Physics Commons^™

Using Superatomic Clusters And Charge Transfer Ligands To Control Electronic Characteristics Of Phosphorene Nanoribbons And Phosphorene Monolayer, Ryan Lambert

Theses and Dissertations

Phosphorene is a two-dimensional electron poor p-type semiconductor with high carrier mobility and great promise for applications in electronics and optoelectronics. As the main theme in this dissertation, the following work represents different investigations of various electronic properties associated with phosphorene. Most notable are the findings on charge transfer doping with metal-chalcogenide superatoms which displays novel control of the two most important properties of a semiconductor – the band gap energy and the nature of carriers. By tuning the width of the gap and p-/n-type character of conduction, we gain control over a material’s capacity to play a certain role …

Molecular Insights Into The Redox Of Atmospheric Mercury Through Laser Spectroscopy, Rongrong Wu Cohen

Theses and Dissertations

The widespread pollution of mercury motivates research into its atmospheric chemistry and transport. Gaseous elemental mercury (Hg(0)) dominates mercury emission to the atmosphere, but the rate of its oxidation to mercury compound (Hg(II)) plays a significant role in controlling where and when mercury deposits to ecosystems. Atomic bromine is regarded as the main oxidant for Hg(0) oxidation, known to initiate the oxidation via a two-step process in the atmosphere – formation of BrHg (R1) and subsequent reactions of BrHg with abundant free radicals Y, i.e., NO2, HOO, etc. (R2), where the reaction of BrHg +Y could also lead to the …

Atomistic Simulation Of Na+ And Cl- Ions Binding Mechanisms To Tobermorite 14Å As A Model For Alkali Activated Cements, Ahmed Abdelkawy

Theses and Dissertations

The production of ordinary Portland cement (OPC) is responsible for ~8% of all man-made CO2 emissions. Unfortunately, due to the continuous increase in the number of construction projects, and since virtually all projects depend on hardened cement from the hydration of OPC as the main binding material, the production of OPC is not expected to decrease. Alkali-activated cement produced from the alkaline activation of byproducts of industries, such as iron and coal industries, or processed clays represents a potential substitute for OPC. However, the interaction of the reaction products of AAC with corrosive ions from the environment, such as Cl-, …

Engineered Nanostructured Nitrogen-Doped Carbon Network (Ndc) Electrodes With Unprecedented Cycling Stability For Water Capacitive Deionization In Harsh Conditions, Soha Essam Anwar

Theses and Dissertations

Capacitive deionization (CDI) is a feasible low-cost desalination technique for low-to-medium (brackish) salinity water. However, cycling stability and regeneration of the CDI electrodes are the bottlenecks hindering the practical application of the technology on large scale. Oxidation of the electrodes during the sequential adsorption-desorption processes is one of the most challenging problems hindering their long-term cycling performance. Herein, we demonstrated the ability to design and fabricate exceptionally stable CDI electrodes via a one-pot pyrolysis protocol. The optimized pyrolysis of nitrogen-carbon precursors at different temperatures enabled the fabrication of carbon materials with a controlled amount nitrogen dopant (NDCs) with exceptional cycling …

Nanoengineered Materials For Energy Conversion & Storage Applications: A Density Functional Theory Study, Ahmed Biby

Theses and Dissertations

The conventional approach for the development of novel materials has become long relative to the desired product development cycle. Thus, the sluggish pace of the development of materials within the conventional approach hinders the rapid transformation of the scientific outcomes into useful technological products. To this end, the field of hierarchical materials informatics evolved to bridge this gap. In this field, the multiscale material internal structure is considered the starting point and the core of this approach. This being said, the density functional theory (DFT) was used to generate useful materials data for the advancement of the hierarchical materials data-bases …

Fabrication Of Metal-Silicon Nanostructures By Reactive Laser Ablation In Liquid, Eric J. Broadhead

Theses and Dissertations

Metal-silicon nanostructures are a growing area of research due to their applications in multiple fields such as biosensing and catalysis. In addition, silicon can provide strong support effects to metal nanoparticles while being more cost effective than traditionally used supports, like titania. Traditional wet-chemical methods are capable of synthesizing metal-silicon nanostructures with a variety of composition and nanoparticle shapes, but they often require high temperatures, toxic solvents, strong reducing agents, or need capping agents added to stabilize the nanoparticles. Laser processing is an emerging technique capable of synthesizing metal-silicon composite surfaces that offers a faster, simpler, and greener synthesis route …

Nebulizer-Based Systems To Improve Pharmaceutical Aerosol Delivery To The Lungs, Benjamin M. Spence

