31 resultados para CASCADE DECAYS


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We simulate incompressible, MHD turbulence using a pseudo-spectral code. Our major conclusions are as follows.

1) MHD turbulence is most conveniently described in terms of counter propagating shear Alfvén and slow waves. Shear Alfvén waves control the cascade dynamics. Slow waves play a passive role and adopt the spectrum set by the shear Alfvén waves. Cascades composed entirely of shear Alfvén waves do not generate a significant measure of slow waves.

2) MHD turbulence is anisotropic with energy cascading more rapidly along k than along k, where k and k refer to wavevector components perpendicular and parallel to the local magnetic field. Anisotropy increases with increasing k such that excited modes are confined inside a cone bounded by k ∝ kγ where γ less than 1. The opening angle of the cone, θ(k) ∝ k-(1-γ), defines the scale dependent anisotropy.

3) MHD turbulence is generically strong in the sense that the waves which comprise it suffer order unity distortions on timescales comparable to their periods. Nevertheless, turbulent fluctuations are small deep inside the inertial range. Their energy density is less than that of the background field by a factor θ2 (k)≪1.

4) MHD cascades are best understood geometrically. Wave packets suffer distortions as they move along magnetic field lines perturbed by counter propagating waves. Field lines perturbed by unidirectional waves map planes perpendicular to the local field into each other. Shear Alfvén waves are responsible for the mapping's shear and slow waves for its dilatation. The amplitude of the former exceeds that of the latter by 1/θ(k) which accounts for dominance of the shear Alfvén waves in controlling the cascade dynamics.

5) Passive scalars mixed by MHD turbulence adopt the same power spectrum as the velocity and magnetic field perturbations.

6) Decaying MHD turbulence is unstable to an increase of the imbalance between the flux of waves propagating in opposite directions along the magnetic field. Forced MHD turbulence displays order unity fluctuations with respect to the balanced state if excited at low k by δ(t) correlated forcing. It appears to be statistically stable to the unlimited growth of imbalance.

7) Gradients of the dynamic variables are focused into sheets aligned with the magnetic field whose thickness is comparable to the dissipation scale. Sheets formed by oppositely directed waves are uncorrelated. We suspect that these are vortex sheets which the mean magnetic field prevents from rolling up.

8) Items (1)-(5) lend support to the model of strong MHD turbulence put forth by Goldreich and Sridhar (1995, 1997). Results from our simulations are also consistent with the GS prediction γ = 2/3. The sole not able discrepancy is that the 1D power law spectra, E(k) ∝ k-∝, determined from our simulations exhibit ∝ ≈ 3/2, whereas the GS model predicts ∝ = 5/3.

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Part I of this thesis deals with 3 topics concerning the luminescence from bound multi-exciton complexes in Si. Part II presents a model for the decay of electron-hole droplets in pure and doped Ge.

Part I.

We present high resolution photoluminescence data for Si doped With Al, Ga, and In. We observe emission lines due to recombination of electron-hole pairs in bound excitons and satellite lines which have been interpreted in terms of complexes of several excitons bound to an impurity. The bound exciton luminescence in Si:Ga and Si:Al consists of three emission lines due to transitions from the ground state and two low lying excited states. In Si:Ga, we observe a second triplet of emission lines which precisely mirror the triplet due to the bound exciton. This second triplet is interpreted as due to decay of a two exciton complex into the bound exciton. The observation of the second complete triplet in Si:Ga conclusively demonstrates that more than one exciton will bind to an impurity. Similar results are found for Si:Al. The energy of the lines show that the second exciton is less tightly bound than the first in Si:Ga. Other lines are observed at lower energies. The assumption of ground state to ground-state transitions for the lower energy lines is shown to produce a complicated dependence of binding energy of the last exciton on the number of excitons in a complex. No line attributable to the decay of a two exciton complex is observed in Si:In.

We present measurements of the bound exciton lifetimes for the four common acceptors in Si and for the first two bound multi-exciton complexes in Si:Ga and Si:Al. These results are shown to be in agreement with a calculation by Osbourn and Smith of Auger transition rates for acceptor bound excitons in Si. Kinetics determine the relative populations of complexes of various sizes and work functions, at temperatures which do not allow them to thermalize with respect to one another. It is shown that kinetic limitations may make it impossible to form two-exciton complexes in Si:In from a gas of free excitons.

