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Articles 7801 - 7830 of 12195
Full-Text Articles in Physical Sciences and Mathematics
Derivatization Of Stable, Soluble Redox-Active Organic Materials For Non-Aqueous Redox Flow Batteries, Thilini Malsha Suduwella
Derivatization Of Stable, Soluble Redox-Active Organic Materials For Non-Aqueous Redox Flow Batteries, Thilini Malsha Suduwella
Theses and Dissertations--Chemistry
In screening active materials for redox flow batteries (RFBs) – in which solubility is important to raise the volumetric energy density – scientists are slave to trial and error, modifying organic molecules in an attempt to optimize (increase) solubility without compromising other important properties such as stability and redox potential. A trained chemist can often predict the trends of solubility with the structural modifications in the neutral state of the materials, but when it’s come to the charged state of the materials, it doesn’t follow the same trend as the neutral species and relative values are hard to predict. The …
Interfaces In Lead-Free Tin Perovskite Photovoltaics: An Investigation Of Energetics, Ion Mobility, Surface Modification, And Performance, Alex Boehm
Theses and Dissertations--Chemistry
Halide perovskites have generated tremendous interest as low-cost semiconductors for optoelectronics, such as photovoltaics, lasers, and light emitting diodes due to their extraordinary optical and transport properties. Perovskite photovoltaics in particular have demonstrated a meteoric rise in power conversion efficiencies and drawn considerable interest as a next-generation solar energy technology. The rapid development has centered around lead-based derivatives, and concerns regarding the toxicity of lead has sparked interest in low toxicity and more environmentally friendly perovskite derivatives. In this regime tin (Sn) is regarded as a prominent alternative owing to the ideal bandgap and reduced toxicity exhibited by Sn-halide perovskites. …
Multiscale Modeling Of Structure-Function Relationships Of Organic Semiconductors, Shi Li
Multiscale Modeling Of Structure-Function Relationships Of Organic Semiconductors, Shi Li
Theses and Dissertations--Chemistry
While optoelectronic devices built from organic semiconductors (OSC) continue to find their way into the commercial landscape, there remain numerous challenges to overcome to supplant traditional semiconductors in many technologies. Chief among these are low performance metrics relative to devices with conventional semiconductors and device stability. In order to overcome these challenges, a wide range of new OSC and processing technologies have been developed. However, there remains limited fundamental understanding of the relationship between molecular structure, packing in the solid state, and the resulting materials properties. Here, we make use of multiscale molecular models and utilize classical all-atom molecular dynamic …
Developing And Testing Redox Active Organic Molecules For Nonaqueous Redox Flow Battery Applications, Nuwan Harsha Attanayake
Developing And Testing Redox Active Organic Molecules For Nonaqueous Redox Flow Battery Applications, Nuwan Harsha Attanayake
Theses and Dissertations--Chemistry
Non-emissive, sustainable energy sources such as solar, wind, and geothermal power have continued to provide an increasing amount of electricity to support electrical grids. Due to the intermittent nature of renewable energy sources like wind and solar, grid energy storage systems must adjust for variations in and mismatches between electricity production and consumption. Among the available energy storage technologies, redox flow batteries (RFBs) are expected to play a critical role in the grid energy storage due to their decoupled energy and power, long service life, and simple manufacturing. However, the worldwide market penetration of RFB systems is still limited due …
Structure, Surface, And Interfacial Modifications Of Carbon And Supported-Metal Electrodes For Electrochemical Carbon Dioxide Conversion, Namal Wanninayake
Structure, Surface, And Interfacial Modifications Of Carbon And Supported-Metal Electrodes For Electrochemical Carbon Dioxide Conversion, Namal Wanninayake
Theses and Dissertations--Chemistry
Currently, the global emission of greenhouse CO2 is over 36 billion tons per year. Consequently, the atmosphere's CO2 concentrations have exceeded 400 ppm, which is the highest reported in the last three million years. The accumulation of CO2 is the most critical origin for today's climate change; thus, closing the carbon cycle is vital to reverse the detrimental impacts of climate change. Under this goal, the electrochemical reduction of CO2 into commodity fuels and chemicals via renewable energy is one of the most promising strategies to recycle CO2. Despite significant progress made in electrocatalysis, …
