Capturing protein dynamics with time-resolved luminescence spectroscopy

The presented doctoral research utilizes time-resolved spectroscopy to characterize protein dynamics and folding mechanisms. We resolve millisecond-timescale folding by coupling time-resolved fluorescence energy transfer (trFRET) to a continuous flow microfluidic mixer to obtain intramolecular distance distributions throughout the folding process. We have elucidated the folding mechanisms of two cytochromes---one that exhibits two-state folding (cytochrome cb₅₆₂) and one that has both a kinetic refolding intermediate ensemble and a distinct equilibrium unfolding intermediate (cytochrome c₅₅₂). Our data reveal that the distinct structural features of cytochrome c₅₅₂ contribute to its thermostability.

We have also investigated intrachain contact dynamics in unfolded cytochrome cb₅₆₂ by monitoring electron transfer, which occurs as the heme collides with a ruthenium photosensitizer, covalently bound to residues along the polypeptide. Intrachain diffusion for chemically denatured proteins proceeds on the microsecond timescale with an upper limit of 0.1 microseconds. The power-law dependence (slope = -1.5) of the rate constants on the number of peptide bonds between the heme and Ru complex indicate that cytochrome cb₅₆₂ is minimally frustrated.

In addition, we have explored the pathway dependence of electron tunneling rates between metal sites in proteins. Our research group has converted cytochrome b₅₆₂ to a c-type cytochrome with the porphyrin covalently bound to cysteine sidechains. We have investigated the effects of the changes to the protein structure (i.e., increased rigidity and potential new equatorial tunneling pathways) on the electron transfer rates, measured by transient absorption, in a series of ruthenium photosensitizer-modified proteins.

Nonlinear optics and wavelength translation via cavity-optomechanics

The field of cavity-optomechanics explores the interaction of light with sound in an ever increasing array of devices. This interaction allows the mechanical system to be both sensed and controlled by the optical system, opening up a wide variety of experiments including the cooling of the mechanical resonator to its quantum mechanical ground state and the squeezing of the optical field upon interaction with the mechanical resonator, to name two.

In this work we explore two very different systems with different types of optomechanical coupling. The first system consists of two microdisk optical resonators stacked on top of each other and separated by a very small slot. The interaction of the disks causes their optical resonance frequencies to be extremely sensitive to the gap between the disks. By careful control of the gap between the disks, the optomechanical coupling can be made to be quadratic to first order which is uncommon in optomechanical systems. With this quadratic coupling the light field is now sensitive to the energy of the mechanical resonator and can directly control the potential energy trapping the mechanical motion. This ability to directly control the spring constant without modifying the energy of the mechanical system, unlike in linear optomechanical coupling, is explored.

Next, the bulk of this thesis deals with a high mechanical frequency optomechanical crystal which is used to coherently convert photons between different frequencies. This is accomplished via the engineered linear optomechanical coupling in these devices. Both classical and quantum systems utilize the interaction of light and matter across a wide range of energies. These systems are often not naturally compatible with one another and require a means of converting photons of dissimilar wavelengths to combine and exploit their different strengths. Here we theoretically propose and experimentally demonstrate coherent wavelength conversion of optical photons using photon-phonon translation in a cavity-optomechanical system. For an engineered silicon optomechanical crystal nanocavity supporting a 4 GHz localized phonon mode, optical signals in a 1.5 MHz bandwidth are coherently converted over a 11.2 THz frequency span between one cavity mode at wavelength 1460 nm and a second cavity mode at 1545 nm with a 93% internal (2% external) peak efficiency. The thermal and quantum limiting noise involved in the conversion process is also analyzed and, in terms of an equivalent photon number signal level, are found to correspond to an internal noise level of only 6 and 4 times 10x^-3 quanta, respectively.

We begin by developing the requisite theoretical background to describe the system. A significant amount of time is then spent describing the fabrication of these silicon nanobeams, with an emphasis on understanding the specifics and motivation. The experimental demonstration of wavelength conversion is then described and analyzed. It is determined that the method of getting photons into the cavity and collected from the cavity is a fundamental limiting factor in the overall efficiency. Finally, a new coupling scheme is designed, fabricated, and tested that provides a means of coupling greater than 90% of photons into and out of the cavity, addressing one of the largest obstacles with the initial wavelength conversion experiment.