We present direct thermodynamic measurements of the work functions of bound multi-exciton complexes in Al, B, P and Li doped Si. We find that in general the work functions are smaller than previously believed. These data remove one obstacle to the bound multi-exciton complex picture which has been the need to explain the very large apparent work functions for the larger complexes obtained by assuming that some of the observed lines are ground-state to ground-state transitions. None of the measured work functions exceed that of the electron-hole liquid.

Part II.

A new model for the decay of electron-hole-droplets in Ge is presented. The model is based on the existence of a cloud of droplets within the crystal and incorporates exciton flow among the drops in the cloud and the diffusion of excitons away from the cloud. It is able to fit the experimental luminescence decays for pure Ge at different temperatures and pump powers while retaining physically reasonable parameters for the drops. It predicts the shrinkage of the cloud at higher temperatures which has been verified by spatially and temporally resolved infrared absorption experiments. The model also accounts for the nearly exponential decay of electron-hole-droplets in lightly doped Ge at higher temperatures.

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I. Foehn winds of southern California.
An investigation of the hot, dry and dust laden winds occurring in the late fall and early winter in the Los Angeles Basin and attributed in the past to the influences of the desert regions to the north revealed that these currents were of a foehn nature. Their properties were found to be entirely due to dynamical heating produced in the descent from the high level areas in the interior to the lower Los Angeles Basin. Any dust associated with the phenomenon was found to be acquired from the Los Angeles area rather than transported from the desert. It was found that the frequency of occurrence of a mild type foehn of this nature during this season was sufficient to warrant its classification as a winter monsoon. This results from the topography of the Los Angeles region which allows an easy entrance to the air from the interior by virtue of the low level mountain passes north of the area. This monsoon provides the mild winter climate of southern California since temperatures associated with the foehn currents are far higher than those experienced when maritime air from the adjacent Pacific Ocean occupies the region.

II. Foehn wind cyclo-genesis.
Intense anticyclones frequently build up over the high level regions of the Great Basin and Columbia Plateau which lie between the Sierra Nevada and Cascade Mountains to the west and the Rocky Mountains to the east. The outflow from these anticyclones produce extensive foehns east of the Rockies in the comparatively low level areas of the middle west and the Canadian provinces of Alberta and Saskatchewan. Normally at this season of the year very cold polar continental air masses are present over this territory and with the occurrence of these foehns marked discontinuity surfaces arise between the warm foehn current, which is obliged to slide over a colder mass, and the Pc air to the east. Cyclones are easily produced from this phenomenon and take the form of unstable waves which propagate along the discontinuity surface between the two dissimilar masses. A continual series of such cyclones was found to occur as long as the Great Basin anticyclone is maintained with undiminished intensity.

III. Weather conditions associated with the Akron disaster.
This situation illustrates the speedy development and propagation of young disturbances in the eastern United States during the spring of the year under the influence of the conditionally unstable tropical maritime air masses which characterise the region. It also furnishes an excellent example of the superiority of air mass and frontal methods of weather prediction for aircraft operation over the older methods based upon pressure distribution.

IV. The Los Angeles storm of December 30, 1933 to January 1, 1934.
This discussion points out some of the fundamental interactions occurring between air masses of the North Pacific Ocean in connection with Pacific Coast storms and the value of topographic and aerological considerations in predicting them. Estimates of rainfall intensity and duration from analyses of this type may be made and would prove very valuable in the Los Angeles area in connection with flood control problems.

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The energy spectra of 235U atoms sputtered from a 93% enriched 235U metal foil and a hot pressed 235U02 pellet by an 80 keV 40Ar+ beam have been measured in the range 1 eV to 1 keV. The measurements were made using a mechanical time-of-flight spectrometer in conjunction with the fission track technique for detecting 235U. The design and construction of this spectrometer are discussed in detail, and its operation is mathematically analyzed.

The results of the experiment are discussed in the context of the random collision cascade model of sputtering. The spectrum obtained by the sputtering of the 235U metal target was found to be well described by the functional form E(E+Eb)-2.77, where Eb = 5.4 eV. The 235U02 target produced a spectrum that peaked at a lower energy (~ 2 eV) and decreased somewhat more rapidly for E ≳ 100 eV.

