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Part I Electrochemical charge transfer at a metallic electrode: a simulation study The factors which affect the rate of heterogeneous electron transfer at a metallic electrode in the context of Marcus theory are investigated through molecular dynamics simulations. The system consists of the ionic melt K3Eu2+ 0:5Eu3+ 0:5Cl5:5 sandwiched between two parallel plate platinum electrodes held at a preset electrical potential. The charges on the electrode atoms are variationally obtained through the method of Siepmann and Sprik [J. Chem. Phys. 102, 511 (1995)] which models the polarization of the electrode by the melt and maintains the condition of constant potential. A two-dimensional Ewald summation is employed to ensure that the absolute value of the potential is known, and the expressions derived by Kawata and Mikami [Chem. Phys. Lett. 340, 157 (2001)] are extended to allow for induced dipoles on the melt ions by their mutual interaction and the interaction with the electrode surface. The Marcus free energy curves are calculated for electron transfer events between a europium ion and the metallic electrode, and their dependence on the position of the redox ion and the applied potential examined. The system is consistently found to be in accord with the linear response regime. A moderately-ranged oscillatory character in the mean electrical (Poisson) potential is observed extending into the fluid, which is in marked disagreement with the predictions of existing mean-field (Gouy-Chapman) predictions. These oscillations are found not to be reflected in the calculated Helmholtz reaction free energy, which indicates that the Poisson potential is not the appropriate potential for discussions of the kinetics of electrode processes. The strong dependence of the reorganization energy on the position of the redox ion is traced to the image charge effect, and appears insensitive to the polarizability of the anion. Following the evolution of the Eu{Cl radial distribution function throughout a redox process reveals that the bond length in the transition complex is exactly in between those of the ground state reactant and product complexes. The potentials of mean force for the approach of a Eu2+ and Eu3+ ion to the electrode calculated through umbrella sampling are found to be in quantitative agreement with those calculated through the position-dependence of the respective concentration profiles. A method to parameterize a model of the interactions between the melt ions and the electrode surface from ab initio density functional theory calculations is described. The method is used to obtain a suitable interaction model for a system consisting of a LiCl liquid electrolyte and a solid aluminium electrode. The electrolyte is found to exhibit a potential-driven phase transition which involves the commensurate ordering of the electrolyte ions with the electrode surface; this leads to a maximum in the differential capacitance as a function of applied potential. Away from the phase transition the capacitance was found to be independent of the applied potential. Part II Are dipolar liquids ferroelectric? The observation of a very sharp low frequency spike in the hyper-Rayleigh spectrum (HRS) of strongly dipolar fluids, such as acetonitrile and water, has been interpreted as reflecting a very slowly relaxing component in the transverse dipole density. This suggestion is at variance with the expectation of dielectric theory for an isotropic fluid and has led to the speculation that the slow relaxation is associated with the reorganization of ferroelectric domains. Very large-scale molecular dynamics simulation ( 28000 molecules) have been carried out using a 3-site potential model of acetonitrile. The simulated fluid shows no suggestion of strong dipole correlations and domain structure. The dipole density correlations behave as predicted by normal dielectric theory and their spectra do not show the low-frequency feature seen in the HRS. In order to examine the characteristics of the spectra which would be seen in a ferroelectric domain, the acetontrile model was transmuted to more closely resemble a Stockmayer-like fluid with the same dipole density and a ferroelectric phase was observed. In this phase the dielectric spectra show (i) a high-frequency spectral feature due to librational motion of the molecules within a domain, and (ii) slowly-relaxing longitudinal and transverse polar modes, again at variance from the experimental HRS characteristics.

