Nanofabrication for On-Chip Optical Levitation, Atom-Trapping, and Superconducting Quantum Circuits

Researchers have spent decades refining and improving their methods for fabricating smaller, finer-tuned, higher-quality nanoscale optical elements with the goal of making more sensitive and accurate measurements of the world around them using optics. Quantum optics has been a well-established tool of choice in making these increasingly sensitive measurements which have repeatedly pushed the limits on the accuracy of measurement set forth by quantum mechanics. A recent development in quantum optics has been a creative integration of robust, high-quality, and well-established macroscopic experimental systems with highly-engineerable on-chip nanoscale oscillators fabricated in cleanrooms. However, merging large systems with nanoscale oscillators often require them to have extremely high aspect-ratios, which make them extremely delicate and difficult to fabricate with an "experimentally reasonable" repeatability, yield and high quality. In this work we give an overview of our research, which focused on microscopic oscillators which are coupled with macroscopic optical cavities towards the goal of cooling them to their motional ground state in room temperature environments. The quality factor of a mechanical resonator is an important figure of merit for various sensing applications and observing quantum behavior. We demonstrated a technique for pushing the quality factor of a micromechanical resonator beyond conventional material and fabrication limits by using an optical field to stiffen and trap a particular motional mode of a nanoscale oscillator. Optical forces increase the oscillation frequency by storing most of the mechanical energy in a nearly loss-less optical potential, thereby strongly diluting the effects of material dissipation. By placing a 130 nm thick SiO₂ pendulum in an optical standing wave, we achieve an increase in the pendulum center-of-mass frequency from 6.2 to 145 kHz. The corresponding quality factor increases 50-fold from its intrinsic value to a final value of Q_m = 5.8(1.1) x 10⁵, representing more than an order of magnitude improvement over the conventional limits of SiO₂ for a pendulum geometry. Our technique may enable new opportunities for mechanical sensing and facilitate observations of quantum behavior in this class of mechanical systems. We then give a detailed overview of the techniques used to produce high-aspect-ratio nanostructures with applications in a wide range of quantum optics experiments. The ability to fabricate such nanodevices with high precision opens the door to a vast array of experiments which integrate macroscopic optical setups with lithographically engineered nanodevices. Coupled with atom-trapping experiments in the Kimble Lab, we use these techniques to realize a new waveguide chip designed to address ultra-cold atoms along lithographically patterned nanobeams which have large atom-photon coupling and near 4π Steradian optical access for cooling and trapping atoms. We describe a fully integrated and scalable design where cold atoms are spatially overlapped with the nanostring cavities in order to observe a resonant optical depth of d₀ ≈ 0.15. The nanodevice illuminates new possibilities for integrating atoms into photonic circuits and engineering quantum states of atoms and light on a microscopic scale. We then describe our work with superconducting microwave resonators coupled to a phononic cavity towards the goal of building an integrated device for quantum-limited microwave-to-optical wavelength conversion. We give an overview of our characterizations of several types of substrates for fabricating a low-loss high-frequency electromechanical system. We describe our electromechanical system fabricated on a Si₃N₄ membrane which consists of a 12 GHz superconducting LC resonator coupled capacitively to the high frequency localized modes of a phononic nanobeam. Using our suspended membrane geometry we isolate our system from substrates with significant loss tangents, drastically reducing the parasitic capacitance of our superconducting circuit to ≈ 2.5$ fF. This opens up a number of possibilities in making a new class of low-loss high-frequency electromechanics with relatively large electromechanical coupling. We present our substrate studies, fabrication methods, and device characterization.

1. Ultrasonic studies of binary liquid structure in the critical region. Theory and experiment for the 2,6-lutidine/water system. 2. Hartree-Fock calculations of electric polarizabilities of some simple atoms and molecules, and their practicality. 3. Calculation of vibrational transition probabilities in collinear atom-diatom and diatom-diatom collisions with Lennard-Jones interaction