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Nitrogen-containing heterocycles, such as indolines and pyrroloindolines, are prevalent in a variety of diverse natural products, many of which exhibit remarkable biological activities. These frameworks have inspired innovative research aimed at discovering novel methods for their stereoselective preparation.

We have developed an enantioselective synthesis of pyrroloindolines based on a formal (3 + 2) cycloaddition of indoles and 2-amidoacrylates. This reaction is promoted by (R)-BINOL•SnCl4; this complex is a Lewis acid-assisted Brønsted acid that effects a highly face-selective catalyst-controlled protonation of an enolate. Mechanistic studies also determined that the initial product of this reaction is an indolinium ion, which upon aqueous workup undergoes cyclization to the pyrroloindoline.

Based on this result, we investigated alternative nucleophiles to trap the indolinium ion. First, addition of sodium borohydride to the optimized reaction conditions yields indoline-containing amino acid derivatives.

Next, carbon nucleophiles were explored. Indole substrates incorporating a tethered alkene were exposed to the conditions for the formal (3 + 2) cycloaddition, resulting in a conjugate addition/asymmetric protonation/Prins cyclization cascade. In this transformation, the indolinium ion is attacked by the olefin, and the resulting carbocation is quenched by a chloride ion. Zirconium tetrachloride was found to be the optimal Lewis acid. Stoichiometric proton and chloride sources were also found to be crucial for reactivity.

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DC and transient measurements of space-charge-limited currents through alloyed and symmetrical n^+ν n^+ structures made of nominally 75 kΩcm ν-type silicon are studied before and after the introduction of defects by 14 MeV neutron radiation. In the transient measurements, the current response to a large turn-on voltage step is analyzed. Right after the voltage step is applied, the current transient reaches a value which we shall call "initial current" value. At longer times, the transient current decays from the initial current value if traps are present.

Before the irradiation, the initial current density-voltage characteristics J(V) agree quantitatively with the theory of trap-free space-charge-limited current in solids. We obtain for the electron mobility a temperature dependence which indicates that scattering due to impurities is weak. This is expected for the high purity silicon used. The drift velocity-field relationships for electrons at room temperature and 77°K, derived from the initial current density-voltage characteristics, are shown to fit the relationships obtained with other methods by other workers. The transient current response for t > 0 remains practically constant at the initial value, thus indicating negligible trapping.

Measurement of the initial (trap-free) current density-voltage characteristics after the irradiation indicates that the drift velocity-field relationship of electrons in silicon is affected by the radiation only at low temperature in the low field range. The effect is not sufficiently pronounced to be readily analyzed and no formal description of it is offered. In the transient response after irradiation for t > 0, the current decays from its initial value, thus revealing the presence of traps. To study these traps, in addition to transient measurements, the DC current characteristics were measured and shown to follow the theory of trap-dominated space-charge-limited current in solids. This theory was applied to a model consisting of two discrete levels in the forbidden band gap. Calculations and experiments agreed and the capture cross-sections of the trapping levels were obtained. This is the first experimental case known to us through which the flow of space-charge-limited current is so simply representable.

These results demonstrate the sensitivity of space-charge-limited current flow as a tool to detect traps and changes in the drift velocity-field relationship of carriers caused by radiation. They also establish that devices based on the mode of space-charge-limited current flow will be affected considerably by any type of radiation capable of introducing traps. This point has generally been overlooked so far, but is obviously quite significant.

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This thesis describes a measurement of B0- B0 mixing in events produced by electron-positron annihilation at a center of mass energy of 29 GeV. The data were taken by the Mark II detector in the PEP storage ring at the Stanford Linear Accelerator Center between 1981 and 1987, and correspond to a total integrated luminosity of 224pb-1.

We used a new method, based on the kinematics of hadronic events containing two leptons, to provide a measurement of the probability, x, that a hadron, initially containing a b (b) quark decays to a positive (negative) lepton to be X = 0.17+0.15-0.08, with 90% confidence level upper and lower limits of 0.38 and 0.06, respectively, including all estimated systematic errors. Because of the good separation of signal and background, this result is relatively insensitive to various systematic effects which have complicated previous measurements.

We interpret this result as evidence for the mixing of neutral B mesons. Based on existing B0d mixing rate measurements, and some assumptions about the fractions of B0d and B0s mesons present in the data, this result favors maximal mixing of B0s mesons, although it cannot rule out zero B0s mixing at the 90% confidence level.