Cu2O substrates and epitaxial Cu2O/ZnO thin film hetero-structures for solar energy conversion

Future fossil fuel scarcity and environmental degradation have demonstrated the need for renewable, low-carbon sources of energy to power an increasingly industrialized world. Solar energy with its infinite supply makes it an extraordinary resource that should not go unused. However with current materials, adoption is limited by cost and so a paradigm shift must occur to get everyone on the same page embracing solar technology. Cuprous Oxide (Cu2O) is a promising earth abundant material that can be a great alternative to traditional thin-film photovoltaic materials like CIGS, CdTe, etc. We have prepared Cu2O bulk substrates by the thermal oxidation of copper foils as well Cu2O thin films deposited via plasma-assisted Molecular Beam Epitaxy. From preliminary Hall measurements it was determined that Cu2O would need to be doped extrinsically. This was further confirmed by simulations of ZnO/Cu2O heterojunctions. A cyclic interdependence between, defect concentration, minority carrier lifetime, film thickness, and carrier concentration manifests itself a primary reason for why efficiencies greater than 4% has yet to be realized. Our growth methodology for our thin-film heterostructures allow precise control of the number of defects that incorporate into our film during both equilibrium and nonequilibrium growth. We also report process flow/device design/fabrication techniques in order to create a device. A typical device without any optimizations exhibited open-circuit voltages Voc, values in excess 500mV; nearly 18% greater than previous solid state devices.

Catalytic conversion of nitrogen to ammonia by an iron model complex

Threefold symmetric Fe phosphine complexes have been used to model the structural and functional aspects of biological N₂ fixation by nitrogenases. Low-valent bridging Fe-S-Fe complexes in the formal oxidation states Fe(II)Fe(II), Fe(II)/Fe(I), and Fe(I)/Fe(I) have been synthesized which display rich spectroscopic and magnetic behavior. A series of cationic tris-phosphine borane (TPB) ligated Fe complexes have been synthesized and been shown to bind a variety of nitrogenous ligands including N₂H₄, NH₃, and NH₂-. These complexes are all high spin S = 3/2 and display EPR and magnetic characteristics typical of this spin state. Furthermore, a sequential protonation and reduction sequence of a terminal amide results in loss of NH₃ and uptake of N₂. These stoichiometric transformations represent the final steps in potential N₂ fixation schemes.

Treatment of an anionic FeN₂ complex with excess acid also results in the formation of some NH₃, suggesting the possibility of a catalytic cycle for the conversion of N₂ to NH₃ mediated by Fe. Indeed, use of excess acid and reductant results in the formation of seven equivalents of NH₃ per Fe center, demonstrating Fe mediated catalytic N₂ fixation with acids and protons for the first time. Numerous control experiments indicate that this catalysis is likely being mediated by a molecular species.

A number of other phosphine ligated Fe complexes have also been tested for catalysis and suggest that a hemi-labile Fe-B interaction may be critical for catalysis. Additionally, various conditions for the catalysis have been investigated. These studies further support the assignment of a molecular species and delineate some of the conditions required for catalysis.

Finally, combined spectroscopic studies have been performed on a putative intermediate for catalysis. These studies converge on an assignment of this new species as a hydrazido(2-) complex. Such species have been known on group 6 metals for some time, but this represents the first characterization of this ligand on Fe. Further spectroscopic studies suggest that this species is present in catalytic mixtures, which suggests that the first steps of a distal mechanism for N₂ fixation are feasible in this system.

