Trapped ion magnetic resonance: concepts and designs

A novel spectroscopy of trapped ions is proposed which will bring single-ion detection sensitivity to the observation of magnetic resonance spectra. The approaches developed here are aimed at resolving one of the fundamental problems of molecular spectroscopy, the apparent incompatibility in existing techniques between high information content (and therefore good species discrimination) and high sensitivity. Methods for studying both electron spin resonance (ESR) and nuclear magnetic resonance (NMR) are designed. They assume established methods for trapping ions in high magnetic field and observing the trapping frequencies with high resolution (<1 Hz) and sensitivity (single ion) by electrical means. The introduction of a magnetic bottle field gradient couples the spin and spatial motions together and leads to a small spin-dependent force on the ion, which has been exploited by Dehmelt to observe directly the perturbation of the ground-state electron's axial frequency by its spin magnetic moment.

A series of fundamental innovations is described m order to extend magnetic resonance to the higher masses of molecular ions (100 amu = 2x 10^5 electron masses) and smaller magnetic moments (nuclear moments = 10^(-3) of the electron moment). First, it is demonstrated how time-domain trapping frequency observations before and after magnetic resonance can be used to make cooling of the particle to its ground state unnecessary. Second, adiabatic cycling of the magnetic bottle off between detection periods is shown to be practical and to allow high-resolution magnetic resonance to be encoded pointwise as the presence or absence of trapping frequency shifts. Third, methods of inducing spindependent work on the ion orbits with magnetic field gradients and Larmor frequency irradiation are proposed which greatly amplify the attainable shifts in trapping frequency.

The dissertation explores the basic concepts behind ion trapping, adopting a variety of classical, semiclassical, numerical, and quantum mechanical approaches to derive spin-dependent effects, design experimental sequences, and corroborate results from one approach with those from another. The first proposal presented builds on Dehmelt's experiment by combining a "before and after" detection sequence with novel signal processing to reveal ESR spectra. A more powerful technique for ESR is then designed which uses axially synchronized spin transitions to perform spin-dependent work in the presence of a magnetic bottle, which also converts axial amplitude changes into cyclotron frequency shifts. A third use of the magnetic bottle is to selectively trap ions with small initial kinetic energy. A dechirping algorithm corrects for undesired frequency shifts associated with damping by the measurement process.

The most general approach presented is spin-locked internally resonant ion cyclotron excitation, a true continuous Stern-Gerlach effect. A magnetic field gradient modulated at both the Larmor and cyclotron frequencies is devised which leads to cyclotron acceleration proportional to the transverse magnetic moment of a coherent state of the particle and radiation field. A preferred method of using this to observe NMR as an axial frequency shift is described in detail. In the course of this derivation, a new quantum mechanical description of ion cyclotron resonance is presented which is easily combined with spin degrees of freedom to provide a full description of the proposals.

Practical, technical, and experimental issues surrounding the feasibility of the proposals are addressed throughout the dissertation. Numerical ion trajectory simulations and analytical models are used to predict the effectiveness of the new designs as well as their sensitivity and resolution. These checks on the methods proposed provide convincing evidence of their promise in extending the wealth of magnetic resonance information to the study of collisionless ions via single-ion spectroscopy.

Studying conscious and unconscious vision with functional Magnetic Resonance Imaging : the BOLD promise

Waking up from a dreamless sleep, I open my eyes, recognize my wife’s face and am filled with joy. In this thesis, I used functional Magnetic Resonance Imaging (fMRI) to gain insights into the mechanisms involved in this seemingly simple daily occurrence, which poses at least three great challenges to neuroscience: how does conscious experience arise from the activity of the brain? How does the brain process visual input to the point of recognizing individual faces? How does the brain store semantic knowledge about people that we know? To start tackling the first question, I studied the neural correlates of unconscious processing of invisible faces. I was unable to image significant activations related to the processing of completely invisible faces, despite existing reports in the literature. I thus moved on to the next question and studied how recognition of a familiar person was achieved in the brain; I focused on finding invariant representations of person identity – representations that would be activated any time we think of a familiar person, read their name, see their picture, hear them talk, etc. There again, I could not find significant evidence for such representations with fMRI, even in regions where they had previously been found with single unit recordings in human patients (the Jennifer Aniston neurons). Faced with these null outcomes, the scope of my investigations eventually turned back towards the technique that I had been using, fMRI, and the recently praised analytical tools that I had been trusting, Multivariate Pattern Analysis. After a mostly disappointing attempt at replicating a strong single unit finding of a categorical response to animals in the right human amygdala with fMRI, I put fMRI decoding to an ultimate test with a unique dataset acquired in the macaque monkey. There I showed a dissociation between the ability of fMRI to pick up face viewpoint information and its inability to pick up face identity information, which I mostly traced back to the poor clustering of identity selective units. Though fMRI decoding is a powerful new analytical tool, it does not rid fMRI of its inherent limitations as a hemodynamics-based measure.