Theses and Dissertations

Combining vibrating mesh nebulizers with additional new technologies leads to substantial improvements in pharmaceutical aerosol delivery to the lungs across therapeutic administration methods. In this dissertation, streamlined components, aerosol administration synchronization, and/or Excipient Enhanced Growth (EEG) technologies were utilized to develop and test several novel devices and aerosol delivery systems. The first focus of this work was to improve the poor delivery efficiency, e.g., 3.6% of nominal dose (Dugernier et al. 2017), of aerosolized medication administration to adult human subjects concurrent with high flow nasal cannula (HFNC) therapy, a form of continuous-flow non-invasive ventilation (NIV). The developed Low-Volume Mixer-Heater (LVMH) …

Ligand Effects On Electronic, Magnetic, And Catalytic Properties Of Clusters And Cluster Assemblies, Dinesh Bista 9288522

Theses and Dissertations

Ligands commonly protect metallic clusters against reacting with outside reactants. However, ligands can also be used to control the redox properties enabling the formation of super donors/acceptors that can donate/accept multiple electrons. This thesis focuses on how the ligands can be used to control the electronic and magnetic features of clusters and ligand stabilized cluster-based assemblies, leading to nano pn junctions with directed transport, the possibility of light-harvesting, and catalysts for cross-coupling reactions. The thesis addresses three distinct classes of clusters and their applications. The first class of cluster “metal chalcogen clusters” is the central idea of the thesis focused …

Adhesion At Solid/Liquid Interfaces, Neda Ojaghlou

Theses and Dissertations

The adhesion at solid/liquid interface plays a fundamental role in diverse fields and helps explain the structure and physical properties of interfaces, at the atomic scale, for example in catalysis, crystal growth, lubrication, electrochemistry, colloidal system, and in many biological reactions. Unraveling the atomic structure at the solid/liquid interface is, therefore, one of the major challenges facing the surface science today to understand the physical processes in the phenomena such as surface coating, self-cleaning, and oil recovery applications. In this thesis, a variety of theory/computational methods in statistical physics and statistical mechanics are used to improve understanding of water adhesion …

Improving Fallout Characterization By Using Multivariate Techniques To Determine Composition, Christopher R. Pitkins

Theses and Dissertations

Multivariate statistical techniques have been applied in order to un-mix nuclear fallout debris chemical data. This information is critical to characterization of fallout particle formation following a nuclear detonation. Understanding the correlation between environmental precursors and actinide concentrations in post-detonation nuclear fallout material aids in understanding the physical and chemical processes that alter nuclear device signatures in the fireball. This research examines 123 nuclear fallout samples from a historical nuclear test. Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) are used to collect chemical compositions of the fallout samples. Principal component analysis (PCA) is applied in order to examine …

Biocidal Defeat Agents Produced By Silver-Iodine Nanoenergetic Gas Generators, Ivan Davila

Theses and Dissertations

Nanostructured aluminum (Al), iodine pentoxide (I2O5) nano-rods, and silver oxide (Ag2O) nanoparticles, (Al-I2O5-Ag 2O) were used to compose the ternary thermite composition that serves as a Nanoenergetic Gas Generator (NGG). This composition produces biocidal gases giving the mixture the ability to destroy highly pathogenic microorganisms or bacteria. The dissemination of the biocidal gas in combustion chamber was observed using a high-speed camera. The testing of NGG combustion process against the living Escherichia coli (E.coli) K-12 strain cells, that were cultivated/placed on the sample/chamber surfaces, demonstrated that iodine and silver atoms clouds were deposited to the bacteria surface. The 10/75/15 wt …

Investigations Into Structure And Properties Of Atomically-Precise Transition Metal-Chalcogenide Clusters Of Crte And Ligated Cr6te8(Pet3)6, Anthony F. Pedicini

Theses and Dissertations

The complete understanding of a clusters electronic structure, the primary mechanisms for its properties and stabilization is necessary in order to functionalize them for use as building blocks within novel materials. First principle theoretical studies have been carried out upon the electronic properties of Cr_xTe_y (x = 1 – 6, y = 0 – 8, x + y ≤ 14), as well as for the larger triethylphosphine (PEt₃) ligated cluster system of Cr₆Te₈(PEt₃)₆. Together, we aim to use the information garnered from the smaller clusters to address …

Theoretical And Experimental Analysis Of Optical Properties Of Defects In Gan:, Ibrahima Castillo Diallo