Nanostructured tungsten trioxide photoanodes for solar energy conversion

Nanostructured tungsten trioxide (WO₃) photoelectrodes are potential candidates for the anodic portion of an integrated solar water-splitting device that generates hydrogen fuel and oxygen from water. These nanostructured materials can potentially offer improved performance in photooxidation reactions compared to unstructured materials because of enhancements in light scattering, increases in surface area, and their decoupling of the directions of light absorption and carrier collection. To evaluate the presence of these effects and their contributions toward energy conversion efficiency, a variety of nanostructured WO₃ photoanodes were synthesized by electrodeposition within nanoporous templates and by anodization of tungsten foils. A robust fabrication process was developed for the creation of oriented WO₃ nanorod arrays, which allows for control nanorod diameter and length. Films of nanostructured WO₃ platelets were grown via anodization, the morphology of the films was controlled by the anodization conditions, and the current-voltage performance and spectral response properties of these films were studied. The observed photocurrents were consistent with the apparent morphologies of the nanostructured arrays. Measurements of electrochemically active surface area and other physical characteristics were correlated with observed differences in absorbance, external quantum yield, and photocurrent density for the anodized arrays. The capability to quantify these characteristics and relate them to photoanode performance metrics can allow for selection of appropriate structural parameters when designing photoanodes for solar energy conversion.

Part I. Efforts directed towards the total synthesis of shionone. Part II. Conversion of estrone to androst-4-EN-3-ONE: a new method for activating the C-9 and C-10 positions of estrogenic steroids for substitution

Part I: An approach to the total synthesis of the triterpene shionone is described, which proceeds through the tetracyclic ketone i. The shionone side chain has been attached to this key intermediate in 5 steps, affording the olefin 2 in 29% yield. A method for the stereo-specific introduction of the angular methyl group at C-5 of shionone has been developed on a model system. The attempted utilization of this method to convert olefin 2 into shionone is described.

Part II: A method has been developed for activating the C-9 and C-10 positions of estrogenic steroids for substitution. Estrone has been converted to 4β,5β-epoxy-10β-hydroxyestr-3-one; cleavage of this epoxyketone using an Eschenmoser procedure, and subsequent modification of the product afforded 4-seco-9-estren-3,5-dione 3-ethylene acetal. This versatile intermediate, suitable for substitution at the 9 and/or 10 position, was converted to androst-4-ene-3-one by known procedures.

Luminescence properties of electron-hole-droplets in pure and doped germanium

This work contains 4 topics dealing with the properties of the luminescence from Ge.

The temperature, pump-power and time dependences of the photoluminescence spectra of Li-, As-, Ga-, and Sb-doped Ge crystals were studied. For impurity concentrations less than about 10¹⁵cm^-3, emissions due to electron-hole droplets can clearly be identified. For impurity concentrations on the order of 10¹⁶cm^-3, the broad lines in the spectra, which have previously been attributed to the emission from the electron-hole-droplet, were found to possess pump-power and time dependent line shape. These properties show that these broad lines cannot be due to emission of electron-hole-droplets alone. We interpret these lines to be due to a combination of emissions from (1) electron-hole- droplets, (2) broadened multiexciton complexes, (3) broadened bound-exciton, and (4) plasma of electrons and holes. The properties of the electron-hole-droplet in As-doped Ge were shown to agree with theoretical predictions.

The time dependences of the luminescence intensities of the electron-hole-droplet in pure and doped Ge were investigated at 2 and 4.2°K. The decay of the electron-hole-droplet in pure Ge at 4.2°K was found to be pump-power dependent and too slow to be explained by the widely accepted model due to Pokrovskii and Hensel et al. Detailed study of the decay of the electron-hole-droplets in doped Ge were carried out for the first time, and we find no evidence of evaporation of excitons by electron-hole-droplets at 4.2°K. This doped Ge result is unexplained by the model of Pokrovskii and Hensel et al. It is shown that a model based on a cloud of electron-hole-droplets generated in the crystal and incorporating (1) exciton flow among electron-hole-droplets in the cloud and (2) exciton diffusion away from the cloud is capable of explaining the observed results.