A thesis submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Doctor of Philosophy. Johannesburg, May 23, 2014. / A systematic experimental investigation was performed of the phenomenon of fine structure, with emphasis on the region of the Isoscalar Giant Quadrupole Resonance (ISGQR), in nuclei across stable even-even neodymium isotopes. The 200 MeV proton beams were delivered by the Separated Sector Cyclotron (SSC) facility of iThemba Laboratory for Accelerator Based Sciences (iThemba LABS). Measurements were made using the state-of-the-art K = 600 magnetic spectrometer, where unique high energy-resolution ( E ≈ 42 − 48 keV FWHM) proton inelastic scattering results were obtained on 142Nd, 144Nd, 146Nd, 148Nd and 150Nd targets. All measurements were taken at θLab = 8◦, where the cross-section of the ISGQR is at a maximum. An additional measurement was also made for the 142Nd at θLab = 7◦. Nuclei with mass number A ≈ 150 and neutron number N ≈ 90 are of special interest since they occupy that region of the nuclide chart wherein the onset of permanent prolate deformation occurs. The stable neodymium (Z = 60) isotopes have been chosen in the present study in order to investigate the effects accompanying the onset of deformation on the excitation energy spectra in the ISGQR region (9 ≤ Ex ≤ 15 MeV). The neodymium isotopes extend from the semi-magic N = 82 nucleus (142Nd) to the permanently deformed N = 90 (150Nd) nucleus. In order to emphasize the ISGQR in the measured excitation energy spectra, a Discrete Wavelet Transform (DWT) background subtraction was carried out. This model independent method for background determination decomposes the spectrum into various approximations and details through the application of high pass and low pass filters. A comparison of the resonance widths extracted shows a systematic broadening of the ISGQR (􀀀 = 3.220 MeV to 5.100 MeV), moving from spherical 142Nd to highly deformed 150Nd nuclei as has already been observed for the Isovector Giant Dipole Resonance (IVGDR) excited by γ-capture. Even though it is known that the IVGDR spectacularly splits and shows a double bump for the deformed 150Nd, no obvious splitting of the ISGQR was observed. In order to investigate the fine structure of the ISGQR, a theoretical microscopic calculation termed the Quasiparticle-Phonon Model (QPM) was applied to predict excitation energy spectra for 142−146Nd targets. These calculations were based on the one- plus two-phonon configuration. Characteristic energy scales were extracted for the resonance region using the Continuous Wavelet Transform (CWT) technique, on both experimental data and theoretical predictions. Comparison of the resulting characteristic energy scales suggests the coupling to low-lying collective vibrations as the dominant contributor to the ISGQR decay width. Level densities of 2+ states were extracted through the application of a fluctuation analysis technique, for full spectra from the ground state upwards in all five Nd targets. Comparisons are made with theoretical predictions from the Back Shifted Fermi Gas, Hartree-Fock-BCS and Hartree-Fock-Bogoluibov models. While there is generally an excellent agreement between experimental level densities and theoretical predictions from the ground state up to less than 10 MeV excitation, there is a marked disagreement beyond 10 MeV in all target nuclei. Comparison of the experimental results for the Nd isotope chain shows a clear systematic trend in which the onset of this disagreement occurs at lower and lower excitation energies, moving from low to high mass. For the spherical 142Nd nucleus the deviation occurs at about 9 MeV while in the case of the deformed 150Nd this occurs much earlier at about 4 MeV, all limited to a maximum of 103 MeV−1 by the energy resolution of the present experiment. Additionally, measurements of elastic scattering and inelastic excitation of lowlying collective states in 144−150Nd has also been possible. Excitation energy spectra in all targets predominantly exhibited various 2+ states, owing to the “spin-filter” effects. A single strong 3− 1 state, together with a weak 4+ 1 state were observed in each target nucleus. Angular distributions were obtained for the various ground and excited states by applying the optical model of elastic scattering and Distorted Wave Born Approximation (DWBA) of inelastic scattering. Deformation lengths δL were obtained for most of the states and these were in good agreement with previously obtained results from the literature.

Approved for public release; distribution is unlimited / Reissued 30 May 2017 with Second Reader’s non-NPS affiliation added to title page. / The scalar reciprocity equation commonly stated in underwater acoustics relates pressure fields and monopole sources. It is often used to predict the pressure measured by a hydrophone for multiple source locations by placing a source at the hydrophone location and calculating the field everywhere for that source. That method, however, does not work when calculating the orthogonal components of the velocity field measured by a fixed receiver. This thesis derives a vector-scalar reciprocity equation that accounts for both monopole and dipole sources. This equation can be used to calculate individual components of the received vector field by altering the source type used in the propagation calculation. This enables a propagation model to calculate the received vector field components for an arbitrary number of source locations with a single model run for each received field component instead of requiring one model run for each source location. Application of the vector-scalar reciprocity principle is demonstrated with analytic solutions for a range-independent environment and with numerical solutions for a range-independent and a range-dependent environment using a parabolic equation model. / Electronics Engineer, Naval Undersea Warfare Center

The Faraday rotation spectrum of composites containing magnetite nanoparticles is found to be dependent on the interparticle spacing of the constituent nanoparticles. The composite materials are prepared by combining chemicallysynthesized Fe3O4 (magnetite) nanoparticles (8 nm diameter) and poly(methylmethacrylate) (PMMA). Composites are made containing a range of nanoparticle concentrations. The peak of the main spectral feature depends on nanoparticle concentration; this peak is observed to shift from approximately 470 nm for (dilute composites) to 560 nm (concentrated). A theory is presented based on the dipole approximation which accounts for optical coupling between magnetite particles. Qualitative correlations between theoretical calculations and experimental data suggest the shifts in spectral peak position depend on both interparticle distance and geometrical configuration.

