

Scripps Senior Theses

Ir2(dimen)42+ (dimen = 1,8-diisocyanomenthane) has been studied extensively as model compound to better understand catalysis of photochemical reactions. Although Ir2(dimen)42+ has been used primarily to observe the photophysical changes of metal-metal transitions, it gives great insight into the transitions that allow other d8-d8 metal complexes to undergo photochemical processes and generate hydrogen gas. The large visible range by which Ir2(dimen)42+ (1) can be electronically excited in solution is indicative of its two solution phase ground states, which interestingly have been hypothesized to resemble two unique packing structures observed in the powder state. In this study, the powder diffraction patterns of …

Modeling, Fabrication, And Characterization Of Rf-Based Passive Wireless Sensors Composed Of Refractory Semiconducting Ceramics For High Temperature Applications, Kavin Sivaneri Varadharajan Idhaiam

Graduate Theses, Dissertations, and Problem Reports

Real-time health monitoring of high temperature systems (>500^oC) in harsh environments is necessary to prevent catastrophic events caused by structural failures, varying pressure, and chemical reactions. Conventional solid-state temperature sensors such as resistance temperature detectors (RTDs) and thermocouples are restricted by their operating environments, sensor dimensions and often require external power sources for their operation. The current work presents the research and development of RF-based passive wireless sensing technology targeting high temperatures and harsh environmental conditions. Passive wireless devices are generally classified as near-field and far-field devices based on the interrogation distance. Near-field sensors are placed at …

Electronic Structure Of Early Transition Metal Complexes Supported By Pyridine Polypyrrolide Ligands, Dylan Connor Leary

Graduate Theses, Dissertations, and Problem Reports

A thorough study of photoluminescent molecules involving the pyridine polypyrrole(ide) ligand platform has been conducted. A detailed analysis on speciation of the proligand H₂(^MesPDP^Ph) (H₂^MesPDP^Ph = 2,6-bis(5-mesityl-3-phenyl-1H-pyrrol-2-yl)-pyridine) and its dilithium salt Li₂(^MesPDP^Ph) revealed temperature- and solvent-dependent effects. These molecules, along with the hydrochloric acid adduct [H₃(^MesPDP^Ph)]Cl were found to exhibit short-lived photoluminescence in both tetrahydrofuran and benzene solution. These findings confirm the hypothesis that heavy-atom involvement is crucial for the favorable photophysical properties observed for the Zr(PDP)_{2 …}

Functional Nanoparticles: Tin Monoxide And Molybdenum Disulfide Quantum Dots On Graphene Nanosheets, Denys Vidish

Electronic Thesis and Dissertation Repository

Light harvesting can be referred to the use of an ensemble of different nanoparticles, or quantum dots, or other absorbers to optimize the ability to capture a given spectrum of electromagnetic radiation (for example the solar spectrum under specific atmospheric conditions) in a light-absorbing system. To this end, different nanoparticles play complementary functions within the system and absorb or scatter light at different wavelength intervals. Light harvesting finds applications in fields as diverse as solar cells, photosynthesis and photocatalysis. Graphene supporting a set of different semiconducting nanoparticles has often been proposed as light harvesters. To further this concept, my thesis …

Fabrication Of Specialized Scintillators For Nuclear Security Applications, Cordell James Delzer

Doctoral Dissertations

Radiation detectors are important for a variety of fields including medical imaging, oil drilling, and nuclear security. Within nuclear security, they can serve a multitude of purposes whether that be imaging, localization, isotopic identification, or even just activity measurement. Even without directly seeing a nuclear material it is often able to notice their existence without a detector. Scintillators make up an important part of these detectors due to their large intrinsic efficiency, low cost, large volume, and relatively low upkeep. Due to the importance of the large number of purposes these scintillators may be used for, it can often be …

Interactions Of Organic Fluorophores With Plasmonic Surface Lattice Resonances, Robert J. Collison