It is shown that impurities, introduced during device fabrication, can lead to the previously reported differences of the spectra of laser-excited high-purity Ge and electrically excited Ge double injection devices. By properly choosing the device geometry so as to minimize this Li contamination, it is shown that the Li concentration in double injection devices may be reduced to less than about 10¹⁵cm^-3 and electrically excited luminescence spectra similar to the photoluminescence spectra of pure Ge may be produced. This proves conclusively that electron-hole-droplets may be created in double injection devices by electrical excitation.

The ratio of the LA- to TO-phonon-assisted luminescence intensities of the electron-hole-droplet is demonstrated to be equal to the high temperature limit of the same ratio of the exciton for Ge. This result gives one confidence to determine similar ratios for the electron-hole-droplet from the corresponding exciton ratio in semiconductors in which the ratio for the electron-hole-droplet cannot be determined (e.g., Si and GaP). Knowing the value of this ratio for the electron-hole-droplet, one can obtain accurate values of many parameters of the electron-hole-droplet in these semiconductors spectroscopically.

Resonance cones and mode conversion in a warm magnetized bounded plasma

The warm plasma resonance cone structure of the quasistatic field produced by a gap source in a bounded magnetized slab plasma is determined theoretically. This is initially determined for a homogeneous or mildly inhomogeneous plasma with source frequency lying between the lower hybrid frequency and the plasma frequency. It is then extended to the complicated case of an inhomogeneous plasma with two internal lower hybrid layers present, which is of interest to radio frequency heating of plasmas.

In the first case, the potential is obtained as a sum of multiply reflected warm plasma resonance cones, each of which has a similar structure, but a different size, amplitude, and position. An important interference between nearby multiply-reflected resonance cones is found. The cones are seen to spread out as they move away from the source, so that this interference increases and the individual resonance cones become obscured far away from the source.

In the second case, the potential is found to be expressible as a sum of multiply-reflected, multiply-tunnelled, and mode converted resonance cones, each of which has a unique but similar structure. The effects of both collisional and collisionless damping are included and their effects on the decay of the cone structure studied. Various properties of the cones such as how they move into and out of the hybrid layers, through the evanescent region, and transform at the hybrid layers are determined. It is found that cones can tunnel through the evanescent layer if the layer is thin, and the effect of the thin evanescent layer is to subdue the secondary maxima of cone relative to the main peak, while slightly broadening the main peak and shifting it closer to the cold plasma cone line.

Energy theorems for quasistatic fields are developed and applied to determine the power flow and absorption along the individual cones. This reveals the points of concentration of the flow and the various absorption mechanisms.

A study of a new electromechanical energy conversion process using superconducting frequency modulated resonators

Experimental demonstrations and theoretical analyses of a new electromechanical energy conversion process which is made feasible only by the unique properties of superconductors are presented in this dissertation. This energy conversion process is characterized by a highly efficient direct energy transformation from microwave energy into mechanical energy or vice versa and can be achieved at high power level. It is an application of a well established physical principle known as the adiabatic theorem (Boltzmann-Ehrenfest theorem) and in this case time dependent superconducting boundaries provide the necessary interface between the microwave energy on one hand and the mechanical work on the other. The mechanism which brings about the conversion is another known phenomenon - the Doppler effect. The resonant frequency of a superconducting resonator undergoes continuous infinitesimal shifts when the resonator boundaries are adiabatically changed in time by an external mechanical mechanism. These small frequency shifts can accumulate coherently over an extended period of time to produce a macroscopic shift when the resonator remains resonantly excited throughout this process. In addition, the electromagnetic energy in s ide the resonator which is proportional to the oscillation frequency is al so accordingly changed so that a direct conversion between electromagnetic and mechanical energies takes place. The intrinsically high efficiency of this process is due to the electromechanical interactions involved in the conversion rather than a process of thermodynamic nature and therefore is not limited by the thermodynamic value.

A highly reentrant superconducting resonator resonating in the range of 90 to 160 MHz was used for demonstrating this new conversion technique. The resonant frequency was mechanically modulated at a rate of two kilohertz. Experimental results showed that the time evolution of the electromagnetic energy inside this frequency modulated (FM) superconducting resonator indeed behaved as predicted and thus demonstrated the unique features of this process. A proposed usage of FM superconducting resonators as electromechanical energy conversion devices is given along with some practical design considerations. This device seems to be very promising in producing high power (~10W/cm^3) microwave energy at 10 - 30 GHz.