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Herein are described the total syntheses of all members of the transtaganolide and basiliolide natural product family. Utilitzation of an Ireland–Claisen rearrangement/Diels–Alder cycloaddition cascade (ICR/DA) allowed for rapid assembly of the transtaganolide and basiliolide oxabicyclo[2.2.2]octane core. This methodology is general and was applicable to all members of the natural product family.

A brief introduction outlines all the synthetic progress previously disclosed by Lee, Dudley, and Johansson. This also includes the initial syntheses of transtaganolides C and D, as well as basiliolide B and epi-basiliolide B accomplished by Stoltz in 2011. Lastly, we discuss our racemic synthesis of basililide C and epi-basiliolide C, which utilized an ICR/DA cascade to constuct the oxabicyclo[2.2.2]octane core and formal [5+2] annulation to form the ketene-acetal containing 7-membered C-ring.

Next, we describe a strategy for an asymmetric ICR/DA cascade, by incorporation of a chiral silane directing group. This allowed for enantioselective construction of the C8 all-carbon quaternary center formed in the Ireland–Claisen rearrangement. Furthermore, a single hydride reduction and subsequent translactonization of a C4 methylester bearing oxabicyclo[2.2.2]octane core demonstrated a viable strategy for the desired skeletal rearrangement to obtain pentacyclic transtaganolides A and B. Application of the asymmetric strategy culminated in the total syntheses of (–)-transtaganolide A, (+)-transtaganolide B, (+)-transtaganolide C, and (–)-transtaganolide D. Comparison of the optical rotation data of the synthetically derived transtaganolides to that from the isolated counterparts has overarching biosynthetic implications which are discussed.

Lastly, improvement to the formal [5+2] annulation strategy is described. Negishi cross-coupling of methoxyethynyl zinc chloride using a palladium Xantphos catalyst is optimized for iodo-cyclohexene. Application of this technology to an iodo-pyrone geranyl ester allowed for formation and isolation of the eneyne product. Hydration of the enenye product forms natural metabolite basiliopyrone. Furthermore, the eneyne product can undergo an ICR/DA cascade and form transtaganolides C and D in a single step from an achiral monocyclic precursor.

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As the worldwide prevalence of diabetes mellitus continues to increase, diabetic retinopathy remains the leading cause of visual impairment and blindness in many developed countries. Between 32 to 40 percent of about 246 million people with diabetes develop diabetic retinopathy. Approximately 4.1 million American adults 40 years and older are affected by diabetic retinopathy. This glucose-induced microvascular disease progressively damages the tiny blood vessels that nourish the retina, the light-sensitive tissue at the back of the eye, leading to retinal ischemia (i.e., inadequate blood flow), retinal hypoxia (i.e., oxygen deprivation), and retinal nerve cell degeneration or death. It is a most serious sight-threatening complication of diabetes, resulting in significant irreversible vision loss, and even total blindness.

Unfortunately, although current treatments of diabetic retinopathy (i.e., laser therapy, vitrectomy surgery and anti-VEGF therapy) can reduce vision loss, they only slow down but cannot stop the degradation of the retina. Patients require repeated treatment to protect their sight. The current treatments also have significant drawbacks. Laser therapy is focused on preserving the macula, the area of the retina that is responsible for sharp, clear, central vision, by sacrificing the peripheral retina since there is only limited oxygen supply. Therefore, laser therapy results in a constricted peripheral visual field, reduced color vision, delayed dark adaptation, and weakened night vision. Vitrectomy surgery increases the risk of neovascular glaucoma, another devastating ocular disease, characterized by the proliferation of fibrovascular tissue in the anterior chamber angle. Anti-VEGF agents have potential adverse effects, and currently there is insufficient evidence to recommend their routine use.

In this work, for the first time, a paradigm shift in the treatment of diabetic retinopathy is proposed: providing localized, supplemental oxygen to the ischemic tissue via an implantable MEMS device. The retinal architecture (e.g., thickness, cell densities, layered structure, etc.) of the rabbit eye exposed to ischemic hypoxic injuries was well preserved after targeted oxygen delivery to the hypoxic tissue, showing that the use of an external source of oxygen could improve the retinal oxygenation and prevent the progression of the ischemic cascade.