Dissertations, Theses, and Capstone Projects

It is common knowledge that metals, alloys and pure elements alike, are lustrous and reflective, the more so when a metal surface is flat, polished, and free from oxidation and surface fouling. However, some metals reflect visible light, in the 380 nm to 740 nm range of wavelengths, much more strongly than others. In particular, some metals reflect wavelengths in certain portions of the ultraviolet (UV), visible, and near-infrared (NIR) regime, let us say 200 nm to 2000 nm, while absorbing light strongly in other segments of this range. There are several factors that account for this difference between various …

Experimental Exploration Of Shared Magnetic Phases Between Diverse Systems Of Iron-Pnictide Superconductors, Ryan Scott Stadel

Graduate Research Theses & Dissertations

The exciting field of iron-pnictide superconductors offers unique opportunities for studying the relationship between magnetism and unconventional superconductivity. This is vital to developing an understanding of the microscopic origin of high-temperature superconductivity, which is itself an important step in harnessing such a potentially revolutionary technology.

Polycrystalline and crystalline samples are synthesized over a diverse collection of related iron-pnictide systems including (Ca,Sr,Ba)1-xNaxFe2As2, Ba(Fe1-xCox)2As2 (122s), and LaFeAs1-xPxO, and TbFeAs1-xPxO (1111s). These compounds are characterized through various types of neutron and x-ray diffraction on multiple instruments, as well as muon spin resonance, and magnetic susceptibility measurements.

A thorough investigation into the conditions under …

The Effects Of Increasing Positively Charged Metal Ions Within Synovial Fluid, Kandisi Anyabwile

Williams Honors College, Honors Research Projects

Osteoarthritis is a degenerative joint disease that affects 10% of men and 13% of women over age of 60. It is the degradation of the cartilage between two bones; obesity, age, overuse, or injury are major contributors to the development of this disease. The joint is incapsulated by the synovial sac filled with a viscous solution that aids in lubrication referred to as synovial fluid. If the synovial sac is ruptured due to injury, positive ions (K⁺, Na⁺, Ca²⁺, and Fe³⁺) may affect viscoelastic properties within the sac. The purpose of this …

Electronic And Local Structures Of Pt-Based Bimetallic Alloy And Core-Shell Systems, Jiatang Chen

Electronic Thesis and Dissertation Repository

This thesis investigates the electronic structure of Pt for catalysis applications. The importance of the Pt 5d band is discussed in terms of the bonding capability of Pt. The oxygen reduction reaction in proton exchange membrane fuel cells is chosen as the catalytic reaction model to illustrate the effect of Pt 5d states on Pt-O interaction. Pt-based bimetallic systems are introduced as a solution for the high price and limited resources of Pt. Despite lower usage of Pt, the tuning capability to optimize the Pt 5d band in bimetallic catalysts is supposed to provide superior catalytic activity. Advanced synchrotron X-ray …

Production Of Medical Radioisotopes Using Titanium Accelerator Targets, Christopher Shaun Loveless

Arts & Sciences Electronic Theses and Dissertations

Theranostic radiopharmaceuticals enable diagnostic imaging and radionuclide therapy in patients using a single molecular agent labeled with a diagnostic-therapeutic pair (e.g., 68Ga/177Lu) or a theranostic radionuclide (e.g., 131I). This theranostic approach can help inform patient-specific treatment plans and improve clinical outcomes. Radionuclide pairs used in theranostic agents fall into two categories: pseudo matched-pairs (e.g., 68Ga/177Lu) and matched-pairs (e.g., 124I/131I). Pseudo matched-pair radionuclides have similar chemistries and pharmacokinetics when bound to the same bioconjugate molecule. In contrast, identical chemistries and pharmacokinetics can be obtained by using the matched-pair radionuclides.

The isotopes of Sc include two diagnostic radioisotopes, 43Sc & 44Sc, and …

Comparison Of The Vibrational Modes Of Thiolated Gold Nanoparticles Undergoing Core-Conversions Via Raman Spectroscopy, William Gregory Cannella Jr.