Part 1. Many interesting visual and mechanical phenomena occur in the critical region of fluids, both for the gas-liquid and liquid-liquid transitions. The precise thermodynamic and transport behavior here has some broad consequences for the molecular theory of liquids. Previous studies in this laboratory on a liquid-liquid critical mixture via ultrasonics supported a basically classical analysis of fluid behavior by M. Fixman (e. g., the free energy is assumed analytic in intensive variables in the thermodynamics)--at least when the fluid is not too close to critical. A breakdown in classical concepts is evidenced close to critical, in some well-defined ways. We have studied herein a liquid-liquid critical system of complementary nature (possessing a lower critical mixing or consolute temperature) to all previous mixtures, to look for new qualitative critical behavior. We did not find such new behavior in the ultrasonic absorption ascribable to the critical fluctuations, but we did find extra absorption due to chemical processes (yet these are related to the mixing behavior generating the lower consolute point). We rederived, corrected, and extended Fixman's analysis to interpret our experimental results in these more complex circumstances. The entire account of theory and experiment is prefaced by an extensive introduction recounting the general status of liquid state theory. The introduction provides a context for our present work, and also points out problems deserving attention. Interest in these problems was stimulated by this work but also by work in Part 3.

Part 2. Among variational theories of electronic structure, the Hartree-Fock theory has proved particularly valuable for a practical understanding of such properties as chemical binding, electric multipole moments, and X-ray scattering intensity. It also provides the most tractable method of calculating first-order properties under external or internal one-electron perturbations, either developed explicitly in orders of perturbation theory or in the fully self-consistent method. The accuracy and consistency of first-order properties are poorer than those of zero-order properties, but this is most often due to the use of explicit approximations in solving the perturbed equations, or to inadequacy of the variational basis in size or composition. We have calculated the electric polarizabilities of H₂, He, Li, Be, LiH, and N₂ by Hartree-Fock theory, using exact perturbation theory or the fully self-consistent method, as dictated by convenience. By careful studies on total basis set composition, we obtained good approximations to limiting Hartree-Fock values of polarizabilities with bases of reasonable size. The values for all species, and for each direction in the molecular cases, are within 8% of experiment, or of best theoretical values in the absence of the former. Our results support the use of unadorned Hartree-Pock theory for static polarizabilities needed in interpreting electron-molecule scattering data, collision-induced light scattering experiments, and other phenomena involving experimentally inaccessible polarizabilities.

Part 3. Numerical integration of the close-coupled scattering equations has been carried out to obtain vibrational transition probabilities for some models of the electronically adiabatic H₂-H₂ collision. All the models use a Lennard-Jones interaction potential between nearest atoms in the collision partners. We have analyzed the results for some insight into the vibrational excitation process in its dependence on the energy of collision, the nature of the vibrational binding potential, and other factors. We conclude also that replacement of earlier, simpler models of the interaction potential by the Lennard-Jones form adds very little realism for all the complication it introduces. A brief introduction precedes the presentation of our work and places it in the context of attempts to understand the collisional activation process in chemical reactions as well as some other chemical dynamics.

The biological sense of smell: olfactory search behavior and a metabolic view for olfactory perception

Part I of the thesis describes the olfactory searching and scanning behaviors of rats in a wind tunnel, and a detailed movement analysis of terrestrial arthropod olfactory scanning behavior. Olfactory scanning behaviors in rats may be a behavioral correlate to hippocampal place cell activity.

Part II focuses on the organization of olfactory perception, what it suggests about a natural order for chemicals in the environment, and what this in tum suggests about the organization of the olfactory system. A model of odor quality space (analogous to the "color wheel") is presented. This model defines relationships between odor qualities perceived by human subjects based on a quantitative similarity measure. Compounds containing Carbon, Nitrogen, or Sulfur elicit odors that are contiguous in this odor representation, which thus allows one to predict the broad class of odor qualities a compound is likely to elicit. Based on these findings, a natural organization for olfactory stimuli is hypothesized: the order provided by the metabolic process. This hypothesis is tested by comparing compounds that are structurally similar, perceptually similar, and metabolically similar in a psychophysical cross-adaptation paradigm. Metabolically similar compounds consistently evoked shifts in odor quality and intensity under cross-adaptation, while compounds that were structurally similar or perceptually similar did not. This suggests that the olfactory system may process metabolically similar compounds using the same neural pathways, and that metabolic similarity may be the fundamental metric about which olfactory processing is organized. In other words, the olfactory system may be organized around a biological basis.

The idea of a biological basis for olfactory perception represents a shift in how olfaction is understood. The biological view has predictive power while the current chemical view does not, and the biological view provides explanations for some of the most basic questions in olfaction, that are unanswered in the chemical view. Existing data do not disprove a biological view, and are consistent with basic hypotheses that arise from this viewpoint.