Weakly coupled FM resonator system is also analytically studied for its potential applications. This system shows an interesting switching characteristic with which the spatial distribution of microwave energies can be manipulated by external means. It was found that if the modulation was properly applied, a high degree (>95%) of unidirectional energy transfer from one resonator to the other could be accomplished. Applications of this characteristic to fabricate high efficiency energy switching devices and high power microwave pulse generators are also found feasible with present superconducting technology.

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.

Injection Locked Clocking and Transmitter Equalization Techniques for Chip to Chip Interconnects

Semiconductor technology scaling has enabled drastic growth in the computational capacity of integrated circuits (ICs). This constant growth drives an increasing demand for high bandwidth communication between ICs. Electrical channel bandwidth has not been able to keep up with this demand, making I/O link design more challenging. Interconnects which employ optical channels have negligible frequency dependent loss and provide a potential solution to this I/O bandwidth problem. Apart from the type of channel, efficient high-speed communication also relies on generation and distribution of multi-phase, high-speed, and high-quality clock signals. In the multi-gigahertz frequency range, conventional clocking techniques have encountered several design challenges in terms of power consumption, skew and jitter. Injection-locking is a promising technique to address these design challenges for gigahertz clocking. However, its small locking range has been a major contributor in preventing its ubiquitous acceptance.

In the first part of this dissertation we describe a wideband injection locking scheme in an LC oscillator. Phase locked loop (PLL) and injection locking elements are combined symbiotically to achieve wide locking range while retaining the simplicity of the latter. This method does not require a phase frequency detector or a loop filter to achieve phase lock. A mathematical analysis of the system is presented and the expression for new locking range is derived. A locking range of 13.4 GHz–17.2 GHz (25%) and an average jitter tracking bandwidth of up to 400 MHz are measured in a high-Q LC oscillator. This architecture is used to generate quadrature phases from a single clock without any frequency division. It also provides high frequency jitter filtering while retaining the low frequency correlated jitter essential for forwarded clock receivers.

To improve the locking range of an injection locked ring oscillator; QLL (Quadrature locked loop) is introduced. The inherent dynamics of injection locked quadrature ring oscillator are used to improve its locking range from 5% (7-7.4GHz) to 90% (4-11GHz). The QLL is used to generate accurate clock phases for a four channel optical receiver using a forwarded clock at quarter-rate. The QLL drives an injection locked oscillator (ILO) at each channel without any repeaters for local quadrature clock generation. Each local ILO has deskew capability for phase alignment. The optical-receiver uses the inherent frequency to voltage conversion provided by the QLL to dynamically body bias its devices. A wide locking range of the QLL helps to achieve a reliable data-rate of 16-32Gb/s and adaptive body biasing aids in maintaining an ultra-low power consumption of 153pJ/bit.

From the optical receiver we move on to discussing a non-linear equalization technique for a vertical-cavity surface-emitting laser (VCSEL) based optical transmitter, to enable low-power, high-speed optical transmission. A non-linear time domain optical model of the VCSEL is built and evaluated for accuracy. The modelling shows that, while conventional FIR-based pre-emphasis works well for LTI electrical channels, it is not optimum for the non-linear optical frequency response of the VCSEL. Based on the simulations of the model an optimum equalization methodology is derived. The equalization technique is used to achieve a data-rate of 20Gb/s with power efficiency of 0.77pJ/bit.