The proposed MEMS device transports oxygen from an oxygen-rich space to the oxygen-deficient vitreous, the gel-like fluid that fills the inside of the eye, and then to the ischemic retina. This oxygen transport process is purely passive and completely driven by the gradient of oxygen partial pressure (pO2). Two types of devices were designed. For the first type, the oxygen-rich space is underneath the conjunctiva, a membrane covering the sclera (white part of the eye), beneath the eyelids and highly permeable to oxygen in the atmosphere when the eye is open. Therefore, sub-conjunctival pO2 is very high during the daytime. For the second type, the oxygen-rich space is inside the device since pure oxygen is needle-injected into the device on a regular basis.

To prevent too fast or too slow permeation of oxygen through the device that is made of parylene and silicone (two widely used biocompatible polymers in medical devices), the material properties of the hybrid parylene/silicone were investigated, including mechanical behaviors, permeation rates, and adhesive forces. Then the thicknesses of parylene and silicone became important design parameters that were fine-tuned to reach the optimal oxygen permeation rate.

The passive MEMS oxygen transporter devices were designed, built, and tested in both bench-top artificial eye models and in-vitro porcine cadaver eyes. The 3D unsteady saccade-induced laminar flow of water inside the eye model was modeled by computational fluid dynamics to study the convective transport of oxygen inside the eye induced by saccade (rapid eye movement). The saccade-enhanced transport effect was also demonstrated experimentally. Acute in-vivo animal experiments were performed in rabbits and dogs to verify the surgical procedure and the device functionality. Various hypotheses were confirmed both experimentally and computationally, suggesting that both the two types of devices are very promising to cure diabetic retinopathy. The chronic implantation of devices in ischemic dog eyes is still underway.

The proposed MEMS oxygen transporter devices can be also applied to treat other ocular and systemic diseases accompanied by retinal ischemia, such as central retinal artery occlusion, carotid artery disease, and some form of glaucoma.

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This thesis describes a series of experimental, numerical, and analytical studies involving the Caltech magnetohydrodynamically (MHD)-driven plasma jet experiment. The plasma jet is created via a capacitor discharge that powers a magnetized coaxial planar electrodes system. The jet is collimated and accelerated by the MHD forces.

We present three-dimensional ideal MHD finite-volume simulations of the plasma jet experiment using an astrophysical magnetic tower as the baseline model. A compact magnetic energy/helicity injection is exploited in the simulation analogous to both the experiment and to astrophysical situations. Detailed analysis provides a comprehensive description of the interplay of magnetic force, pressure, and flow effects. We delineate both the jet structure and the transition process that converts the injected magnetic energy to other forms.

When the experimental jet is sufficiently long, it undergoes a global kink instability and then a secondary local Rayleigh-Taylor instability caused by lateral acceleration of the kink instability. We present an MHD theory of the Rayleigh-Taylor instability on the cylindrical surface of a plasma flux rope in the presence of a lateral external gravity. The Rayleigh-Taylor instability is found to couple to the classic current-driven instability, resulting in a new type of hybrid instability. The coupled instability, produced by combination of helical magnetic field, curvature of the cylindrical geometry, and lateral gravity, is fundamentally different from the classic magnetic Rayleigh-Taylor instability occurring at a two-dimensional planar interface.

In the experiment, this instability cascade from macro-scale to micro-scale eventually leads to the failure of MHD. When the Rayleigh-Taylor instability becomes nonlinear, it compresses and pinches the plasma jet to a scale smaller than the ion skin depth and triggers a fast magnetic reconnection. We built a specially designed high-speed 3D magnetic probe and successfully detected the high frequency magnetic fluctuations of broadband whistler waves associated with the fast reconnection. The magnetic fluctuations exhibit power-law spectra. The magnetic components of single-frequency whistler waves are found to be circularly polarized regardless of the angle between the wave propagation direction and the background magnetic field.

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The two lowest T = 3/2 levels in 21Na have been studied in the 19F(3He, n), 20Ne (p,p) and 20Ne (p,p’) reactions, and their excitation energies, spins, parities and widths have been determined. In a separate investigation, branching ratios were measured for the isospin-nonconserving particle decays of the lowest T = 3/2 levels in 17O and 17F to the ground state and first two excited states of 16O, by studying the 15N(3He,n) 17F*(p) 16O and 18O(3He, α)17O*(n) 16O reactions.

