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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

The influence of association and substitution on the infrared absorption spectrum of acetic acid

Gillette, Roger Henry, January 1936 (has links)
Thesis (Ph. D.)--University of Wisconsin--Madison, 1936. / Typescript. Includes abstract and vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references.
2

Electric Field Modulation of Near Infrared Absorption at Room Temperature in Electrochemically Self Assembled Quantum Dots

Wang, Yanbin 01 January 2006 (has links)
This thesis is an investigation of infrared electro-absorption at room temperature in electrochemically self assembled Cadmium Sulfide quantum dots produced by electrodepositing the semiconductor in 50nm pores of an anodic alumina film. Infrared absorption in these systems is associated with real space transitions of electrons between electronic states in the Cadmium Sulfide quantum dots and trap states in the surrounding alumina. When an electric field is applied on a quantum dot, it modulates the absorption by altering the overlap between the wavefunctions of dot states and the trap states in the alumina. This results in a change in the matrix element for absorption. Such a phenomenon is reminiscent of the quantum confined Stark effect. The ability to electrically modulate absorption in these structures can result in inexpensive infrared signal processing devices operating at room temperature.
3

Far-Infrared Absorption in Insb

Koteles, Emil Steve 03 1900 (has links)
<p> A high-resolution, low-noise far-infrared Fourier transform spectrometer system has been developed and utilized to study optical absorption in the III-V compound semiconductor InSb.</p> <p> Its electron effective mass was investigated, using cyclotron resonance absorption, as a function of magnetic field and compared with a theory originated by Kane (1957). The agreement was good and accurate values of the band edge effective mass and effective g factors were determined. Resonant electron-LO phonon coupling between the n = 2 and n = 0 + wLO Landau levels was observed and the polaron effective mass enhancement measured as a function of magnetic field. Comparison with Larsen's theory (1966), permitted an accurate value of the coupling constant to be derived. The temperature dependence of the electron effective mass was shown to be primarily due to dilation of the crystal lattice in confirmation of other workers' suggestions. However, some discrepancy, whose origin is unknown, was found to exist between experiment and theory.</p> <p> Single phonon absorption by the longitudinal optic phonon mode at the zone center was observed on the side of the main Reststrahl band in a thin sample. The shapes, frequencies and intensities of far-infrared absorptions attributable to two-phonon processes were found to compare favourably with a theoretical two-phonon density of states curve calculated by G. Dolling (1972). The parameters used in the theory were derived from inelastic neutron scattering experiments. Two phonon combinations and their locations in the Brillouin zone which give rise to strong features in the two-phonon density of states were identified by comparing theory and experiment. Important critical points were discovered to be located on or near the zone boundary and not only at the symmetry points X and L as previously suggested. The frequency shifts of some two-phonon features were measured as a function of temperature and analyzed in terms of a quasi-harmonic lattice dilation component and an anharmonic component. The two terms were found to be mirror images as a function of temperature.</p> / Thesis / Doctor of Philosophy (PhD)
4

Impurity Induced Far-Infrared Absorption in KBr and KCl

Ward, Roger William 10 1900 (has links)
<p> High resolution measurements of the far-infrared absorption spectra due to a number of substitutional impurities in KBr and KCl are presented. Several Van Hove singularities of the phonon spectrum of the host lattice are directly observed and found to shift to higher frequencies as the impurity concentration is increased. The first direct experimental evidence for the change of shape or metamorphism of singularities is also presented. The experimental spectra are compared with numerical calculations based on the ordinary shell model for the defect together with phonon data obtained from inelastic neutron scattering experiments. Agreement between experiment and calculation is generally good when impurity resonant modes are absent.</p> / Thesis / Doctor of Philosophy (PhD)
5

Linear programming to determine molecular orientation at surfaces through vibrational spectroscopy

Chen, Fei 03 May 2017 (has links)
Applying linear programming (LP) to spectroscopy techniques, such as IR, Raman and SFG, is a new approach to extract the molecular orientation information at surfaces. In Hung’s previous research, he has shown how applying LP results in the computational gain from O(n!) to O(n). However, this LP approach does not always return the known molecular orientation distribution information when mock spectral information is used to build the instance of the model. The first goal of our study is to figure out the cause for the failed LP instances. After that, we also want to know for different cases with what spectral information, can the correct molecular orientation be expected when using LP. To achieve these goals, a simplified molecular model is designated to study the nature of our LP model. With the information gained, we further apply the LP approach to various test cases in order to verify whether it can be systematically applied to different circumstances. We have achieved the following conclusions: with the help of simplified molecular model, the inability to extract a sufficient data set from the given spectral information to build the LP instances is the reason that the LP solver does not return the target composition. When candidates coming from one same molecule, even combining all three spectral information of IR, Raman and SFG, the data set extracted is still not sufficient in order to obtain the target composition for most cases. When candidates are coming from different molecules, Raman or SFG spectral information alone contains sufficient data set to obtain the target composition when candidates of each molecule expanded in [0◦, 90◦) on θ. When candidates of each molecule expanded in [0◦, 180◦] on θ, excluding 90◦, SFG spectral information needs to combine with IR or Raman in order to obtain the sufficient data set to obtain the target composition. When the slack variable is introduced to each spectral technique, for the case of candidates coming from different molecules, when candidates expanded in [0◦, 90◦) on θ, Raman spectral information carries sufficient data set to obtain the target composition. When candidates expanded in [0◦, 180◦] on θ, excluding 90◦, SFG and Raman spectral information together carries sufficient data set in order to obtain the target composition. / Graduate / chenfei.cp@gmail.com
6