Investigations of group IVA transition metal mediated carbon-carbon bond forming reactions

Zirconocene aldehyde and ketone complexes were synthesized in high yield by treatment of zirconocene acyl complexes with trimethylaluminum or diisobutylaluminum hydride. These complexes, which are activated by dialkylaluminum chloride ligands, inserted unsaturated substrates such as alkynes, allenes, ethylene, nitriles, ketenes, aldehydes, ketones, lactones, and acid chlorides with moderate to high conversion. Insertion of aldehyde substrates yielded zirconocene diolate complexes with up to 20:1 (anti:syn) diastereoselectivity. The zirconocene diolates were hydrolyzed to afford unsymmetrical 1,2-diols in 40-80% isolated yield. Unsymmetrical ketones gave similar insertion yields with little or no diastereoselectivity. A high yielding one-pot method was developed that coupled carbonyl substrates with zirconocene aldehyde complexes that were derived from olefins by hydrozirconation and carbonylation. The zirconocene aldehyde complexes also inserted carbon monoxide and gave acyloins in 50% yield after hydrolysis.

The insertion reaction of aryl epoxides with the trimethylphoshine adduct of titanocene methylidene was examined. The resulting oxytitanacyclopentanes were carbonylated and oxidatively cleaved with dioxygen to afford y-lactones in moderate yields. Due to the instability and difficult isolation of titanocene methylidene trimethylphoshine adducts, a one-pot method involving the addition of catalytic amounts of trimethylphosphine to β,β-dimethyltitanacyclobutane was developed. A series of disubstituted aryl epoxides were examined which gave mixtures of diastereomeric insertion products. Based on these results, as well as earlier Hammett studies and labeling experiments, a biradical transition state intermediate is proposed. The method is limited to aryl substituted epoxide substrates with aliphatic examples showing no insertion reactivity.

The third study involved the use of magnesium chloride supported titanium catalysts for the Lewis acid catalyzed silyl group transfer condensation of enol silanes with aldehydes. The reaction resulted in silylated aldol products with as many as 140 catalytic turnovers before catalyst inactivation. Low diastereoselectivities favoring the anti-isomer were consistent with an open transition state involving a titanium atom bound to the catalyst surface. The catalysts were also used for the aldol group transfer polymerization of t-butyldimethylsilyloxy-1-ethene resulting in polymers with molecular weights of 5000-31,000 and molar mass dispersities of 1.5-2.8. Attempts to polymerize methylmethacrylate using GTP proved unsuccessful with these catalysts.

Anomalous electric dipole internal conversion

Electric dipole internal conversion has been experimentally studied for several nuclei in the rare earth region. Anomalies in the conversion process have been interpreted in terms of nuclear structure effects. It was found that all the experimental results could be interpreted in terms of the j ∙ r type of penetration matrix element; the j ∙ ∇ type of penetration matrix element was not important. The ratio λ of the El j ∙ r penetration matrix element to the El gamma-ray matrix element was determined from the experiments to be:

Lu¹⁷⁵,396 keV, λ = - 1000 ± 100;

282 keV, λ = 500 ± 100;

144 keV, λ = 500 ± 250;

Hf¹⁷⁷, 321 keV λ = - 1400 ± 200;

208 keV λ = - 90 ± 40;

72 keV |λ| ≤ 650;

Gd¹⁵⁵, 86 keV λ = - 150 ± 100;

Tm¹⁶⁹, 63 keV λ = - 100 ± 100;

W¹⁸², 152 keV, λ = - 160 ±80;

67 keV, λ = - 100 ± 100.

Predictions for λ are made using the unified nuclear model.

SteelConverter and Caltech VirtualShaker: Rapid Nonlinear Cloud-Based Structural Model Conversion and Analysis

STEEL, the Caltech created nonlinear large displacement analysis software, is currently used by a large number of researchers at Caltech. However, due to its complexity, lack of visualization tools (such as pre- and post-processing capabilities) rapid creation and analysis of models using this software was difficult. SteelConverter was created as a means to facilitate model creation through the use of the industry standard finite element solver ETABS. This software allows users to create models in ETABS and intelligently convert model information such as geometry, loading, releases, fixity, etc., into a format that STEEL understands. Models that would take several days to create and verify now take several hours or less. The productivity of the researcher as well as the level of confidence in the model being analyzed is greatly increased.