Honors Theses

In this project, the vibrational characteristics/vibrational modes are explored via Raman Spectroscopy for thiolated-gold nanoparticles. This class of compounds is also known as gold nanoparticles (AuNPs). They remain of great interest in research areas such as catalysis, gold dependent nanoelectronics, drug delivery, and sensing, due to their unique size-dependent optical, chiroptical, and electronic properties. Vibrational spectroscopy of thiolated gold nanoparticles are oftentimes considered nontrivial as the compounds strongly absorb light in the visible region of the electromagnetic spectrum, are generally considered weak scatterers, and give off large amounts of fluorescence. This combined with their black appearance, susceptibility to localized heating, …

Methodologies For Metal Functionalization Of Phosphorus Based Photopolymer Networks, Vanessa Béland

Electronic Thesis and Dissertation Repository

Photopolymer networks with phosphonium cation, alkyl phosphine and olefin functionality were designed, synthesized and functionalized with metals by metathesis, coordination and hydrometallation reactions, respectively. The materials were strategically designed so that the metal functionalization step could be monitored and quantified. In some cases, this involved characterization by IR, NMR, or X-ray spectroscopic techniques, or by comparison to molecular analogues. It was found that by using a bi-functional photopolymer network, the material could be bi-metallized by orthogonal mechanisms. All metallized polymer networks were tested for their suitability as precursors to metal-containing ceramics. The polymers were pyrolyzed, and on analysis it was …

An In-Situ Study Of The Aqueous Speciation Of Uranium (Vi) Under Hydrothermal Conditions, Diwash Dhakal

MSU Graduate Theses

Rigorous study of the speciation distribution of uranyl-chloride bearing solutions under hydrothermal conditions is important to understand the transport mechanism of uranium underground, which is of uttermost interest to parties studying the geological uranium deposits and those studying the possibilities of geological repositories for spent nuclear waste. I report an in-situ Raman spectroscopic study of the speciation distribution of aqueous uranyl-chloride complexes upto 500°C conducted using a HDAC as the high PT spectroscopic cell. The samples studied contained the species UO₂²⁺, UO₂Cl⁺, UO₂Cl₂⁰ and UO₂Cl₃^{- …}

Energy Transfer Between Eu2+ And Mn2+ For Na(Sr,Ba)Po4 And Ba2mg(Bo3)2, Kevin Bertschinger

Dissertations, Master's Theses and Master's Reports

There is no debate of the affect that solid-state lighting has had on the world we live in. Throughout the centuries, lighting has continued to improve from kerosene lanterns to white light emitting diodes. Even though lighting today is sufficient there is still much room to improve color rendering index and efficiency. An active area of research to improve today's lighting technology is by doping inorganic phosphors with luminescent ion centers. There have been numerous reports of inorganic phosphors showing a variety of emission color and luminescence. In this thesis we discuss two new inorganic phosphors codoped with Eu^{2+ …}

A Hydrogen-Bond Stabilized Mechanism Of Oxygen Evolution In Photosystem Ii: A Proposed Computational Experiment, Christopher King

Undergraduate Theses, Professional Papers, and Capstone Artifacts

The ability of plants to take in water and release oxygen into the atmosphere is crucial to the survival of life on Earth. During photosynthesis, water is oxidized to O₂ (dioxygen) at the Oxygen Evolving Complex (OEC) of Photosystem II. Structurally, the OEC resembles a box with an open lid, consisting of metal atoms (four manganese and one calcium) bridged by oxygen atoms. The mechanism of action of this complex, however, is not well understood. Various mechanisms have been proposed in recent years to explain how the OEC oxidizes water to dioxygen, but all of these mechanisms contain gaps …

Crystallographic Exploration Of Fundamental Technetium Species At Nonambient Conditions, Daniel S. Mast