I. Impact spallation experiments: fracture patterns and spall velocities. II. Craters in carbonate rocks: an electron paramagnetic resonance analysis of shock damage

This work is divided into two independent papers.

PAPER 1.

Spall velocities were measured for nine experimental impacts into San Marcos gabbro targets. Impact velocities ranged from 1 to 6.5 km/sec. Projectiles were iron, aluminum, lead, and basalt of varying sizes. The projectile masses ranged from a 4 g lead bullet to a 0.04 g aluminum sphere. The velocities of fragments were measured from high-speed films taken of the events. The maximum spall velocity observed was 30 m/sec, or 0.56 percent of the 5.4 km/sec impact velocity. The measured velocities were compared to the spall velocities predicted by the spallation model of Melosh (1984). The compatibility between the spallation model for large planetary impacts and the results of these small scale experiments are considered in detail.

The targets were also bisected to observe the pattern of internal fractures. A series of fractures were observed, whose location coincided with the boundary between rock subjected to the peak shock compression and a theoretical "near surface zone" predicted by the spallation model. Thus, between this boundary and the free surface, the target material should receive reduced levels of compressive stress as compared to the more highly shocked region below.

PAPER 2.

Carbonate samples from the nuclear explosion crater, OAK, and a terrestrial impact crater, Meteor Crater, were analyzed for shock damage using electron para- magnetic resonance, EPR. The first series of samples for OAK Crater were obtained from six boreholes within the crater, and the second series were ejecta samples recovered from the crater floor. The degree of shock damage in the carbonate material was assessed by comparing the sample spectra to spectra of Solenhofen limestone, which had been shocked to known pressures.

The results of the OAK borehole analysis have identified a thin zone of highly shocked carbonate material underneath the crater floor. This zone has a maximum depth of approximately 200 ft below sea floor at the ground zero borehole and decreases in depth towards the crater rim. A layer of highly shocked material is also found on the surface in the vicinity of the reference bolehole, located outside the crater. This material could represent a fallout layer. The ejecta samples have experienced a range of shock pressures.

It was also demonstrated that the EPR technique is feasible for the study of terrestrial impact craters formed in carbonate bedrock. The results for the Meteor Crater analysis suggest a slight degree of shock damage present in the β member of the Kaibab Formation exposed in the crater walls.

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.

Surface effects on spinwave resonance in thin magnetic films

Over the past few decades, ferromagnetic spinwave resonance in magnetic thin films has been used as a tool for studying the properties of magnetic materials. A full understanding of the boundary conditions at the surface of the magnetic material is extremely important. Such an understanding has been the general objective of this thesis. The approach has been to investigate various hypotheses of the surface condition and to compare the results of these models with experimental data. The conclusion is that the boundary conditions are largely due to thin surface regions with magnetic properties different from the bulk. In the calculations these regions were usually approximated by uniform surface layers; the spins were otherwise unconstrained except by the same mechanisms that exist in the bulk (i.e., no special "pinning" at the surface atomic layer is assumed). The variation of the ferromagnetic spinwave resonance spectra in YIG films with frequency, temperature, annealing, and orientation of applied field provided an excellent experimental basis for the study.

This thesis can be divided into two parts. The first part is ferromagnetic resonance theory; the second part is the comparison of calculated with experimental data in YIG films. Both are essential in understanding the conclusion that surface regions with properties different from the bulk are responsible for the resonance phenomena associated with boundary conditions.

The theoretical calculations have been made by finding the wave vectors characteristic of the magnetic fields inside the magnetic medium, and then combining the fields associated with these wave vectors in superposition to match the specified boundary conditions. In addition to magnetic boundary conditions required for the surface layer model, two phenomenological magnetic boundary conditions are discussed in detail. The wave vectors are easily found by combining the Landau-Lifshitz equations with Maxwell's equations. Mode positions are most easily predicted from the magnetic wave vectors obtained by neglecting damping, conductivity, and the displacement current. For an insulator where the driving field is nearly uniform throughout the sample, these approximations permit a simple yet accurate calculation of the mode intensities. For metal films this calculation may be inaccurate but the mode positions are still accurately described. The techniques necessary for calculating the power absorbed by the film under a specific excitation including the effects of conductivity, displacement current and damping are also presented.