Designing Metal-Halide Perovskites With Enhanced Optical Properties And Stability Using Surface Ligands, Md Aslam Uddin
Designing Metal-Halide Perovskites With Enhanced Optical Properties And Stability Using Surface Ligands, Md Aslam Uddin
Theses and Dissertations--Chemistry
Metal-halide perovskites (MHPs), with formula ABX3 (A = methylammonium, formamidinium, or Cs+; B = Sn2+ or Pb2+; and X = Cl-, Br-, or I-) are versatile and attractive materials because of their tunable optical and electronic properties. These optical and electronic properties include tunable direct band gaps, high absorption coefficients, low exciton binding energies, relatively high electron and hole mobilities, narrow emission line-widths, and high photoluminescence (PL) quantum yields (ΦPL). Much of the initial excitement around organic metal-halide perovskites focused on their application in photovoltaics (PVs) …
Identification Of Adsorbate Ft-Ir Bands Using In-Situ Techniques: Pd Speciation And Adsorption Chemistry Of Pd-Zeolites For Passive Nox Adsorption, Robert Bruce Pace Iii
Identification Of Adsorbate Ft-Ir Bands Using In-Situ Techniques: Pd Speciation And Adsorption Chemistry Of Pd-Zeolites For Passive Nox Adsorption, Robert Bruce Pace Iii
Theses and Dissertations--Chemistry
To meet increasingly stringent automotive emissions standards, further improvements in catalytic converter design are necessary. Current automotive catalyst systems are effective at eliminating emission of nitrogen oxides (NOx) once the catalyst reaches operational temperature (~200 °C). NOx emitted at lower catalyst temperatures now comprises most of the NOx released during a typical test cycle. Referred to as “the cold start problem” this issue has come to the forefront of automotive catalyst development, as mitigating these emissions is necessary to further reduce automotive emissions. Passive NOx adsorbers present an appealing solution to the cold start problem, …
The Direct Scattering Map For The Intermediate Long Wave Equation, Joel Klipfel
The Direct Scattering Map For The Intermediate Long Wave Equation, Joel Klipfel
Theses and Dissertations--Mathematics
In the early 1980's, Kodama, Ablowitz and Satsuma, together with Santini, Ablowitz and Fokas, developed the formal inverse scattering theory of the Intermediate Long Wave (ILW) equation and explored its connections with the Benjamin-Ono (BO) and KdV equations. The ILW equation\begin{align*} u_t + \frac{1}{\delta} u_x + 2 u u_x + Tu_{xx} = 0, \end{align*} models the behavior of long internal gravitational waves in stratified fluids of depth $0< \delta < \infty$, where $T$ is a singular operator which depends on the depth $\delta$. In the limit $\delta \to 0$, the ILW reduces to the Korteweg de Vries (KdV) equation, and in the limit $\delta \to \infty$, the ILW (at least formally) reduces to the Benjamin-Ono (BO) equation.
While the KdV equation is very well understood, a rigorous analysis of inverse scattering for the ILW equation remains to be accomplished. There is currently no rigorous proof that the Inverse Scattering …
A Comparative Analysis Of Reinforcement Learning Applied To Task-Space Reaching With A Robotic Manipulator With And Without Gravity Compensation, Jonathan Fugal
A Comparative Analysis Of Reinforcement Learning Applied To Task-Space Reaching With A Robotic Manipulator With And Without Gravity Compensation, Jonathan Fugal
Theses and Dissertations--Electrical and Computer Engineering
Advances in computing power in recent years have facilitated developments in autonomous robotic systems. These robotic systems can be used in prosthetic limbs, wearhouse packaging and sorting, assembly line production, as well as many other applications. Designing these autonomous systems typically requires robotic system and world models (for classical control based strategies) or time consuming and computationally expensive training (for learning based strategies). Often these requirements are difficult to fulfill. There are ways to combine classical control and learning based strategies that can mitigate both requirements. One of these ways is to use a gravity compensated torque control with reinforcement …
Eigenvalue Statistics And Localization For Random Band Matrices With Fixed Width And Wegner Orbital Model, Benjamin Brodie
Eigenvalue Statistics And Localization For Random Band Matrices With Fixed Width And Wegner Orbital Model, Benjamin Brodie
Theses and Dissertations--Mathematics
We discuss two models from the study of disordered quantum systems. The first is the Random Band Matrix with a fixed band width and Gaussian or more general disorder. The second is the Wegner $n$-orbital model. We establish that the point process constructed from the eigenvalues of finite size matrices converge to a Poisson Point Process in the limit as the matrix size goes to infinity.