UNLV Theses, Dissertations, Professional Papers, and Capstones

The study of mater under extreme conditions has yielded fascinating insight into the physical and chemical nature of materials that under more modest conditions are considered mundane but have quite unusual properties when under pressure. Examples of this are the lightest of elements found in the first two rows and in the heaviest elements of the lanthanide and actinide series. Pure elements, though the simplest possible chemical systems, have proven to be among the most complex and interesting. Technetium metal is a simple HCP transition metal that, due to its half-filled d-shell, has a rich chemistry and an important place …

Improved Partial Charge Models In Siliceous Zeolites For The Simulation Of Adsorption And Identification Of Catalytic Sites, Jarod J. Wolffis

UNLV Theses, Dissertations, Professional Papers, and Capstones

Utilization of computational modelling and simulation is expanding as computer processing power has increased and as new tools have been developed. This thesis focuses on efforts to improve the accuracy of simulations in aluminosilicate zeolites, an industrially important category of materials for catalysis and separations. For these sorbents, partial atomic charge represents a critical parameter in molecular mechanics simulations, determining the Coulombic non-bonding interaction. Partial charges may also be used as a measure of important physical parameters of the system such as the degree of covalency or the relative acidity of catalytic sites. We compare several common methods for predicting …

Improving Predictive Capabilities Of Classical Cascade Theory For Nonproliferation Analysis, David Allen Vermillion

Doctoral Dissertations

Uranium enrichment finds a direct and indispensable function in both peaceful and nonpeaceful nuclear applications. Today, over 99% of enriched uranium is produced by gas centrifuge technology. With the international dissemination of the Zippe archetypal design in 1960 followed by the widespread illicit centrifuge trafficking efforts of the A.Q. Khan network, traditional barriers to enrichment technologies are no longer as effective as they once were. Consequently, gas centrifuge technology is now regarded as a high-priority nuclear proliferation threat, and the international nonproliferation community seeks new avenues to effectively and efficiently respond to this emergent threat.

Effective response first requires an …

Ultrafast Spectroscopy And Energy Transfer In An Organic/Inorganic Composite Of Zinc Oxide And Graphite Oxide, Jeff A. Secor

Dissertations, Theses, and Capstone Projects

The energy transfers and nature of defect levels of an organic/inorganic composite of Zinc Oxide and Graphite are studied with multidimensional spectroscopy. The edge and surface states of each composite are uncovered using excitation emission experiments showing which defect states are mediating the energy transfer from the metal oxide to the graphite oxide. Multidimensional time resolved spectroscopy further describes the effect of the carbon phase on the energy transfer pathways in the material.

The Dawn Of New Quantum Dots: Synthesis And Characterization Of Ge1-Xsnx Nanocrystals For Tunable Bandgaps., Richard J. Esteves

Theses and Dissertations

Ge_1-xSn_x alloys are among a small class of benign semiconductors with composition tunable bandgaps in the near-infrared spectrum. As the amount of Sn is increased the band energy decreases and a transition from indirect to direct band structure occurs. Hence, they are prime candidates for fabrication of Si-compatible electronic and photonic devices, field effect transistors, and novel charge storage device applications. Success has been achieved with the growth of Ge_1-xSn_x thin film alloys with Sn compositions up to 34%. However, the synthesis of nanocrystalline alloys has proven difficult due to larger discrepancies (~14%) in …

Non-Conventional Approaches To Syntheses Of Ferromagnetic Nanomaterials, Dustin M. Clifford

Theses and Dissertations

The work of this dissertation is centered on two non-conventional synthetic approaches to ferromagnetic nanomaterials: high-throughput experimentation (HTE) (polyol process) and continuous flow (CF) synthesis (aqueous reduction and the polyol process). HTE was performed to investigate phase control between Fe_xCo_1-x and Co_3-xFe_xO_y. Exploration of synthesis limitations based on magnetic properties was achieved by reproducing M_s=210 emu/g. Morphological control of Fe_xCo_1-x alloy was achieved by formation of linear chains using an H_ext. The final study of the Fe_xCo_1-x chains used DoE to …

Electronic Structure And Stability Of Ligated Superatoms And Bimetallic Clusters, William H. Blades