The strategic behavior of rational novices

There is a growing amount of experimental evidence that suggests people often deviate from the predictions of game theory. Some scholars attempt to explain the observations by introducing errors into behavioral models. However, most of these modifications are situation dependent and do not generalize. A new theory, called the rational novice model, is introduced as an attempt to provide a general theory that takes account of erroneous behavior. The rational novice model is based on two central principals. The first is that people systematically make inaccurate guesses when they are evaluating their options in a game-like situation. The second is that people treat their decisions similar to a portfolio problem. As a result, non optimal actions in a game theoretic sense may be included in the rational novice strategy profile with positive weights.

The rational novice model can be divided into two parts: the behavioral model and the equilibrium concept. In a theoretical chapter, the mathematics of the behavioral model and the equilibrium concept are introduced. The existence of the equilibrium is established. In addition, the Nash equilibrium is shown to be a special case of the rational novice equilibrium. In another chapter, the rational novice model is applied to a voluntary contribution game. Numerical methods were used to obtain the solution. The model is estimated with data obtained from the Palfrey and Prisbrey experimental study of the voluntary contribution game. It is found that the rational novice model explains the data better than the Nash model. Although a formal statistical test was not used, pseudo R^2 analysis indicates that the rational novice model is better than a Probit model similar to the one used in the Palfrey and Prisbrey study.

The rational novice model is also applied to a first price sealed bid auction. Again, computing techniques were used to obtain a numerical solution. The data obtained from the Chen and Plott study were used to estimate the model. The rational novice model outperforms the CRRAM, the primary Nash model studied in the Chen and Plott study. However, the rational novice model is not the best amongst all models. A sophisticated rule-of-thumb, called the SOPAM, offers the best explanation of the data.

Phase behavior of complex superprotonic solid acids

Superprotonic phase transitions and thermal behaviors of three complex solid acid systems are presented, namely Rb3H(SO4)2-RbHSO4 system, Rb3H(SeO4)2-Cs3H(SeO4)2 solid solution system, and Cs6(H2SO4)3(H1.5PO4)4. These material systems present a rich set of phase transition characteristics that set them apart from other, simpler solid acids. A.C. impedance spectroscopy, high-temperature X-ray powder diffraction, and thermal analysis, as well as other characterization techniques, were employed to investigate the phase behavior of these systems.

Rb3H(SO4)2 is an atypical member of the M3H(XO4)2 class of compounds (M = alkali metal or NH4+ and X = S or Se) in that a transition to a high-conductivity state involves disproportionation into two phases rather than a simple polymorphic transition [1]. In the present work, investigations of the Rb3H(SO4)2-RbHSO4 system have revealed the disproportionation products to be Rb2SO4 and the previously unknown compound Rb5H3(SO4)4. The new compound becomes stable at a temperature between 25 and 140 °C and is isostructural to a recently reported trigonal phase with space group P3̅m of Cs5H3(SO4)4 [2]. At 185 °C the compound undergoes an apparently polymorphic transformation with a heat of transition of 23.8 kJ/mol and a slight additional increase in conductivity.

The compounds Rb3H(SeO4)2 and Cs3H(SeO4)2, though not isomorphous at ambient temperatures, are quintessential examples of superprotonic materials. Both adopt monoclinic structures at ambient temperatures and ultimately transform to a trigonal (R3̅m) superprotonic structure at slightly elevated temperatures, 178 and 183 °C, respectively. The compounds are completely miscible above the superprotonic transition and show extensive solubility below it. Beyond a careful determination of the phase boundaries, we find a remarkable 40-fold increase in the superprotonic conductivity in intermediate compositions rich in Rb as compared to either end-member.

The compound Cs6(H2SO4)3(H1.5PO4)4 is unusual amongst solid acid compounds in that it has a complex cubic structure at ambient temperature and apparently transforms to a simpler cubic structure of the CsCl-type (isostructural with CsH2PO4) at its transition temperature of 100-120 °C [3]. Here it is found that, depending on the level of humidification, the superprotonic transition of this material is superimposed with a decomposition reaction, which involves both exsolution of (liquid) acid and loss of H2O. This reaction can be suppressed by application of sufficiently high humidity, in which case Cs6(H2SO4)3(H1.5PO4)4 undergoes a true superprotonic transition. It is proposed that, under conditions of low humidity, the decomposition/dehydration reaction transforms the compound to Cs6(H2-0.5xSO4)3(H1.5PO4)4-x, also of the CsCl structure type at the temperatures of interest, but with a smaller unit cell. With increasing temperature, the decomposition/dehydration proceeds to greater and greater extent and unit cell of the solid phase decreases. This is identified to be the source of the apparent negative thermal expansion behavior.