Sensor-based machine olfaction with neuromorphic models of the olfactory system

Raman, Baranidharan 25 April 2007 (has links)
Electronic noses combine an array of cross-selective gas sensors with a pattern recognition engine to identify odors. Pattern recognition of multivariate gas sensor response is usually performed using existing statistical and chemometric techniques. An alternative solution involves developing novel algorithms inspired by information processing in the biological olfactory system. The objective of this dissertation is to develop a neuromorphic architecture for pattern recognition for a chemosensor array inspired by key signal processing mechanisms in the olfactory system. Our approach can be summarized as follows. First, a high-dimensional odor signal is generated from a chemical sensor array. Three approaches have been proposed to generate this combinatorial and high dimensional odor signal: temperature-modulation of a metal-oxide chemoresistor, a large population of optical microbead sensors, and infrared spectroscopy. The resulting high-dimensional odor signals are subject to dimensionality reduction using a self-organizing model of chemotopic convergence. This convergence transforms the initial combinatorial high-dimensional code into an organized spatial pattern (i.e., an odor image), which decouples odor identity from intensity. Two lateral inhibitory circuits subsequently process the highly overlapping odor images obtained after convergence. The first shunting lateral inhibition circuits perform gain control enabling identification of the odorant across a wide range of concentration. This shunting lateral inhibition is followed by an additive lateral inhibition circuit with center-surround connections. These circuits improve contrast between odor images leading to more sparse and orthogonal patterns than the one available at the input. The sharpened odor image is stored in a neurodynamic model of a cortex. Finally, anti-Hebbian/ Hebbian inhibitory feedback from the cortical circuits to the contrast enhancement circuits performs mixture segmentation and weaker odor/background suppression, respectively. We validate the models using experimental datasets and show our results are consistent with recent neurobiological findings.
7

Sensor-based machine olfaction with neuromorphic models of the olfactory system

Raman, Baranidharan 25 April 2007 (has links)
Electronic noses combine an array of cross-selective gas sensors with a pattern recognition engine to identify odors. Pattern recognition of multivariate gas sensor response is usually performed using existing statistical and chemometric techniques. An alternative solution involves developing novel algorithms inspired by information processing in the biological olfactory system. The objective of this dissertation is to develop a neuromorphic architecture for pattern recognition for a chemosensor array inspired by key signal processing mechanisms in the olfactory system. Our approach can be summarized as follows. First, a high-dimensional odor signal is generated from a chemical sensor array. Three approaches have been proposed to generate this combinatorial and high dimensional odor signal: temperature-modulation of a metal-oxide chemoresistor, a large population of optical microbead sensors, and infrared spectroscopy. The resulting high-dimensional odor signals are subject to dimensionality reduction using a self-organizing model of chemotopic convergence. This convergence transforms the initial combinatorial high-dimensional code into an organized spatial pattern (i.e., an odor image), which decouples odor identity from intensity. Two lateral inhibitory circuits subsequently process the highly overlapping odor images obtained after convergence. The first shunting lateral inhibition circuits perform gain control enabling identification of the odorant across a wide range of concentration. This shunting lateral inhibition is followed by an additive lateral inhibition circuit with center-surround connections. These circuits improve contrast between odor images leading to more sparse and orthogonal patterns than the one available at the input. The sharpened odor image is stored in a neurodynamic model of a cortex. Finally, anti-Hebbian/ Hebbian inhibitory feedback from the cortical circuits to the contrast enhancement circuits performs mixture segmentation and weaker odor/background suppression, respectively. We validate the models using experimental datasets and show our results are consistent with recent neurobiological findings.
8