The 19F(3He,n) 21Na reaction was studied at incident energies between 4.2 and 5.9 MeV using a pulsed-beam neutron-time-of-flight spectrometer. Two T = 3/2 levels were identified at excitation energies of 8.99 ± 0.05 MeV (J > ½) and 9.22 ± 0.015 MeV (J π = ½+, Γ ˂ 40 keV). The spins and parities were determined by a comparison of the measured angular distributions with the results of DWBA calculations.

These two levels were also obsesrved as isospin-forbidden resonances in the 20Ne(p,p) and 20Ne(p,p’) reactions. Excitation energies were measured and spins, parities, and widths were determined from a single level dispersion theory analysis. The following results were obtained:

Ex = 8.973 ± 0.007 MeV, J π = 5/2 + or 3/2+, Γ ≤ 1.2 keV,

Γpo = 0.1 ± 0.05 keV; Ex = 9.217 ± 0.007 MeV, Jπ = ½ +,

Γ = 2.3 ± 0.5 keV, Γpo = 1.1 ± 0.3 keV.

Isospin assignments were made on the basis of excitation energies, spins, parities, and widths.

Branching ratios for the isospin-nonconserving proton decays of the 11.20 MeV, T = 3/2 level in 17F were measured by the 15N(3He,n) 17 F*(p) 16O reaction to be 0.088 ± 0.016 to the ground state of 16O and 0.22 ± 0.04 to the unresolved 6.05 and 6.13 MeV levels of 16O. Branching ratios for the neutron decays of the analogous T = 3/2 level, at 11.08 MeV in 17O, were measured by the 16O(3He, α)17O*(n)16O reaction to be 0.91 ± 0.15 to the ground state of 16O and 0.05 ± 0.02 to the unresolved 6.05 and 6.13 MeV states. By comparing the ratios of reduced widths for the mirror decays, the form of the isospin impurity in the T = 3/2 levels is shown to depend on Tz.

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This thesis presents investigations in four areas of theoretical astrophysics: the production of sterile neutrino dark matter in the early Universe, the evolution of small-scale baryon perturbations during the epoch of cosmological recombination, the effect of primordial magnetic fields on the redshifted 21-cm emission from the pre-reionization era, and the nonlinear stability of tidally deformed neutron stars.

In the first part of the thesis, we study the asymmetry-driven resonant production of 7 keV-scale sterile neutrino dark matter in the primordial Universe at temperatures T >~ 100 MeV. We report final DM phase space densities that are robust to uncertainties in the nature of the quark-hadron transition. We give transfer functions for cosmological density fluctuations that are useful for N-body simulations. We also provide a public code for the production calculation.

In the second part of the thesis, we study the instability of small-scale baryon pressure sound waves during cosmological recombination. We show that for relevant wavenumbers, inhomogenous recombination is driven by the transport of ionizing continuum and Lyman-alpha photons. We find a maximum growth factor less than ≈ 1.2 in 107 random realizations of initial conditions. The low growth factors are due to the relatively short duration of the recombination epoch.

In the third part of the thesis, we propose a method of measuring weak magnetic fields, of order 10-19 G (or 10-21 G if scaled to the present day), with large coherence lengths in the inter galactic medium prior to and during the epoch of cosmic reionization. The method utilizes the Larmor precession of spin-polarized neutral hydrogen in the triplet state of the hyperfine transition. We perform detailed calculations of the microphysics behind this effect, and take into account all the processes that affect the hyperfine transition, including radiative decays, collisions, and optical pumping by Lyman-alpha photons.

In the final part of the thesis, we study the non-linear effects of tidal deformations of neutron stars (NS) in a compact binary. We compute the largest three- and four-mode couplings among the tidal mode and high-order p- and g-modes of similar radial wavenumber. We demonstrate the near-exact cancellation of their effects, and resolve the question of the stability of the tidally deformed NS to leading order. This result is significant for the extraction of binary parameters from gravitational wave observations.

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A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x109sec-1 in N,N-dimethylformamide to 1.15x1010 Sec-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG0'(R)| ≤ 1.0 eV until a maximum is reached (κET = 3 x 108 sec-1 rising to 1.15 x 1010 sec-1 in acetonitrile). The rate remains insensitive to ΔG0 for ~ 300 mV from 1.0 eV≤ |ΔG0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κET = 5 x 109 sec-1).