The proof is based on the method of Minami for the Anderson tight-binding model. As a first step, we expand upon the localization results by Schenker and Peled-Schenker-Shamis-Sodin to account for complex energies. We …
Simultaneous Zeros Of A System Of Two Quadratic Forms, Nandita Sahajpal
Simultaneous Zeros Of A System Of Two Quadratic Forms, Nandita Sahajpal
Theses and Dissertations--Mathematics
In this dissertation we investigate the existence of a nontrivial solution to a system of two quadratic forms over local fields and global fields. We specifically study a system of two quadratic forms over an arbitrary number field. The questions that are of particular interest are:
- How many variables are necessary to guarantee a nontrivial zero to a system of two quadratic forms over a global field or a local field? In other words, what is the u-invariant of a pair of quadratic forms over any global or local field?
- What is the relation between u-invariants of a …
Algebraic And Geometric Properties Of Hierarchical Models, Aida Maraj
Algebraic And Geometric Properties Of Hierarchical Models, Aida Maraj
Theses and Dissertations--Mathematics
In this dissertation filtrations of ideals arising from hierarchical models in statistics related by a group action are are studied. These filtrations lead to ideals in polynomial rings in infinitely many variables, which require innovative tools. Regular languages and finite automata are used to prove and explicitly compute the rationality of some multivariate power series that record important quantitative information about the ideals. Some work regarding Markov bases for non-reducible models is shown, together with advances in the polyhedral geometry of binary hierarchical models.
Resource Efficient Design Of Quantum Circuits For Cryptanalysis And Scientific Computing Applications, Edgard Munoz-Coreas
Resource Efficient Design Of Quantum Circuits For Cryptanalysis And Scientific Computing Applications, Edgard Munoz-Coreas
Theses and Dissertations--Electrical and Computer Engineering
Quantum computers offer the potential to extend our abilities to tackle computational problems in fields such as number theory, encryption, search and scientific computation. Up to a superpolynomial speedup has been reported for quantum algorithms in these areas. Motivated by the promise of faster computations, the development of quantum machines has caught the attention of both academics and industry researchers. Quantum machines are now at sizes where implementations of quantum algorithms or their components are now becoming possible. In order to implement quantum algorithms on quantum machines, resource efficient circuits and functional blocks must be designed. In this work, we …
Moment Kernels For T-Central Subspace, Weihang Ren
Moment Kernels For T-Central Subspace, Weihang Ren
Theses and Dissertations--Statistics
The T-central subspace allows one to perform sufficient dimension reduction for any statistical functional of interest. We propose a general estimator using a third moment kernel to estimate the T-central subspace. In particular, in this dissertation we develop sufficient dimension reduction methods for the central mean subspace via the regression mean function and central subspace via Fourier transform, central quantile subspace via quantile estimator and central expectile subsapce via expectile estima- tor. Theoretical results are established and simulation studies show the advantages of our proposed methods.
Scrollar Invariants Of Tropical Chains Of Loops, Kalila Joelle Sawyer
Scrollar Invariants Of Tropical Chains Of Loops, Kalila Joelle Sawyer
Theses and Dissertations--Mathematics
We define scrollar invariants of tropical curves with a fixed divisor of rank 1. We examine the behavior of scrollar invariants under specialization, and compute these invariants for a much-studied family of tropical curves. Our examples highlight many parallels between the classical and tropical theories, but also point to some substantive distinctions.