Functionalization of polymer electrolytes for electrochromic windows

Bayrak Pehlivan, İlknur January 2013 (has links)
Saving energy in buildings is of great importance because about 30 to 40 % of the energy in the world is used in buildings. An electrochromic window (ECW), which makes it possible to regulate the inflow of visible light and solar energy into buildings, is a promising technology providing a reduction in energy consumption in buildings along with indoor comfort. A polymer electrolyte is positioned at the center of multi-layer structure of an ECW and plays a significant role in the working of the ECW. In this study, polyethyleneimine: lithium (bis(trifluoromethane)sulfonimide (PEI:LiTFSI)-based polymer electrolytes were characterized by using dielectric/impedance spectroscopy, differential scanning calorimetry, viscosity recording, optical spectroscopy, and electrochromic measurements. In the first part of the study, PEI:LiTFSI electrolytes were characterized at various salt concentrations and temperatures. Temperature dependence of viscosity and ionic conductivity of the electrolytes followed Arrhenius behavior. The viscosity was modeled by the Bingham plastic equation. Molar conductivity, glass transition temperature, viscosity, Walden product, and iso-viscosity conductivity analysis showed effects of segmental flexibility, ion pairs, and mobility on the conductivity. A connection between ionic conductivity and ion-pair relaxation was seen by means of (i) the Barton-Nakajima-Namikawa relation, (ii) activation energies of the bulk relaxation, and ionic conduction and (iii) comparing two equivalent circuit models, containing different types of Havriliak-Negami elements, for the bulk response. In the second part, nanocomposite PEI:LiTFSI electrolytes with SiO2, In2O3, and In2O3:Sn (ITO) were examined. Adding SiO2 to the PEI:LiTFSI enhanced the ionic conductivity by an order of magnitude without any degradation of the optical properties. The effect of segmental flexibility and free ion concentration on the conduction in the presence of SiO2 is discussed. The PEI:LiTFSI:ITO electrolytes had high haze-free luminous transmittance and strong near-infrared absorption without diminished ionic conductivity. Ionic conductivity and optical clarity did not deteriorate for the PEI:LiTFSI:In2O3 and the PEI:LiTFSI:SiO2:ITO electrolytes. Finally, propylene carbonate (PC) and ethylene carbonate (EC) were added to PEI:LiTFSI in order to perform electrochromic measurements. ITO and SiO2 were added to the PEI:LiTFSI:PC:EC and to a proprietary electrolyte. The nanocomposite electrolytes were tested for ECWs with the configuration of the ECWs being plastic/ITO/WO3/polymer electrolyte/NiO (or IrO2)/ITO/plastic. It was seen that adding nanoparticles to polymer electrolytes can improve the coloring/bleaching dynamics of the ECWs. From this study, we show that nanocomposite polymer electrolytes can add new functionalities as well as enhancement in ECW applications.
9

Hydrothermal synthesis methods to influence active site and crystallite properties of zeolites and consequences for catalytic alkane activation