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The wave-theoretical analysis of acoustic and elastic waves refracted by a spherical boundary across which both velocity and density increase abruptly and thence either increase or decrease continuously with depth is formulated in terms of the general problem of waves generated at a steady point source and scattered by a radially heterogeneous spherical body. A displacement potential representation is used for the elastic problem that results in high frequency decoupling of P-SV motion in a spherically symmetric, radially heterogeneous medium. Through the application of an earth-flattening transformation on the radial solution and the Watson transform on the sum over eigenfunctions, the solution to the spherical problem for high frequencies is expressed as a Weyl integral for the corresponding half-space problem in which the effect of boundary curvature maps into an effective positive velocity gradient. The results of both analytical and numerical evaluation of this integral can be summarized as follows for body waves in the crust and upper mantle:

1) In the special case of a critical velocity gradient (a gradient equal and opposite to the effective curvature gradient), the critically refracted wave reduces to the classical head wave for flat, homogeneous layers.

2) For gradients more negative than critical, the amplitude of the critically refracted wave decays more rapidly with distance than the classical head wave.

3) For positive, null, and gradients less negative than critical, the amplitude of the critically refracted wave decays less rapidly with distance than the classical head wave, and at sufficiently large distances, the refracted wave can be adequately described in terms of ray-theoretical diving waves. At intermediate distances from the critical point, the spectral amplitude of the refracted wave is scalloped due to multiple diving wave interference.

These theoretical results applied to published amplitude data for P-waves refracted by the major crustal and upper mantle horizons (the Pg, P*, and Pn travel-time branches) suggest that the 'granitic' upper crust, the 'basaltic' lower crust, and the mantle lid all have negative or near-critical velocity gradients in the tectonically active western United States. On the other hand, the corresponding horizons in the stable eastern United States appear to have null or slightly positive velocity gradients. The distribution of negative and positive velocity gradients correlates closely with high heat flow in tectonic regions and normal heat flow in stable regions. The velocity gradients inferred from the amplitude data are generally consistent with those inferred from ultrasonic measurements of the effects of temperature and pressure on crustal and mantle rocks and probable geothermal gradients. A notable exception is the strong positive velocity gradient in the mantle lid beneath the eastern United States (2 x 10-3 sec-1), which appears to require a compositional gradient to counter the effect of even a small geothermal gradient.

New seismic-refraction data were recorded along a 800 km profile extending due south from the Canadian border across the Columbia Plateau into eastern Oregon. The source for the seismic waves was a series of 20 high-energy chemical explosions detonated by the Canadian government in Greenbush Lake, British Columbia. The first arrivals recorded along this profile are on the Pn travel-time branch. In northern Washington and central Oregon their travel time is described by T = Δ/8.0 + 7.7 sec, but in the Columbia Plateau the Pn arrivals are as much as 0.9 sec early with respect to this line. An interpretation of these Pn arrivals together with later crustal arrivals suggest that the crust under the Columbia Plateau is thinner by about 10 km and has a higher average P-wave velocity than the 35-km-thick, 62-km/sec crust under the granitic-metamorphic terrain of northern Washington. A tentative interpretation of later arrivals recorded beyond 500 km from the shots suggests that a thin 8.4-km/sec horizon may be present in the upper mantle beneath the Columbia Plateau and that this horizon may form the lid to a pronounced low-velocity zone extending to a depth of about 140 km.

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A simple, direct and accurate method to predict the pressure distribution on supercavitating hydrofoils with rounded noses is presented. The thickness of body and cavity is assumed to be small. The method adopted in the present work is that of singular perturbation theory. Far from the leading edge linearized free streamline theory is applied. Near the leading edge, however, where singularities of the linearized theory occur, a non-linear local solution is employed. The two unknown parameters which characterize this local solution are determined by a matching procedure. A uniformly valid solution is then constructed with the aid of the singular perturbation approach.

The present work is divided into two parts. In Part I isolated supercavitating hydrofoils of arbitrary profile shape with parabolic noses are investigated by the present method and its results are compared with the new computational results made with Wu and Wang's exact "functional iterative" method. The agreement is very good. In Part II this method is applied to a linear cascade of such hydrofoils with elliptic noses. A number of cases are worked out over a range of cascade parameters from which a good idea of the behavior of this type of important flow configuration is obtained.

Some of the computational aspects of Wu and Wang's functional iterative method heretofore not successfully applied to this type of problem are described in an appendix.