References

[1] L.A. Cowan, R.M. Morcos, N. Hatada, A. Navrotsky, S.M. Haile, Solid State Ionics 179 (2008) (9-10) 305.

[2] M. Sakashita, H. Fujihisa, K.I. Suzuki, S. Hayashi, K. Honda, Solid State Ionics 178 (2007) (21-22) 1262.

[3] C.R.I. Chisholm, Superprotonic Phase Transitions in Solid Acids: Parameters affecting the presence and stability of superprotonic transitions in the MHnXO4 family of compounds (X=S, Se, P, As; M=Li, Na, K, NH4, Rb, Cs), Materials Science, California Institute of Technology, Pasadena, California (2003).

Using space geodesy to constrain variations in seismogenic behavior on subduction megathrusts

The concept of seismogenic asperities and aseismic barriers has become a useful paradigm within which to understand the seismogenic behavior of major faults. Since asperities and barriers can be thought of as defining the potential rupture area of large megathrust earthquakes, it is thus important to identify their respective spatial extents, constrain their temporal longevity, and to develop a physical understanding for their behavior. Space geodesy is making critical contributions to the identification of slip asperities and barriers but progress in many geographical regions depends on improving the accuracy and precision of the basic measurements. This thesis begins with technical developments aimed at improving satellite radar interferometric measurements of ground deformation whereby we introduce an empirical correction algorithm for unwanted effects due to interferometric path delays that are due to spatially and temporally variable radar wave propagation speeds in the atmosphere. In chapter 2, I combine geodetic datasets with complementary spatio-temporal resolutions to improve our understanding of the spatial distribution of crustal deformation sources and their associated temporal evolution – here we use observations from Long Valley Caldera (California) as our test bed. In the third chapter I apply the tools developed in the first two chapters to analyze postseismic deformation associated with the 2010 Mw=8.8 Maule (Chile) earthquake. The result delimits patches where afterslip occurs, explores their relationship to coseismic rupture, quantifies frictional properties associated with inferred patches of afterslip, and discusses the relationship of asperities and barriers to long-term topography. The final chapter investigates interseismic deformation of the eastern Makran subduction zone by using satellite radar interferometry only, and demonstrates that with state-of-art techniques it is possible to quantify tectonic signals with small amplitude and long wavelength. Portions of the eastern Makran for which we estimate low fault coupling correspond to areas where bathymetric features on the downgoing plate are presently subducting, whereas the region of the 1945 M=8.1 earthquake appears to be more highly coupled.

The short-timescale behavior of glacial ice

Glaciers are often assumed to deform only at slow (i.e., glacial) rates. However, with the advent of high rate geodetic observations of ice motion, many of the intricacies of glacial deformation on hourly and daily timescales have been observed and quantified. This thesis explores two such short timescale processes: the tidal perturbation of ice stream motion and the catastrophic drainage of supraglacial meltwater lakes. Our investigation into the transmission length-scale of a tidal load represents the first study to explore the daily tidal influence on ice stream motion using three-dimensional models. Our results demonstrate both that the implicit assumptions made in the standard two-dimensional flow-line models are inherently incorrect for many ice streams, and that the anomalously large spatial extent of the tidal influence seen on the motion of some glaciers cannot be explained, as previously thought, through the elastic or viscoelastic transmission of tidal loads through the bulk of the ice stream. We then discuss how the phase delay between a tidal forcing and the ice stream’s displacement response can be used to constrain in situ viscoelastic properties of glacial ice. Lastly, for the problem of supraglacial lake drainage, we present a methodology for implementing linear viscoelasticity into an existing model for lake drainage. Our work finds that viscoelasticity is a second-order effect when trying to model the deformation of ice in response to a meltwater lake draining to a glacier’s bed. The research in this thesis demonstrates that the first-order understanding of the short-timescale behavior of naturally occurring ice is incomplete, and works towards improving our fundamental understanding of ice behavior over the range of hours to days.