In the second part of the thesis the properties of magnetic garnet materials are summarized and the properties believed associated with the two surface regions of a YIG film are presented. Finally, the experimental data and calculated data for the surface layer model and other proposed models are compared. The conclusion of this study is that the remarkable variety of spinwave spectra that arises from various preparation techniques and subsequent treatments can be explained by surface regions with magnetic properties different from the bulk.

Spin dynamics of pulsed nuclear magnetic double resonance in solids

In the first part of this thesis, experiments utilizing an NMR phase interferometric concept are presented. The spinor character of two-level systems is explicitly demonstrated by using this concept. Following this is the presentation of an experiment which uses this same idea to measure relaxation times of off-diagonal density matrix elements corresponding to magnetic-dipole-forbidden transitions in a ^(13)C-^1H, AX spin system. The theoretical background for these experiments and the spin dynamics of the interferometry are discussed also.

The second part of this thesis deals with NMR dipolar modulated chemical shift spectroscopy, with which internuclear bond lengths and bond angles with respect to the chemical shift principal axis frame are determined from polycrystalline samples. Experiments using benzene and calcium formate verify the validity of the technique in heteronuclear (^(13)C-^1H) systems. Similar experiments on powdered trichloroacetic acid confirm the validity in homonuclear (^1H- ^1H) systems. The theory and spin dynamics are explored in detail, and the effects of a number of multiple pulse sequences are discussed.

The last part deals with an experiment measuring the ^(13)C chemical shift tensor in K_2Pt(CN)_4Br_(0.3) • 3H_2O, a one-dimensional conductor. The ^(13)C spectra are strongly affected by ^(14)N quadrupolar interactions via the ^(13)C - ^(14)N dipolar interaction. Single crystal rotation spectra are shown.

An appendix discussing the design, construction, and performance of a single-coil double resonance NMR sample probe is included.

Upper hybrid resonance absorption and scattering from a plasma column

The electromagnetic scattering and absorption properties of small (kr~1/2) inhomogeneous magnetoplasma columns are calculated via the full set of Maxwell's equations with tensor dielectric constitutive relation. The cold plasma model with collisional damping is used to describe the column. The equations are solved numerically, subject to boundary conditions appropriate to an infinite parallel strip line and to an incident plane wave. The results are similar for several density profiles and exhibit semiquantitative agreement with measurements in waveguide. The absorption is spatially limited, especially for small collision frequency, to a narrow hybrid resonant layer and is essentially zero when there is no hybrid layer in the column. The reflection is also enhanced when the hybrid layer is present, but the value of the reflection coefficient is strongly modified by the presence of the glass tube. The nature of the solutions and an extensive discussion of the conditions under which the cold collisional model should yield valid results is presented.

Geochemistry and resonance ionization of platinum-group elements

Experimental studies were conducted with the goals of 1) determining the origin of Pt- group element (PGE) alloys and associated mineral assemblages in refractory inclusions from meteorites and 2) developing a new ultrasensitive method for the in situ chemical and isotopic analysis of PGE. A general review of the geochemistry and cosmochemistry of the PGE is given, and specific research contributions are presented within the context of this broad framework.

An important step toward understanding the cosmochemistry of the PGE is the determination of the origin of POE-rich metallic phases (most commonly εRu-Fe) that are found in Ca, AJ-rich refractory inclusions (CAI) in C3V meteorites. These metals occur along with γNi-Fe metals, Ni-Fe sulfides and Fe oxides in multiphase opaque assemblages. Laboratory experiments were used to show that the mineral assemblages and textures observed in opaque assemblages could be produced by sulfidation and oxidation of once homogeneous Ni-Fe-PGE metals. Phase equilibria, partitioning and diffusion kinetics were studied in the Ni-Fe-Ru system in order to quantify the conditions of opaque assemblage formation. Phase boundaries and tie lines in the Ni-Fe-Ru system were determined at 1273, 1073 and 873K using an experimental technique that allowed the investigation of a large portion of the Ni-Fe-Ru system with a single experiment at each temperature by establishing a concentration gradient within which local equilibrium between coexisting phases was maintained. A wide miscibility gap was found to be present at each temperature, separating a hexagonal close-packed εRu-Fe phase from a face-centered cubic γNi-Fe phase. Phase equilibria determined here for the Ni-Fe-Ru system, and phase equilibria from the literature for the Ni-Fe-S and Ni-Fe-O systems, were compared with analyses of minerals from opaque assemblages to estimate the temperature and chemical conditions of opaque assemblage formation. It was determined that opaque assemblages equilibrated at a temperature of ~770K, a sulfur fugacity 10 times higher than an equilibrium solar gas, and an oxygen fugacity 10⁶ times higher than an equilibrium solar gas.