Periodic Points On Tori: Vanishing And Realizability, Shane Clark
Periodic Points On Tori: Vanishing And Realizability, Shane Clark
Theses and Dissertations--Mathematics
Let $X$ be a finite simplicial complex and $f\colon X \to X$ be a continuous map. A point $x\in X$ is a fixed point if $f(x)=x$. Classically fixed point theory develops invariants and obstructions to the removal of fixed points through continuous deformation. The Lefschetz Fixed number is an algebraic invariant that obstructs the removal of fixed points through continuous deformation. \[L(f)=\sum_{i=0}^\infty (-1)^i \tr\left(f_i:H_i(X;\bQ)\to H_i(X;\bQ)\right). \] The Lefschetz Fixed Point theorem states if $L(f)\neq 0$, then $f$ (and therefore all $g\simeq f$) has a fixed point. In general, the converse is not true. However, Lefschetz Number is a complete invariant …
Sensitivity Of Electron-Proton Coincidence Asymmetries In Neutron Beta-Decay To Scalar And Tensor Interactions, Subash C. Nepal
Sensitivity Of Electron-Proton Coincidence Asymmetries In Neutron Beta-Decay To Scalar And Tensor Interactions, Subash C. Nepal
Theses and Dissertations--Physics and Astronomy
We study the combined sensitivity of measurements of electron-proton coincidence asymmetries in polarized neutron beta-decay together with a measurement of the electron energy spectrum in unpolarized neutron beta-decay to beyond Standard Model (BSM) scalar and tensor interactions, via the appearance of such BSM physics in the Fierz interference terms b and bv. Whereas measurements of the electron energy spectrum directly probe b, both the proton and neutrino asymmetries for which experimental results exist are not sensitive to bv, but effectively to b - bv. This results in reduced sensitivity to BSM scalar and …
Transverse And Longitudinal Thermal Diffusivity Measurements Of Polymer And Small Molecule Organic Semiconductors With Different Techniques, Maryam Shahi
Theses and Dissertations--Physics and Astronomy
The main thrust of this research was to develop new probes to measure thermal conductivities (κ) of small-molecule crystals, as well as polymer blends of organic semiconductors, both to screen these for possible applications, e.g. as thermoelectric power generators, and to gain an understanding of thermal transport in them. Emphasis has been on the crystals of “TIPS pentacene” [TIPS = 6,13 bis(triisopropylsilylethynyl), and free-standing films of PEDOT:PSS [poly(3,4-ethylenedioxythiophene) polystyrene sulfonate] for different electrochemical and thermoelectric applications. Separate techniques were used for in-plane and transverse thermal conductivities in which 𝜅𝜅 is determined indirectly from measurements of the thermal diffusivity (D ≡ …
Large N Fields And Holography, Animik Ghosh
Large N Fields And Holography, Animik Ghosh
Theses and Dissertations--Physics and Astronomy
We study (nearly) AdS/CFT holography within the context of the Sachdev-Ye- Kitaev (SYK) model. We present a systematic procedure to extract the dynamics of the low energy Schwarzian mode in SYK type models with a single energy scale J and emergent reparametrization symmetry in the infrared within the framework of perturbation theory. We develop a systematic approach using Feynman diagrams in bilocal theory to obtain a formal expression for the enhanced and O(1) corrections to the bilocal propagator and apply this general technique to large q SYK. We show that the Schwarzian theory describes a sector of a general class …
Correlating The Physicochemical Properties Of Magnesium Stearate With Tablet Dissolution And Lubrication, Julie L. Calahan
Correlating The Physicochemical Properties Of Magnesium Stearate With Tablet Dissolution And Lubrication, Julie L. Calahan
Theses and Dissertations--Pharmacy
Magnesium stearate (MgSt) is the most commonly used pharmaceutical excipient and is present in over half the tablet formulations on the market. In spite of its popularity as an effective lubricant, it has been repeatedly recognized that there is significant variability between MgSt samples, which can cause inconsistent lubrication between batches of MgSt. The hypothesis of this research is that the batch-to-batch variability in tablet lubrication and dissolution observed in tablet formulations containing different MgSt samples can be correlated with differences in MgSt physicochemical properties (fatty acid salt composition, crystal hydrate form, particle size and surface area). Developing correlations between …
Effects Of Aperiodicity And Frustration On The Magnetic Properties Of Artificial Quasicrystals, Barry Farmer
Effects Of Aperiodicity And Frustration On The Magnetic Properties Of Artificial Quasicrystals, Barry Farmer
Theses and Dissertations--Physics and Astronomy