Theses and Dissertations

Quantum confinement in small metal clusters leads to a bunching of states into electronic shells reminiscent of shells in atoms. The addition of ligands can tune the valence electron count and electron distribution in metal clusters. A combined experimental and theoretical study of the reactivity of methanol with Al_nI_m⁻ clusters reveals that ligands can enhance the stability of clusters. In some cases the electronegative ligand may perturb the charge density of the metallic core generating active sites that can lead to the etching of the cluster. Also, an investigation is conducted to understand how the bonding …

The Electrochemistry Of Hydrogen Peroxide On Uranium Dioxide And The Modelling Of Used Nuclear Fuel Corrosion Under Permanent Disposal Conditions, Linda Wu

Electronic Thesis and Dissertation Repository

This thesis reports a series of investigations examining the corrosion process of used nuclear fuel under permanent disposal conditions. The motivation of the project is that the safety assessment of deep geological disposal of spent nuclear fuel requires a fundamental understanding of the processes controlling fuel corrosion which could lead to the release of radionuclides to the geosphere from a failed container.

One primary objective of this project was to develop a computational model in order to simulate fuel corrosion under the disposal conditions. A series of simulations based on COMSOL were designed and developed to determine the influence of …

Magnetic And Orbital Orders Coupled To Negative Thermal Expansion In Mott Insulators, Ca2ru1-Xmxo4 (M = 3d Transition Metal Ion), Tongfei Qi

Theses and Dissertations--Physics and Astronomy

Ca₂RuO₄ is a structurally-driven Mott insulator with a metal-insulator (MI) transition at T_MI = 357K, followed by a well-separated antiferromagnetic order at T_N = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts T_MI and induces exotic magnetic behavior below T_N. Moreover, M doping for Ru produces negative thermal expansion in Ca₂Ru_1-xM_xO₄ (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio reaching as high as 1%. The onset of the …

Extraction Chromatographic Studies Of Rutherfordium And Dubnium Homologs, Megan E. Bennett

UNLV Theses, Dissertations, Professional Papers, and Capstones

Studying the chemistry of transactinide elements does not only allow for these elements to be properly placed in the Periodic Table, but it also permits for the extrapolation of the electronic structure based upon the position of the element in the Periodic Table. In addition it enable for the assessment of the role that relativistic effects play in the chemical behavior of the heaviest elements. An improved understanding of the role of relativistic effects in chemistry of the heaviest elements allows for a better understanding of the fundamentals principles that govern the Periodic Table. In order to investigate the chemistry …

Electronic Structure Of Lithium Tetraborate, David J. Wooten

Theses and Dissertations

Due to interest as neutron detection material, an investigation of Li₂B₄O₇(110) and Li₂B₄O₇(100) was undertaken, utilizing photoemission and inverse photoemission spectroscopic techniques. The measured band gap depended on crystallographic direction with the band gaps ranging from 8.9±0.5 eV to 10.1±0.5 eV. The measurement yielded a density of states that qualitatively agreed with the theoretical results from model bulk band structure calculations for Li₂B₄O₇; albeit with a larger band gap than predicted, but consistent with the known deficiencies of LDA and DFT calculations. …

Three Dimensional Positron Annihilation Momentum Measurement Technique (3dpamm) Applied To Measure Oxygen-Atom Defects In 6h Silicon Carbide, Christopher S. Williams

Theses and Dissertations

A three-dimensional Positron Annihilation Spectroscopy System (3DPASS) capable to simultaneously measure three-dimensional electron-positron (e--e+) momentum densities measuring photons derived from e--e+ annihilation events was designed and characterized. 3DPASS simultaneously collects a single data set of correlated energies and positions for two coincident annihilation photons using solid-state double-sided strip detectors (DSSD). Positions of photons were determined using an interpolation method which measures a figure-of-merit proportional to the areas of transient charges induced on both charge collection strips directly adjacent to the charge collection strips interacting with the annihilation photons. The subpixel resolution was measured for both double-sided strip detectors (DSSD) and …