Diffusion rates between -γNi-Fe and εRu-Fe metal play a critical role in determining the time (with respect to CAI petrogenesis) and duration of the opaque assemblage equilibration process. The diffusion coefficient for Ru in Ni (D^Ru_Ni) was determined as an analog for the Ni-Fe-Ru system by the thin-film diffusion method in the temperature range of 1073 to 1673K and is given by the expression:

D^Ru_Ni (cm² sec^-1) = 5.0(±0.7) x 10^-3 exp(-2.3(±0.1) x 10¹² erg mole^-1/RT) where R is the gas constant and T is the temperature in K. Based on the rates of dissolution and exsolution of metallic phases in the Ni-Fe-Ru system it is suggested that opaque assemblages equilibrated after the melting and crystallization of host CAI during a metamorphic event of ≥ 10³ years duration. It is inferred that opaque assemblages originated as immiscible metallic liquid droplets in the CAI silicate liquid. The bulk compositions of PGE in these precursor alloys reflects an early stage of condensation from the solar nebula and the partitioning of V between the precursor alloys and CAI silicate liquid reflects the reducing nebular conditions under which CAI were melted. The individual mineral phases now observed in opaque assemblages do not preserve an independent history prior to CAI melting and crystallization, but instead provide important information on the post-accretionary history of C3V meteorites and allow the quantification of the temperature, sulfur fugacity and oxygen fugacity of cooling planetary environments. This contrasts with previous models that called upon the formation of opaque assemblages by aggregation of phases that formed independently under highly variable conditions in the solar nebula prior to the crystallization of CAI.

Analytical studies were carried out on PGE-rich phases from meteorites and the products of synthetic experiments using traditional electron microprobe x-ray analytical techniques. The concentrations of PGE in common minerals from meteorites and terrestrial rocks are far below the ~100 ppm detection limit of the electron microprobe. This has limited the scope of analytical studies to the very few cases where PGE are unusually enriched. To study the distribution of PGE in common minerals will require an in situ analytical technique with much lower detection limits than any methods currently in use. To overcome this limitation, resonance ionization of sputtered atoms was investigated for use as an ultrasensitive in situ analytical technique for the analysis of PGE. The mass spectrometric analysis of Os and Re was investigated using a pulsed primary Ar⁺ ion beam to provide sputtered atoms for resonance ionization mass spectrometry. An ionization scheme for Os that utilizes three resonant energy levels (including an autoionizing energy level) was investigated and found to have superior sensitivity and selectivity compared to nonresonant and one and two energy level resonant ionization schemes. An elemental selectivity for Os over Re of ≥ 10³ was demonstrated. It was found that detuning the ionizing laser from the autoionizing energy level to an arbitrary region in the ionization continuum resulted in a five-fold decrease in signal intensity and a ten-fold decrease in elemental selectivity. Osmium concentrations in synthetic metals and iron meteorites were measured to demonstrate the analytical capabilities of the technique. A linear correlation between Os⁺ signal intensity and the known Os concentration was observed over a range of nearly 10⁴ in Os concentration with an accuracy of ~ ±10%, a millimum detection limit of 7 parts per billion atomic, and a useful yield of 1%. Resonance ionization of sputtered atoms samples the dominant neutral-fraction of sputtered atoms and utilizes multiphoton resonance ionization to achieve high sensitivity and to eliminate atomic and molecular interferences. Matrix effects should be small compared to secondary ion mass spectrometry because ionization occurs in the gas phase and is largely independent of the physical properties of the matrix material. Resonance ionization of sputtered atoms can be applied to in situ chemical analysis of most high ionization potential elements (including all of the PGE) in a wide range of natural and synthetic materials. The high useful yield and elemental selectivity of this method should eventually allow the in situ measurement of Os isotope ratios in some natural samples and in sample extracts enriched in PGE by fire assay fusion.