Quasicrystals have been shown to exhibit physical properties that are dramatically different from their periodic counterparts. A limited number of magnetic quasicrystals have been fabricated and measured, and they do not exhibit long-range magnetic order, which is in direct conflict with simulations that indicate such a state should be accessible. This dissertation adopts a metamaterials approach in which artificial quasicrystals are fabricated and studied with the specific goal of identifying how aperiodicity affects magnetic long-range order. Electron beam lithography techniques were used to pattern magnetic thin films into two types of aperiodic tilings, the Penrose P2, and Ammann-Beenker tilings. SQUID …
“The Tale Of 3,000 Zircons”: An Investigation Of Grenville Sedimentation In Amazonia Using U/Pb Detrital Zircon Geochronology, Felicia R. Harris
“The Tale Of 3,000 Zircons”: An Investigation Of Grenville Sedimentation In Amazonia Using U/Pb Detrital Zircon Geochronology, Felicia R. Harris
Theses and Dissertations--Earth and Environmental Sciences
The continental collision between Laurentia and Amazonia that generated Rodinia and the Grenville Orogen is proposed to be one of the largest, hottest and longest-lived orogens in Earth history. Subsequent erosion and weathering led to a mountain range’s worth of sediment recycled into clastic systems across North America, otherwise known as the “Great Grenville Sedimentation Event”. The Sunsas orogeny in Amazonia is correlative to the Grenville in North America and is proposed to be the result of final Rodinian collision at 1200-1000 Ma. Despite the connection between the two ranges and the robust sedimentary record in North America, little work …
Filtered-Dynamic-Inversion Control For Unknown Minimum-Phase Systems With Unknown Relative Degree, Sumit Suryakant Kamat
Filtered-Dynamic-Inversion Control For Unknown Minimum-Phase Systems With Unknown Relative Degree, Sumit Suryakant Kamat
Theses and Dissertations--Mechanical Engineering
We present filtered-dynamic-inversion (FDI) control for unknown linear time-invariant systems that are multi-input multi-output and minimum phase with unknown-but-bounded relative degree. This FDI controller requires limited model information, specifically, knowledge of an upper bound on the relative degree and knowledge of the first nonzero Markov parameter. The FDI controller is a single-parameter high-parameter-stabilizing controller that is robust to uncertainty in the relative degree. We characterize the stability of the closed-loop system. We present numerical examples, where the FDI controller is implemented in feedback with mathematical and physical systems. The numerical examples demonstrate that the FDI controller for unknown relative degree …
Biogeomorphology Of Bedrock Fluvial Systems: Example From Shawnee Run, Kentucky, Usa, Tasnuba Jerin
Biogeomorphology Of Bedrock Fluvial Systems: Example From Shawnee Run, Kentucky, Usa, Tasnuba Jerin
Theses and Dissertations--Geography
The dynamic interactions between fluvial processes and vegetation vary in different environments and are uncertain in bedrock settings. Bedrock streams are much less studied than alluvial in all aspects, and in many respects act in qualitatively different ways. This research seeks to fill this lacuna by studying bedrock streams from a biogeomorphic perspective. The first part of this research aims to identify the impacts of woody vegetation that may be common to fluvial systems and rocky hillslopes in general, or that may be unique to bedrock channels. A review of the existing literature on biogeomorphology — mostly fluvial and rocky …
Carbon Oxidation At The Atomic Level: A Computational Study On Oxidative Graphene Etching And Pitting Of Graphitic Carbon Surfaces, Simon Schmitt
Carbon Oxidation At The Atomic Level: A Computational Study On Oxidative Graphene Etching And Pitting Of Graphitic Carbon Surfaces, Simon Schmitt
Theses and Dissertations--Mechanical Engineering
In order to understand the oxidation of solid carbon materials by oxygen-containing gases, carbon oxidation has to be studied on the atomic level where the surface reactions occur. Graphene and graphite are etched by oxygen to form characteristic pits that are scattered across the material surface, and pitting in turn leads to microstructural changes that determine the macroscopic oxidation behavior. While this is a well-documented phenomenon, it is heretofore poorly understood due to the notorious difficulty of experiments and a lack of comprehensive computational studies. The main objective of the present work is the development of a computational framework from …
Quantifying Nitrogen Fate In Karst Agroecosystem Streams Of Central Kentucky: Development And Application Of Numerical Modeling And Insight From High-Resolution Sensors, Nolan Lewis Bunnell