Coupled effects of mechanics, geometry, and chemistry on bio-membrane behavior

Lipid bilayer membranes are models for cell membranes--the structure that helps regulate cell function. Cell membranes are heterogeneous, and the coupling between composition and shape gives rise to complex behaviors that are important to regulation. This thesis seeks to systematically build and analyze complete models to understand the behavior of multi-component membranes.

We propose a model and use it to derive the equilibrium and stability conditions for a general class of closed multi-component biological membranes. Our analysis shows that the critical modes of these membranes have high frequencies, unlike single-component vesicles, and their stability depends on system size, unlike in systems undergoing spinodal decomposition in flat space. An important implication is that small perturbations may nucleate localized but very large deformations. We compare these results with experimental observations.

We also study open membranes to gain insight into long tubular membranes that arise for example in nerve cells. We derive a complete system of equations for open membranes by using the principle of virtual work. Our linear stability analysis predicts that the tubular membranes tend to have coiling shapes if the tension is small, cylindrical shapes if the tension is moderate, and beading shapes if the tension is large. This is consistent with experimental observations reported in the literature in nerve fibers. Further, we provide numerical solutions to the fully nonlinear equilibrium equations in some problems, and show that the observed mode shapes are consistent with those suggested by linear stability. Our work also proves that beadings of nerve fibers can appear purely as a mechanical response of the membrane.

Characterization of diverse megathrust fault behavior related to seismic supercycles, Mentawai Islands, Sumatra

Long paleoseismic histories are necessary for understanding the full range of behavior of faults, as the most destructive events often have recurrence intervals longer than local recorded history. The Sunda megathrust, the interface along which the Australian plate subducts beneath Southeast Asia, provides an ideal natural laboratory for determining a detailed paleoseismic history over many seismic cycles. The outer-arc islands above the seismogenic portion of the megathrust cyclically rise and subside in response to processes on the underlying megathrust, providing uncommonly good illumination of megathrust behavior. Furthermore, the growth histories of coral microatolls, which record tectonic uplift and subsidence via relative sea level, can be used to investigate the detailed coseismic and interseismic deformation patterns. One particularly interesting area is the Mentawai segment of the megathrust, which has been shown to characteristically fail in a series of ruptures over decades, rather than a single end-to-end rupture. This behavior has been termed a seismic “supercycle.” Prior to the current rupture sequence, which began in 2007, the segment previously ruptured during the 14th century, the late 16th to late 17th century, and most recently during historical earthquakes in 1797 and 1833. In this study, we examine each of these previous supercycles in turn.

First, we expand upon previous analysis of the 1797–1833 rupture sequence with a comprehensive review of previously published coral microatoll data and the addition of a significant amount of new data. We present detailed maps of coseismic uplift during the two great earthquakes and of interseismic deformation during the periods 1755–1833 and 1950–1997 and models of the corresponding slip and coupling on the underlying megathrust. We derive magnitudes of Mw 8.7–9.0 for the two historical earthquakes, and determine that the 1797 earthquake fundamentally changed the state of coupling on the fault for decades afterward. We conclude that while major earthquakes generally do not involve rupture of the entire Mentawai segment, they undoubtedly influence the progression of subsequent ruptures, even beyond their own rupture area. This concept is of vital importance for monitoring and forecasting the progression of the modern rupture sequence.

Turning our attention to the 14th century, we present evidence of a shallow slip event in approximately A.D. 1314, which preceded the “conventional” megathrust rupture sequence. We calculate a suite of slip models, slightly deeper and/or larger than the 2010 Pagai Islands earthquake, that are consistent with the large amount of subsidence recorded at our study site. Sea-level records from older coral microatolls suggest that these events occur at least once every millennium, but likely far less frequently than their great downdip neighbors. The revelation that shallow slip events are important contributors to the seismic cycle of the Mentawai segment further complicates our understanding of this subduction megathrust and our assessment of the region’s exposure to seismic and tsunami hazards.

Finally, we present an outline of the complex intervening rupture sequence that took place in the 16th and 17th centuries, which involved at least five distinct uplift events. We conclude that each of the supercycles had unique features, and all of the types of fault behavior we observe are consistent with highly heterogeneous frictional properties of the megathrust beneath the south-central Mentawai Islands. We conclude that the heterogeneous distribution of asperities produces terminations and overlap zones between fault ruptures, resulting in the seismic “supercycle” phenomenon.