Phase equilibria and diffusion experiments have provided the basis for a reinterpretation of the origin of opaque assemblages in CAI and have yielded quantitative information on conditions in the primitive solar nebula and cooling planetary environments. Development of the method of resonance ionization of sputtered atoms for the analysis of Os has shown that this technique has wide applications in geochemistry and will for the first time allow in situ studies of the distribution of PGE at the low concentration levels at which they occur in common minerals.

Ferromagnetic Resonance Force Microscopy

A new approach to magnetic resonance was introduced in 1992 based upon detection of spin-induced forces by J. Sidles [1]. This technique, now called magnetic resonance force microscopy (MRFM), was first demonstrated that same year via electron paramagnetic resonance (EPR) by D. Rugar et al. [2]. This new method combines principles of magnetic resonance with those of scanned probe technology to detect spin resonance through mechanical, rather than inductive, means. In this thesis the development and use of ferromagnetic resonance force microscopy (FMRFM) is described. This variant of MRFM, which allows investigation of ferromagnetic samples, was first demonstrated in 1996 by Z. Zhang et al. [3]. FMRFM enables characterization of (a) the dynamic magnetic properties of microscale magnetic devices, and (b) the spatial dependence of ferromagnetic resonance within a sample. Both are impossible with conventional ferromagnetic resonance techniques.

Ferromagnetically coupled systems, however, pose unique challenges for force detection. In this thesis the attainable spatial resolution - and the underlying physical mechanisms that determine it - are established. We analyze the dependence of the magnetostatic modes upon sample dimensions using a series of microscale yttrium iron garnet (YIG) samples. Mapping of mode amplitudes within these sample is attained with an unprecedented spatial resolution of 15μm. The modes, never before analyzed on this scale, fit simple models developed in this thesis for samples of micron dimensions. The application of stronger gradient fields induces localized perturbation of the ferromagnetic resonance modes. The first demonstrations of this effect are presented in this study, and a simple theoretical model is developed to explain our observations. The results indicate that the characteristics of the locally-detected ferromagnetic modes are still largely determined by the external fields and dimensions of the entire sample, rather than by the localized interaction volume (i.e., the locale most strongly affected by the local gradient field). Establishing this is a crucial first step toward understanding FMRFM in the high gradient field limit where the dispersion relations become locally determined. In this high gradient field regime, FMRFM imaging becomes analogous with that of EPR MRFM.

FMRFM has also been employed to characterize magnetic multilayers, similar to those utilized in giant magnetoresistance (GMR) devices, on a lateral scale 40 x 40μm. This is orders of magnitude smaller than possible via conventional methods. Anisotropy energies, thickness, and interface qualities of individual layers have been resolved.

This initial work clearly demonstrates the immense and unique potential that FMRFM offers for characterizing advanced magnetic nanostructures and magnetic devices.

Multipole moments in general relativity and dynamical perturbations of black-hole magnetospheres

This thesis consists of two parts. In Part I, we develop a multipole moment formalism in general relativity and use it to analyze the motion and precession of compact bodies. More specifically, the generic, vacuum, dynamical gravitational field of the exterior universe in the vicinity of a freely moving body is expanded in positive powers of the distance r away from the body's spatial origin (i.e., in the distance r from its timelike-geodesic world line). The expansion coefficients, called "external multipole moments,'' are defined covariantly in terms of the Riemann curvature tensor and its spatial derivatives evaluated on the body's central world line. In a carefully chosen class of de Donder coordinates, the expansion of the external field involves only integral powers of r ; no logarithmic terms occur. The expansion is used to derive higher-order corrections to previously known laws of motion and precession for black holes and other bodies. The resulting laws of motion and precession are expressed in terms of couplings of the time derivatives of the body's quadrupole and octopole moments to the external moments, i.e., to the external curvature and its gradient.