Philip Morgan Kester (8604438) 16 April 2020 (has links)
Zeolites are crystalline microporous solid acids composed of silica-rich frameworks with aliovalent Al heteroatoms substituted in crystallographically-distinct location sand arrangements, which generate anionic lattice charges that can be compensated by protons and extra framework metal cations or complexes that behave as catalytic active sites. Protons that charge-compensate Al are similar in Brønsted acid strength, yet differ in reactivity because their bound intermediates and transition states are stabilized by van der Waals interactions with confining microporous cavities, and by electrostatic interactions with proximal heteroatoms and adjacent protons. A diverse array of framework Al and extra framework H<sup>+ </sup>site ensembles are ubiquitous in low-silica and low-symmetry zeolite frameworks (e.g., MFI, MOR), which cause measured turnover rates to reflect the reactivity-weighted average of contributions from each distinct site ensemble. The reactivity of distinct sites can be further masked by diffusion barriers often imparted by microporous domains and secondary reactions of primary products, which become increasingly prevalent as products encounter higher numbers of active sites during diffusion prior to egress from zeolite crystallites. Consequently,catalytic behavior often depends on zeolite material properties at orders-of-magnitude different length scales, which depend on the specific protocols used in their synthesis and crystallization.<div><br></div><div><div>In this work, CHA zeolites that contain only one symmetrically-distinct lattice site for Al substitution are used as model materials to decouple the effects of proton</div><div>location and proximity in vibrational spectra and turnover rates for acid catalysis. Interactions between proximal protons influence their equilibrium distribution among anionic lattice O atoms in AlO<sup>−</sup><sub>4/2 </sub>tetrahedra, and result in temperature-dependent changes to vibrational frequencies and intensities of the asymmetric OH stretching region in infrared spectra measured experimentally and computed by density functional theory (DFT). Protolytic propane cracking and dehydrogenation, a catalytic probe reaction of the intrinsic reactivity of Brønsted acid protons, occur with turnover rates (748 K, per H<sup>+</sup>) that are an order-of-magnitude higher on paired protons than isolated protons, resulting from entropic benefits provided to late carbonium ion-pair transition states by proximal protons. These results indicate that cationic transition states can be stabilized entropically through multi-ion interactions with lattice anion and cation sites. Precise interpretation and quantification of the reactivity of different types and ensembles of Brønsted acid protons in zeolites requires that protolytic chemistry prevails in the absence of secondary active sites or other kinetically-relevant processes, a requirement generally met for alkane cracking but not dehydrogenation on H-form zeolites. Propane dehydrogenation activation energies vary widely (by >100 kJ mol<sup>−1</sup>) among H-form zeolites of different structure (MFI, MOR, CHA) and composition (Si/Al = 10 – 140) because reactant-derived carbonaceous deposits form in situ and catalyze alkane dehydrogenation under non-oxidative conditions through hydride transfer pathways. Contributions of reactant-derived active sites to propane dehydrogenation rates are quantified through a series of transient and steady-state kinetic experiments with co-fed alkene and dihydrogen products, and are found to depend on gradients in product pressures that are present in integral reactors under non-ideal plug-flow hydrodynamics. Propane dehydrogenation rates collected at initial time-on-stream and in the presence of co-fed H<sub>2</sub> solely reflect protolytic reaction events and can be used to interpret differences in the reactivity of distinct proton sites and ensembles for alkane activation catalysis. The reaction conditions identified here can be used to remove or suppress the reactivity of carbonaceous active sites during catalysis, or to engineer the formation of organocatalysts on zeolite surfaces for selective dehydrogenation or hydride transfer reactions.</div></div><div><br></div><div><div>Synthetic strategies to decouple bulk and active site properties at disparate length scales, which are typically correlated in MFI zeolites crystallized hydrothermally, are developed by adding a second heteroatom and organic structure directing agent (SDA) to synthesis media. Crystallite size and morphology are independently varied from Al content by incorporating B heteroatoms into zeolitic frameworks, which generate protons that are catalytically irrelevant compared to those compensating Al, and NH<sub>3</sub> temperature-programmed desorption methods are developed to differentiate between these two types of proton sites. The siting of Al heteroatoms in distinct locations and ensembles is influenced by the decrease in cationic charge density among occluded SDAs, in cases where ethylenediamine is co-occluded with tetra-<i>n</i>-propylammonium cations. The co-occlusion of organic SDAs enables crystallizing MFI zeolites with different bulk properties but similar Al distributions, or with similar bulk properties and different Al distributions. MFI zeolites crystallized with these methods provide model materials that can be interrogated to decouple the effects of bulk and atomicscale properties on acid catalysis, and open opportunities to exploit these material properties by designing active site ensembles and crystallite diffusion properties for catalytic chemistries that depend on coupled reaction-transport phenomena.</div></div>
10

Infrared Intersubband Transitions in Non-Polar III-Nitrides

Trang Nguyen (12091136) 27 April 2022 (has links)
<p>Infrared intersubband absorption of III-nitride materials has been studied rigorously due to its broad potential applications into optoelectronic devices. III-nitrides have advantages of large conduction band offset, large longitudinal-optical phonon energy, and fast intersubband relaxation time. These special characteristics make nitrides promising materials for intersubband devices in the near-infrared range. However, the existence of challenges from these materials delays the progress towards the realization of high performance nitride intersubband devices. In this document, we discuss the challenges of III-nitrides and our efforts towards high intersubband transitions strength of different nitrides, in particular non-polar m-plane AlGaN/GaN, non-polar m-plane near strain-balanced (In)AlGaN/InGaN, and polar lattice-matched InAlN/GaN. Samples are characterized by multiple methods including atomic force microscopy, high-resolution x-ray diffraction, high-resolution (scanning) transmission electron microscopy, and Fourier transform infrared spectroscopy.</p> <p>Polar c-plane AlGaN/GaN exhibits good agreement between experimental and predicted results for the intersubband transition energy. However, the lattice strain between layers caused by the lattice mismatch between materials leads to a large number of defects, affecting the vertical transport and resulting in low-quality devices. Lattice-matched InAlN/GaN was suggested as an alternative to eliminate this lattice strain, thus providing a better quality material for devices. We discuss the challenges of growing homogeneous InAlN alloys that persist after exploring a wide range of growth conditions. Additionally, the non-polar mplane AlGaN/GaN is also being investigated. Low Al-composition m-plane AlGaN/GaN experimental intersubband absorption shows good agreement with the theoretical results. As the Al composition exceeds 60%, however, the m-plane AlGaN alloy becomes kinetically unstable during plasma-assisted molecular beam epitaxy growth, resulting in unique nanostructures that affect the intersubband transition energy and linewidth. For the first time, we reported the ISBA energy of near strain-balanced non-polar m-plane (In)AlGaN/InGaN heterostructures in the mid-infrared range with narrow linewidths comparable to tdth-half-max published in the literature for non-polar m-plane AlGaN/GaN superlattices. Additionally, we propose polar near lattice-matched Sc0.15Al0.85N/GaN as an alternative to c-plane lattice-matched InAlN/GaN. </p>

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