Complex behavior and perception in Drosophila emerges from iterative feedback-regulated reflexes

For a hungry fruit fly, locating and landing on a fermenting fruit where it can feed, find mates, and lay eggs, is an essential and difficult task requiring the integration of both olfactory and visual cues. Understanding how flies accomplish this will help provide a comprehensive ethological context for the expanding knowledge of their neural circuits involved in processing olfaction and vision, as well as inspire novel engineering solutions for control and estimation in computationally limited robotic applications. In this thesis, I use novel high throughput methods to develop a detailed overview of how flies track odor plumes, land, and regulate flight speed. Finally, I provide an example of how these insights can be applied to robotic applications to simplify complicated estimation problems. To localize an odor source, flies exhibit three iterative, reflex-driven behaviors. Upon encountering an attractive plume, flies increase their flight speed and turn upwind using visual cues. After losing the plume, flies begin zigzagging crosswind, again using visual cues to control their heading. After sensing an attractive odor, flies become more attracted to small visual features, which increases their chances of finding the plume source. Their changes in heading are largely controlled by open-loop maneuvers called saccades, which they direct towards and away from visual features. If a fly decides to land on an object, it begins to decelerate so as to maintain a stereotypical ratio of expansion to retinal size. Once they reach a stereotypical distance from the target, flies extend their legs in preparation for touchdown. Although it is unclear what cues they use to trigger this behavior, previous studies have indicated that it is likely under visual control. In Chapter 3, I use a nonlinear control theoretic analysis and robotic testbed to propose a novel and putative mechanism for how a fly might visually estimate distance by actively decelerating according to a visual control law. Throughout these behaviors, a common theme is the visual control of flight speed. Using genetic tools I show that the neuromodulator octopamine plays an important role in regulating flight speed, and propose a neural circuit for how this controller might be implemented in the flies brain. Two general biological and engineering principles are evident across my experiments: (1) complex behaviors, such as foraging, can emerge from the interactions of simple independent sensory-motor modules; (2) flies control their behavior in such a way that simplifies complex estimation problems.

Modeling and analysis of hysteretic structural behavior

For damaging response, the force-displacement relationship of a structure is highly nonlinear and history-dependent. For satisfactory analysis of such behavior, it is important to be able to characterize and to model the phenomenon of hysteresis accurately. A number of models have been proposed for response studies of hysteretic structures, some of which are examined in detail in this thesis. There are two popular classes of models used in the analysis of curvilinear hysteretic systems. The first is of the distributed element or assemblage type, which models the physical behavior of the system by using well-known building blocks. The second class of models is of the differential equation type, which is based on the introduction of an extra variable to describe the history dependence of the system.

Owing to their mathematical simplicity, the latter models have been used extensively for various applications in structural dynamics, most notably in the estimation of the response statistics of hysteretic systems subjected to stochastic excitation. But the fundamental characteristics of these models are still not clearly understood. A response analysis of systems using both the Distributed Element model and the differential equation model when subjected to a variety of quasi-static and dynamic loading conditions leads to the following conclusion: Caution must be exercised when employing the models belonging to the second class in structural response studies as they can produce misleading results.

The Massing's hypothesis, originally proposed for steady-state loading, can be extended to general transient loading as well, leading to considerable simplification in the analysis of the Distributed Element models. A simple, nonparametric identification technique is also outlined, by means of which an optimal model representation involving one additional state variable is determined for hysteretic systems.

On the behavior of pliable plate dynamics in wind : application to vertical axis wind turbines

Numerous studies have shown that flexible materials improve resilience and durability of a structure. Several studies have investigated the behavior of elastic plates under the influence of a free stream, such as studies of the fluttering flag and others of shape reconfiguration, due to a free stream.

The principle engineering contribution of this thesis is the design and development of a vertical axis wind turbine that features pliable blades which undergo various modes of behavior, ultimately leading to rotational propulsion of the turbine. The wind turbine design was tested in a wind tunnel and at the Caltech Laboratory for Optimized Wind Energy. Ultimately, the flexible blade vertical axis wind turbine proved to be an effective way of harnessing the power of the wind.

In addition, this body of work builds on the current knowledge of elastic cantilever plates in a free stream flow by investigating the inverted flag. While previous studies have focused on the fluid structure interaction of a free stream on elastic cantilever plates, none had studied the plate configuration where the trailing edge was clamped, leaving the leading edge free to move. Furthermore, the studies presented in this thesis establish the geometric boundaries of where the large-amplitude flapping occurs.