In part II, we study the interaction of magnetohydrodynamic (MHD) waves in a black-hole magnetosphere with the "dragging of inertial frames" effect of the hole's rotation - i.e., with the hole's "gravitomagnetic field." More specifically: we first rewrite the laws of perfect general relativistic magnetohydrodynamics (GRMHD) in 3+1 language in a general spacetime, in terms of quantities (magnetic field, flow velocity, ...) that would be measured by the ''fiducial observers” whose world lines are orthogonal to (arbitrarily chosen) hypersurfaces of constant time. We then specialize to a stationary spacetime and MHD flow with one arbitrary spatial symmetry (e.g., the stationary magnetosphere of a Kerr black hole); and for this spacetime we reduce the GRMHD equations to a set of algebraic equations. The general features of the resulting stationary, symmetric GRMHD magnetospheric solutions are discussed, including the Blandford-Znajek effect in which the gravitomagnetic field interacts with the magnetosphere to produce an outflowing jet. Then in a specific model spacetime with two spatial symmetries, which captures the key features of the Kerr geometry, we derive the GRMHD equations which govern weak, linealized perturbations of a stationary magnetosphere with outflowing jet. These perturbation equations are then Fourier analyzed in time t and in the symmetry coordinate x, and subsequently solved numerically. The numerical solutions describe the interaction of MHD waves with the gravitomagnetic field. It is found that, among other features, when an oscillatory external force is applied to the region of the magnetosphere where plasma (e⁺e^-) is being created, the magnetosphere responds especially strongly at a particular, resonant, driving frequency. The resonant frequency is that for which the perturbations appear to be stationary (time independent) in the common rest frame of the freshly created plasma and the rotating magnetic field lines. The magnetosphere of a rotating black hole, when buffeted by nonaxisymmetric magnetic fields anchored in a surrounding accretion disk, might exhibit an analogous resonance. If so then the hole's outflowing jet might be modulated at resonant frequencies ω=(m/2) Ω_H where m is an integer and Ω_H is the hole's angular velocity.

Relativistic mean field theory: methods and applications

We develop a method for performing one-loop calculations in finite systems that is based on using the WKB approximation for the high energy states. This approximation allows us to absorb all the counterterms analytically and thereby avoids the need for extreme numerical precision that was required by previous methods. In addition, the local approximation makes this method well suited for self-consistent calculations. We then discuss the application of relativistic mean field methods to the atomic nucleus. Self-consistent, one loop calculations in the Walecka model are performed and the role of the vacuum in this model is analyzed. This model predicts that vacuum polarization effects are responsible for up to five percent of the local nucleon density. Within this framework the possible role of strangeness degrees of freedom is studied. We find that strangeness polarization can increase the kaon-nucleus scattering cross section by ten percent. By introducing a cutoff into the model, the dependence of the model on short-distance physics, where its validity is doubtful, is calculated. The model is very sensitive to cutoffs around one GeV.

I. Thermochemistry and reaction kinetics of disolvated protons by ion cyclotron resonance spectroscopy. II. Thermochemical studies of small fluorocarbons by photoionization mass spectrometry

The disolvated proton, H(OH₂)₂⁺ is employed as a chemical reagent in low pressure (˂ 10^-5 torr) investigations by ion cyclotron resonance spectroscopy. Since termolecular reactions are absent at low pressure, disolvated protons are not generally observed. However H(OH₂)₂⁺ is produced in a sequence of bimolecular reactions in mixtures containing H₂O and one of a small number of organohalide precursors. Then a series of hydrated Lewis bases is produced by H₃O⁺ transfer from H(OH₂)₂⁺. In Chapter II, the relative stability of hydrated bases containing heteroatoms of both first and second row elements is determined from the preferred direction of H₃O⁺ transfer between BH(OH₂)⁺ complexes. S and P containing bases are shown to bind H₃O⁺ more weakly than O and N bases with comparable proton affinities. A simple model of hydrogen bonding is proposed to account for these observations.

H⁺ transfer from H(OH₂)₂⁺ to several Lewis bases also occurs at low pressure. In Chapter III the relative importance of H₃O⁺ transfer and H⁺ transfer from H(OH₂)₂⁺ to a series of bases is observed to be a function of base strength. Beginning with CH₃COOH, the weakest base for which H⁺ transfer is observed, the importance of H⁺ transfer increases with increasing proton affinity of the acceptor base. The nature of neutral products formed from H(OH₂)₂⁺ by loss of H⁺ is also considered.

Chapters IV and V deal with thermochemistry of small fluorocarbons determined by photoionization mass spectrometry. The enthalpy of formation of CF₂ is considered in Chapter IV. Photoionization of perfluoropropylene, perfluorocyclopropane, and trifluoromethyl benzene yield onsets for ions formed by loss of a CF₂ neutral fragment. Earlier determinations of ΔH^°_f298 (CF₂) are reinterpreted using updated thermochemical values and compared with results of this study. The heat of formation of neutral perfluorocyclopropane is also derived. Finally, the energetics of interconversion of perfluoropropylene and perfluorocyclopropane are considered for both the neutrals and their molecular ions.