Quantifying Nitrogen Fate In Karst Agroecosystem Streams Of Central Kentucky: Development And Application Of Numerical Modeling And Insight From High-Resolution Sensors, Nolan Lewis Bunnell
Theses and Dissertations--Biosystems and Agricultural Engineering
In-stream fate of nutrients in karst agroecosystems remains poorly understood, despite the known impact of karst on water resources at local to global scales. In the Inner-Bluegrass region of central Kentucky, heterogeneity of karst maturity, flow pathways, and nutrient sources adds to the complexity of quantifying nutrient dynamics, thus requiring novel monitoring and modeling approaches. The significance of these streams is recognized given spring/surface water confluences have been identified as hotspots for biogeochemical transformations. In slow-moving streams high in dissolved inorganic nutrients (particularly dissolved inorganic nitrogen (DIN) and dissolved reactive phosphorus (DRP)), benthic and floating aquatic macrophytes are recognized to …
Threshold Ionization Spectroscopy And Spin-Orbit Coupling Of Lanthanide Complexes, Yuchen Zhang
Threshold Ionization Spectroscopy And Spin-Orbit Coupling Of Lanthanide Complexes, Yuchen Zhang
Theses and Dissertations--Chemistry
The C-C and C-H bonds have high bond strength and low polarization, which make many small hydrocarbons too inert to react with other molecules under ambient pressure and temperature conditions. Therefore, activation of these bonds is required to convert such small molecules into other value-added chemicals. Among various bond activation methods, metal activation is widely used and reported in the literature, because of its relatively mild reaction conditions and high selectivity.
In this work, Ce atom reactions with several small hydrocarbons are carried out in a pulsed laser vaporization supersonic molecular beam source, and Ce -hydrocarbon species are observed with …
Uncovering Structure-Property Relationships Of Inorganic Nanomaterials Via Transmission Electron Microscopy, Melonie Thomas
Uncovering Structure-Property Relationships Of Inorganic Nanomaterials Via Transmission Electron Microscopy, Melonie Thomas
Theses and Dissertations--Chemistry
The rapid increase of research in nanoscale devices and nanotechnology in the past few decades has revealed that nanomaterials may possess exceptional properties that are significantly different from the bulk counterpart, due to local rearrangements of the atoms at surfaces and defects. Transmission electron microscopy (TEM) is an indispensable tool when it comes to the characterization of nanomaterials, primarily due to its ability to resolve the local-structure of materials at the atomic-scale. To study dynamic processes, however, regular TEM experiments are inadequate, as they provide only before and after information rather than the real-time data essential to understanding a reaction …
Deconvolution Tools For Extracting Insight From Challenging Two-Flavin Systems, Dallas Michael Bell
Deconvolution Tools For Extracting Insight From Challenging Two-Flavin Systems, Dallas Michael Bell
Theses and Dissertations--Chemistry
Flavoproteins have long been explored for their ubiquity among a number of metabolic and energetic reactions. The flavin cofactor has the inherent benefit of distinct spectral changes associated with redox transitions; however, the double-edged sword is incurred as these distinct signatures overlap and take up much of the UV-vis spectral range. Therefore, it is crucial to create a method to demarcate the expressed redox transitions for studying these systems. The first portion of these studies discusses the creation of a program that deduces spectra for redox transitions in a single-flavin containing model protein: flavodoxin. The latter portions discuss the application …
Flavodoxin, The Hydrogen Atom Of Flavoproteins: A 19f Nmr Study Of Dynamics And Conformational Changes Utilizing Flavodoxin From Rhodopseudomonas Palustris, Taylor Varner
Theses and Dissertations--Chemistry
Flavodoxin is a small, highly stable protein that contain a single FMN cofactor used to transfer single electrons at low potentials. The organism Rhodopseudomonas palustris contains a long-chain flavodoxin. Long-chain flavodoxins are characterized by a 20 amino acid loop that is proposed to allow interactions with partner proteins. We plan to utilize this protein as a model to build our repertoire with protein fluorination and fluorine NMR in flavoproteins. This tool kit will then be applied to the study of a partner protein of interest that is capable of performing electron bifurcation. We have incorporated m-fluoro tyrosine into flavodoxin and …