Theses and Dissertations

Using the Heyd-Scuseria-Ernzherof (HSE06) hybrid functional method along with photoluminescence experimental measurements, we analyze the properties of intrinsic defects such as vacancies, interstitials, antisites, and common complexes. By using configurational coordinate diagrams, we estimate the likelihood of defects to be radiative or non-radiative. Our calculations show that gallium vacancies exhibit a large magnetic moment in the neutral charge state and are most likely non-radiative. We also investigate the correlation between the observed infrared PL bands created in 2.5 MeV electron-irradiated GaN samples and the formation of native defects. It is found that gallium-nitrogen divacancies are possible sources of the broad …

Experimental Methods In Cryogenic Spectroscopy: Stark Effect Measurements In Substituted Myoglobin, Bradley Michael Moran

Theses and Dissertations

Dawning from well-defined tertiary structure, the active regions of enzymatic proteins exist as specifically tailored electrostatic microenvironments capable of facilitating chemical interaction. The specific influence these charge distributions have on ligand binding dynamics, and their impact on specificity, reactivity, and biological functionality, have yet to be fully understood. A quantitative determination of these intrinsic fields would offer insight towards the mechanistic aspects of protein functionality. This work seeks to investigate the internal molecular electric fields that are present at the oxygen binding site of myoglobin.

Experiments are performed at 1 K on samples located within a glassy matrix, using the …

Variable Pathlength Cavity Spectroscopy Development Of An Automated Prototype, Ryan Schmeling

Theses and Dissertations

ABSTRACT

VARIABLE PATHLENGTH CAVITY SPECTROSCOPY

DEVELOPMENT OF AN AUTOMATED PROTOTYPE

by

Ryan Andrew Schmeling

The University of Wisconsin-Milwaukee, 2016

Under the Supervision of Professor Joseph H. Aldstadt III

Spectroscopy is the study of the interaction of electromagnetic radiation (EMR) with matter to probe the chemical and physical properties of atoms and molecules. The primary types of analytical spectroscopy are absorption, emission, and scattering methods. Absorption spectroscopy can quantitatively determine the chemical concentration of a given species in a sample by the relationship described by Beer’s Law. Upon inspection of Beer’s Law, it becomes apparent that for a given analyte concentration, …

Fabricating Superhydrophobic And Superoleophobic Surfaces With Multiscale Roughness Using Airbrush And Electrospray, Karam N. Almilaji

Theses and Dissertations

Examples of superhydrophobic surfaces found in nature such as self-cleaning property of lotus leaf and walking on water ability of water strider have led to an extensive investigation in this area over the past few decades. When a water droplet rests on a textured surface, it may either form a liquid-solid-vapor composite interface by which the liquid droplet partially sits on air pockets or it may wet the surface in which the water replaces the trapped air depending on the surface roughness and the surface chemistry. Super water repellent surfaces have numerous applications in our daily life such as drag …

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 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 …

Drying Methods For The Fabrication Of Polymer Foam Material, Dalton Echard

Theses and Dissertations

This is a report on the study of the drying of nanoporous polymer foam material fabricated by photolithogtaphic methods. Three drying methods were employed, which were air drying, supercritical drying and freeze drying. After fabrication and drying, physical properties of the polymer foams were measured. These measurements included density of the material, Young’s modulus, surface area, and the shape of the skeletal particles. The measurements determined the effect of the polymer concentration and the effect of drying methods. It was determined that polymer concentration had a much larger effect on the properties of the materials than the drying method.

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 …

Probing Bonding And Dynamics At Heterogeneous Adsorbate/Graphene Interfaces, Eric Charles Mattson

Theses and Dissertations

Graphene-based materials are becoming an astoundingly promising choice for many relevant technological and environmental applications. Deriving graphene from the reduction of graphene oxide (GO) is becoming a popular and inexpensive route toward the synthesis of these materials. While the desired product from GO reduction is pristine graphene, defects and residual oxygen functional groups inherited from the parent GO render reduced graphene oxide (RGO) distinct from graphene. In this work, the structure and bonding for GO and RGO is investigated to the end of a working understanding of the composition and properties of these materials. In situ selected area electron diffraction …

Structure And Chemistry Of Model Catalysts In Ultrahigh Vacuum, Joshua D. Walker

Theses and Dissertations

The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. …

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. …

The Material Properties Of Cssnbr3 And Csbr:Sn-1% And Their Potential As Scintillator Detector Material, Neal B. Kleinschmidt