In Chapter V the heats of formation of CF₃⁺ and CF₃I⁺are derived from photoionization of CF₃I. These are considered with respect to ion-molecule reactions observed in CF₃I monitored by the techniques of ion cyclotron resonance spectroscopy. Results obtained in previous experiments are also compared.

Toward Understanding Astrophysical Phenomena

Fast radio bursts (FRBs), a novel type of radio pulse, whose physics is not yet understood at all. Only a handful of FRBs had been detected when we started this project. Taking account of the scant observations, we put physical constraints on FRBs. We excluded proposals of a galactic origin for their extraordinarily high dispersion measures (DM), in particular stellar coronas and HII regions. Therefore our work supports an extragalactic origin for FRBs. We show that the resolved scattering tail of FRB 110220 is unlikely to be due to propagation through the intergalactic plasma. Instead the scattering is probably caused by the interstellar medium in the FRB's host galaxy, and indicates that this burst sits in the central region of that galaxy. Pulse durations of order $\ms$ constrain source sizes of FRBs implying enormous brightness temperatures and thus coherent emission. Electric fields near FRBs at cosmological distances would be so strong that they could accelerate free electrons from rest to relativistic energies in a single wave period. When we worked on FRBs, it was unclear whether they were genuine astronomical signals as distinct from `perytons', clearly terrestrial radio bursts, sharing some common properties with FRBs. Recently, in April 2015, astronomers discovered that perytons were emitted by microwave ovens. Radio chirps similar to FRBs were emitted when their doors opened while they were still heating. Evidence for the astronomical nature of FRBs has strengthened since our paper was published. Some bursts have been found to show linear and circular polarizations and Faraday rotation of the linear polarization has also been detected. I hope to resume working on FRBs in the near future. But after we completed our FRB paper, I decided to pause this project because of the lack of observational constraints.

The pulsar triple system, J0733+1715, has its orbital parameters fitted to high accuracy owing to the precise timing of the central $\ms$ pulsar. The two orbits are highly hierarchical, namely $P_{\mathrm{orb,1}}\ll P_{\mathrm{orb,2}}$, where 1 and 2 label the inner and outer white dwarf (WD) companions respectively. Moreover, their orbital planes almost coincide, providing a unique opportunity to study secular interaction associated purely with eccentricity beyond the solar system. Secular interaction only involves effect averaged over many orbits. Thus each companion can be represented by an elliptical wire with its mass distributed inversely proportional to its local orbital speed. Generally there exists a mutual torque, which vanishes only when their apsidal lines are parallel or anti-parallel. To maintain either mode, the eccentricity ratio, $e_1/e_2$, must be of the proper value, so that both apsidal lines precess together. For J0733+1715, $e_1\ll e_2$ for the parallel mode, while $e_1\gg e_2$ for the anti-parallel one. We show that the former precesses $\sim 10$ times slower than the latter. Currently the system is dominated by the parallel mode. Although only a little anti-parallel mode survives, both eccentricities especially $e_1$ oscillate on $\sim 10^3\yr$ timescale. Detectable changes would occur within $\sim 1\yr$. We demonstrate that the anti-parallel mode gets damped $\sim 10^4$ times faster than its parallel brother by any dissipative process diminishing $e_1$. If it is the tidal damping in the inner WD, we proceed to estimate its tidal quantity parameter ($Q$) to be $\sim 10^6$, which was poorly constrained by observations. However, tidal damping may also happen during the preceding low-mass X-ray binary (LMXB) phase or hydrogen thermal nuclear flashes. But, in both cases, the inner companion fills its Roche lobe and probably suffers mass/angular momentum loss, which might cause $e_1$ to grow rather than decay.

Several pairs of solar system satellites occupy mean motion resonances (MMRs). We divide these into two groups according to their proximity to exact resonance. Proximity is measured by the existence of a separatrix in phase space. MMRs between Io-Europa, Europa-Ganymede and Enceladus-Dione are too distant from exact resonance for a separatrix to appear. A separatrix is present only in the phase spaces of the Mimas-Tethys and Titan-Hyperion MMRs and their resonant arguments are the only ones to exhibit substantial librations. When a separatrix is present, tidal damping of eccentricity or inclination excites overstable librations that can lead to passage through resonance on the damping timescale. However, after investigation, we conclude that the librations in the Mimas-Tethys and Titan-Hyperion MMRs are fossils and do not result from overstability.