It has always been a major goal of Caltech to spread the knowledge created here to other universities. However, due to the complexity of STEEL it was difficult for researchers or engineers from other universities to conduct analyses. While SteelConverter did help researchers at Caltech improve their research, sending SteelConverter and its documentation to other universities was less than ideal. Issues of version control, individual computer requirements, and the difficulty of releasing updates made a more centralized solution preferred. This is where the idea for Caltech VirtualShaker was born. Through the creation of a centralized website where users could log in, submit, analyze, and process models in the cloud, all of the major concerns associated with the utilization of SteelConverter were eliminated. Caltech VirtualShaker allows users to create profiles where defaults associated with their most commonly run models are saved, and allows them to submit multiple jobs to an online virtual server to be analyzed and post-processed. The creation of this website not only allowed for more rapid distribution of this tool, but also created a means for engineers and researchers with no access to powerful computer clusters to run computationally intensive analyses without the excessive cost of building and maintaining a computer cluster.

In order to increase confidence in the use of STEEL as an analysis system, as well as verify the conversion tools, a series of comparisons were done between STEEL and ETABS. Six models of increasing complexity, ranging from a cantilever column to a twenty-story moment frame, were analyzed to determine the ability of STEEL to accurately calculate basic model properties such as elastic stiffness and damping through a free vibration analysis as well as more complex structural properties such as overall structural capacity through a pushover analysis. These analyses showed a very strong agreement between the two softwares on every aspect of each analysis. However, these analyses also showed the ability of the STEEL analysis algorithm to converge at significantly larger drifts than ETABS when using the more computationally expensive and structurally realistic fiber hinges. Following the ETABS analysis, it was decided to repeat the comparisons in a software more capable of conducting highly nonlinear analysis, called Perform. These analyses again showed a very strong agreement between the two softwares in every aspect of each analysis through instability. However, due to some limitations in Perform, free vibration analyses for the three story one bay chevron brace frame, two bay chevron brace frame, and twenty story moment frame could not be conducted. With the current trend towards ultimate capacity analysis, the ability to use fiber based models allows engineers to gain a better understanding of a building’s behavior under these extreme load scenarios.

Following this, a final study was done on Hall’s U20 structure [1] where the structure was analyzed in all three softwares and their results compared. The pushover curves from each software were compared and the differences caused by variations in software implementation explained. From this, conclusions can be drawn on the effectiveness of each analysis tool when attempting to analyze structures through the point of geometric instability. The analyses show that while ETABS was capable of accurately determining the elastic stiffness of the model, following the onset of inelastic behavior the analysis tool failed to converge. However, for the small number of time steps the ETABS analysis was converging, its results exactly matched those of STEEL, leading to the conclusion that ETABS is not an appropriate analysis package for analyzing a structure through the point of collapse when using fiber elements throughout the model. The analyses also showed that while Perform was capable of calculating the response of the structure accurately, restrictions in the material model resulted in a pushover curve that did not match that of STEEL exactly, particularly post collapse. However, such problems could be alleviated by choosing a more simplistic material model.

Nuclear structure effects in internal conversion

Experimental studies of nuclear effects in internal conversion in Ta¹⁸¹ and Lu¹⁷⁵ have been performed. Nuclear structure effects (“penetration” effects), in internal conversion are described in general. Calculation of theoretical conversion coefficients are outlined. Comparisons with the theoretical conversion coefficient tables of Rose and Sliv and Band are made. Discrepancies between our results and those of Rose and Sliv are noted. The theoretical conversion coefficients of Sliv and Band are in substantially better agreement with our results than are those of Rose. The ratio of the M1 penetration matrix element to the M1 gamma-ray matrix element, called λ, is equal to + 175 ± 25 for the 482 keV transition in Ta¹⁸¹ . The results for the 343 keV transition in Lu¹⁷⁵ indicate that λ may be as large as – 8 ± 5. These transitions are discussed in terms of the unified collective model. Precision L subshell measurements in Tm¹⁶⁹ (130keV), W¹⁸² (100 keV), and Ta¹⁸¹ (133 keV) show definite systematic deviations from the theoretical conversion coefficients. The possibility of explaining these deviations by penetration effects is investigated and is shown to be excluded. Other explanations of these anomalies are discussed.