Theses and Dissertations

The search for superior nuclear radiation detection materials is ongoing. Current scintillator materials using Thallium doped Sodium Iodide or Cesium Iodide are the benchmarks for ease of use and quick identification of isotope species. This research aims to explore Cesium Bromide doped with 1% molar tin (CsBr:Sn-1%) and Cesium Tin Bromide (CsSnBr₃) as candidate materials for a new scintillator. The techniques of Extended X-Ray Absorption Fine Structure (EXAFS), X-Ray Absorption Near Edge Structure (XANES) and Cathodoluminescence are used to determine the suit- ability of CsSnBr3 and CsBr:Sn-1% with Sn⁴⁺ as a potential scintillator materials and explore their …

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 …

In-Situ, Gate Bias Dependent Study Of Neutron Irradiation Effects On Algan/Gan Hfets, Janusz K. Mikina

Theses and Dissertations

AlGaN/GaN Heterostructure Field Effect Transistors (HFETs) have come under increased study in recent years due to their highly desirable material and electrical properties and survivability even during and after exposure to extreme temperature and radiation environments. In this study, unpassivated and SiN passivated Al_0.27Ga_0.73N/GaN HFETs were subjected to neutron radiation at 120 K. The primary focus of the research was the effects of neutron irradiation on drain current, gate leakage current, threshold voltage shift, gate-channel capacitance, and the effects of biasing the gate during irradiation. In-situ measurements were conducted on transistor current, gate-channel capacitance, and gate …

Q-Switched And Mode Locked Short Pulses From A Diode Pumped, Yb-Doped Fiber Laser, Seth M. Swift

Theses and Dissertations

A diode-pumped, ytterbium (Yb)-doped fiber laser system was designed and demonstrated to operate in continuous wave (cw), passively Q-switched and possibly passively mode locked operation. To our knowledge, this was the first fiber laser oscillator built at the Air Force Institute of Technology. A Cr⁴⁺:YAG (Chromium: Ytterbium Aluminum Garnett) crystal was used as a saturable absorber to generate Q-switched pulses. Attempts to mode lock the laser were performed using a semiconductor saturable absorber mirror (SESAM) and through nonlinear polarization rotation (NPR). The best output power result was 5 Watts (W) while pumping at 8.3 W, yielding 60% efficiency …

Investigation Of Electrical And Optical Properties Of Bulk Iii-V Ternary Semiconductors, Travis C. Gomez

Theses and Dissertations

Bulk grown III-V ternary semiconductors of In_0.08Ga_0.92Sb and In_0.15Ga_0.85As were investigated through Hall-effect and photoluminescence measurements to determine carrier concentration, mobility, sheet resistivity, and luminescence spectrum. In the past, epitaxial layers of ternary compounds have been grown on binary compound substrates, and thus very limited lattice matched ternary alloys were available. Recently, bulk grown ternary substrates have been developed, and it has presented a renewed interest in using these substrates to grow high quality ternary compounds for use in many next generation optoelectronic devices. The results of photoluminescence (PL) study for the …

The Effective Potential Energy Surfaces Of The Nonadiabatic Collision B(2PJA) + H2(1Σ+G,Ν,J) ↔ B(2PJ'A) + H2(1Σ+G,Ν',J'), Matthew B. Garvin

Theses and Dissertations

Effective potential energy surfaces (PESs) are calculated for a nonadiabatic collision . This calculation employed 1 ²A', 2 ²A' and 1 ²A" adiabatic PESs numerically calculated at the state-averaged multiconfigurational self-consistent field (SA-MCSCF)/configuration interaction (CI) level for several values of the H₂ bond length, H₂ orientation angle, and boron distance. The associated nonadiabatic coupling terms (NACTs) were calculated from the SA-MCSCF/CI wave functions using analytic gradient techniques. A line integral through the NACTs was then used to determine the adiabatic-to-diabatic mixing angle required to transform from the 1 ²A' and 2 ²A' …

Use Of Quantum Mechanical Calculations To Investigate Small Silicon Carbide Clusters, Jean W. Henry

Theses and Dissertations

Density Functional Theory (DFT) method was employed to model silicon carbide small clusters. Comparing the DFT calculation results with experimental results that observed by using photoelectron spectroscopy (PES), DFT predicts the same structures that experiment observed. For electron affinity, DFT results are in good agreement with experimental results, the root mean square negative offset 0.1 eV found using medium size of basis set (cc-pVDZ+) calculation. DFT results for vibrational frequencies are in good agreement with experiment results; the root mean square error is 72.5 cm^-1 wave number. 16 ground state structures of Si_mC_n (m ≤ 4, …