Rubble piles are common in the solar system. Monolithic elements touch their neighbors in small localized areas. Voids occupy a significant fraction of the volume. In a fluid-free environment, heat cannot conduct through voids; only radiation can transfer energy across them. We model the effective thermal conductivity of a rubble pile and show that it is proportional the square root of the pressure, $P$, for $P\leq \epsy^3\mu$ where $\epsy$ is the material's yield strain and $\mu$ its shear modulus. Our model provides an excellent fit to the depth dependence of the thermal conductivity in the top $140\,\mathrm{cm}$ of the lunar regolith. It also offers an explanation for the low thermal inertias of rocky asteroids and icy satellites. Lastly, we discuss how rubble piles slow down the cooling of small bodies such as asteroids.

Electromagnetic (EM) follow-up observations of gravitational wave (GW) events will help shed light on the nature of the sources, and more can be learned if the EM follow-ups can start as soon as the GW event becomes observable. In this paper, we propose a computationally efficient time-domain algorithm capable of detecting gravitational waves (GWs) from coalescing binaries of compact objects with nearly zero time delay. In case when the signal is strong enough, our algorithm also has the flexibility to trigger EM observation {\it before} the merger. The key to the efficiency of our algorithm arises from the use of chains of so-called Infinite Impulse Response (IIR) filters, which filter time-series data recursively. Computational cost is further reduced by a template interpolation technique that requires filtering to be done only for a much coarser template bank than otherwise required to sufficiently recover optimal signal-to-noise ratio. Towards future detectors with sensitivity extending to lower frequencies, our algorithm's computational cost is shown to increase rather insignificantly compared to the conventional time-domain correlation method. Moreover, at latencies of less than hundreds to thousands of seconds, this method is expected to be computationally more efficient than the straightforward frequency-domain method.

Geometrical effects on the resonance absorption of neutrons

An investigation was conducted to estimate the error when the flat-flux approximation is used to compute the resonance integral for a single absorber element embedded in a neutron source.

The investigation was initiated by assuming a parabolic flux distribution in computing the flux-averaged escape probability which occurs in the collision density equation. Furthermore, also assumed were both wide resonance and narrow resonance expressions for the resonance integral. The fact that this simple model demonstrated a decrease in the resonance integral motivated the more detailed investigation of the thesis.

An integral equation describing the collision density as a function of energy, position and angle is constructed and is subsequently specialized to the case of energy and spatial dependence. This equation is further simplified by expanding the spatial dependence in a series of Legendre polynomials (since a one-dimensional case is considered). In this form, the effects of slowing-down and flux depression may be accounted for to any degree of accuracy desired. The resulting integral equation for the energy dependence is thus solved numerically, considering the slowing down model and the infinite mass model as separate cases.

From the solution obtained by the above method, the error ascribable to the flat-flux approximation is obtained. In addition to this, the error introduced in the resonance integral in assuming no slowing down in the absorber is deduced. Results by Chernick for bismuth rods, and by Corngold for uranium slabs, are compared to the latter case, and these agree to within the approximations made.

Applications of nuclear magnetic resonance spectroscopy to the study of medium-sized rings. I. Conformational properties of cycloheptane. II. Conformational properties of cycloöctane

Conformational equilibrium in medium-sized rings has been investigated by the temperature variation of the fluorine-19 n.m.r. spectra of 1, 1-difluorocycloalkanes and various substituted derivatives of them. Inversion has been found to be fast on the n.m.r. time scale at -180˚ for 1, 1-difluorocycloheptane, but slow for 1, 1-difluoro-4, 4-dimethylcycloheptane at -150˚. At low temperature, the latter compound affords a single AB pattern with a chemical-shift difference of 841 cps. which has been interpreted in terms of the twist-chair conformation with the methyl groups on the axis position and the fluorine atoms in the 4-position. At room temperature, the n.m.r. spectrum of 1, 1-difluoro-4-t-butylcycloheptane affords an AB pattern with a chemical-shift difference of 185 cps. The presence of distinct trans and gauche couplings from the adjacent hydrogens has been interpreted to suggest the existence of a single predominant form, the twist chair with the fluorine atoms on the axis position.

Investigation of 1, 1-difluorocycloöctane and 1, 1, 4, 4-tetrafluorocycloöctane has led to the detection of two kinetic processes both having activation energies of 8-10 kcal./mole but quite different A values. In light of these results eleven different conformations of cycloöctane along with a detailed description of the ways in which they may be interconverted are discussed. An interpretation involving the twist-boat conformation rapidly equilibrating through the saddle and the parallel-boat forms at room temperature is compatible with the results.