Electrocatalytic activity of transition metal substituted heteropolytungstates

The electrochemical and electrocatalytic behavior of a series of heteropolytungstate anions in which a tungsten atom in the well known Keggin structure has been replaced by an iron atom is described. All of the iron substituted ions exhibit a one electron reversible couple associated with the Fe³⁺ center and a pair of two electron waves attributed to electron addition and removal from the tungsten oxo framework. The pH and ionic strength effects upon the various electrochemical processes are discussed and interpreted in terms of a competition between protonation and ion pairing of the highly negatively charged ions.

The anions are efficient catalysts for the electroreduction of hydrogen peroxide. A catalytic mechanism involving a formally Fe(IV) intermediate is proposed. Pulse radiolysis experiments were employed to detect the intermediate and evaluate the rate constants for the reactions in which it is formed and decomposed. A chain mechanism for the catalytic decomposition of hydrogen peroxide in which the Fe center shuttles between the +2, +3, and +4 oxidation states is proposed to explain the non-integral stoichiometry observed for the iron substituted polytungstate catalyzed electroreduction of hydrogen peroxide.

The anions are also efficient electrocatalyst for the electrochemical conversion of nitric oxide to ammonia. The catalyzed reduction does not produce hydroxylamine as an intermediate and appears to depend upon the ability of the multiply reduced heteropolytungstates to deliver several electrons to the bound NO group in a concerted step. A valuable feature of the heteropolytungstates is the ease at which the formal potentials of the several redox couples they exhibit may be shifted by changing the identity of the central heteroatom. Exploitation of this feature provided diagnostic information that was decisive in establishing the mechanism of electrocatalytic reduction.

The iron substituted heteropolytungstates are not degraded by repeated cycling between their oxidized and reduced states. They also show superior activity compared to their unsubstituted analogues, indicating that the Fe center acts as a binding site that facilitates inner-sphere electron transfer processes. The basic electrochemistry of several other transition metal substituted Keggin ions is also described.

Hydrogen-Atom Transfer Photochemistry of Tetrakis(µ-pyrophosphito)diplatinate(II)

In many senses, the hydrogen-atom transfer reactions observed with the triplet excited state of pyrophosphito-bridged platinum(II) dimers resemble the reactions of organic ketone nπ* states. The first two chapters describe our attempts to understand the reactivity differences between these two chromophores. Reactivity of the metal dimers is strongly regulated by the detailed nature of the ligands that ring the axial site, the hydrogen-abstraction center. A hydrogen-bonded network linking the ligands facilitates H-atom transfer quenching with alcohols through the formation of a hydrogen-bonded complex between the alcohol and a dimer. For substrates of equal C-H bond strength that lack a hydroxyl group (e.g., benzyl hydrocarbons), the quenching rate is several orders of magnitude slower.

The shape and size of the axial site, as determined by the ligands, also discriminate among quenchers by their steric characteristics. Very small quenchers quench slowly because of high entropies of activation, while very large ones have large enthalpic barriers. The two effects find a balance with quenchers of "just the right size."

The third chapter discusses the design of a mass spectrometer that uses positron annihilation to ionize neutral molecules. The mass spectrometer creates positron-molecule adducts whose annihilation produces fragmentation products that may yield information on the bonding of positrons in such complexes.

Hall coefficient and resistivity of an amorphous palladium-silicon alloy

The Hall coefficient and resistance in several specimens of an amorphous metallic alloy containing 80 at.% palladium and 20 at.% silicon have been investigated at temperatures between 4.2°K and room temperature. An ideal limiting behavior of these transport coefficients was analyzed on the basis of the nearly free electron model to yield a carrier density of 9 x 10²² cm.^-3, or about 1.7 electrons per palladium atom, and a mean free path of about 9Å which is almost constant with temperature. The deviations of the individual specimens from this ideal behavior, which were small but noticeable in the relative resistivity and much greater in the Hall coefficient, can be explained by invoking disk-shaped crystalline regions with low resistivity and a positive Hall coefficient. A detailed calculation shows how a volume fraction of such crystalline material too small to be noticed in X-ray diffraction could have a significant effect on the resistivity and a much greater effect on the Hall coefficient.