"A small “spiralpole” antenna – the hybrid structure where one dipole wing is kept, but another wing is replaced by a coaxial single-arm spiral, is studied both theoretically and experimentally. Such a structure implies the implementation of an impedance-matching network (an inductor in series with a small dipole) directly as a part of the antenna body. The antenna impedance behavior thus resembles the impedance behavior of a small dipole in series with an extra inductance, which is that of the spiral. However, there are two improvements compared to the case when an equivalent small dipole is matched with an extra lumped inductor. First, the spiralpole antenna has a significantly larger radiation resistance – the radiation resistance increases by a factor of two or more. This is because the volume of the enclosing sphere is used more efficiently. Second, a potentially lower loss is expected since we only need a few turns of a greater radius. The radiation pattern of a small spiralpole antenna is that of a small dipole, so is the first (series) resonance. The Q-factor of the antenna has been verified against the standard curves. The antenna is convenient in construction and is appealing when used in conjunction with passive RFID tags such as SAW temperature sensors. "

The exchange flow through tidal inlets generates two-dimensional large coherent vortical structures (2DLCS), that are much broader than the water depth and exist because of the inherent instability of shallow shear flows. These vortical starting jets are critical to the mixing that occurs in the inlet area. Depending on the tidal period T, the width of the inlet W, and the maximum velocity in the inlet UMAX, the mixing will vary from poor exchange to efficient exchange. Here, we present laboratory and numerical experiments that study the formation of the 2DLCS at the mouth of the inlets. Experiments were conducted at large scale, in the shallow flat-bottomed water basin at the Institute of Hydromechanics of the University of Karlsruhe, Germany, which has the capability to generate a sinusoidal flow that simulates a series of tidal cycles. A set of idealized inlets were arranged in the tank, and by varying the tidal period and the maximum velocity, three different types of life-history were obtained (stationary dipole, dipole entrains, and dipole escapes). These types of life-history are defined by the mixing number depending if KW is equal, less or greater than a critical value. The experiments were visualized using color dye tracers. To quantify the shallow water velocity field, the Particle Image Velocimetry (PIV) technique was used. From the PIV data the vorticity field was obtained, and the regions where the vortex formed were identified. Then, a vortex time-evolution analysis was developed using iv physical parameters such as the position on the basin of the vortex, the equivalent diameter, and the maximum vorticity among others. The mixing number accurately predicts the behavior of the vortex for the first cycle on idealized inlets for the subsequent cycles; the structures behave differently than predicted by KW, because the blocking effect of the vortex /formed in the previous cycle. For characteristic times t*  tUWless than about 2, the dipole is attached to the inlet and forms rapidly. For later times, the dipole advects downstream, and slowly dissipates. Numerical experiments are also presented. Comparing the numerical data with the laboratory data, good agreement is reached, but important limitations are identified for the grid resolution and domain size.

Estuaries depend on the transport of nutrients and sediments from the open sea to help maintain a prosperous environment. One of the major transport mechanisms is the propagation of large two dimensional vortical structures. At the mouth of an inlet, tidal flow forces the formation of two dimensional vortical structures whose lateral extent is much greater than the water depth. After the starting jet vortex dipole detaches from the inlet, secondary vortices shed due to separation from the inlet boundary and eventually reach the starting-jet dipole. An idealized inlet con figuration was utilized for laboratory experiments detailing the formation and propagation of the vortex structures with water depths of 3, 5, and 9 centimeters and flow Froude scaled to inlets along the Texas coast. Using surface particle image velocimetry, the entrainment of the secondary structures into the vortex system are shown as well as variations in characteristics such as trajectory, size, vorticity, and circulation for the vortices as they move downstream.

Thesis (Ph. D.)--Auburn University, 2008. / Abstract. Includes bibliographical references (p. 121-127).

Thesis (Ph. D.)--University of Canterbury, 2009. / Typescript (photocopy). "May 2009." Includes bibliographical references (p. 10/1-10/9). Also available via the World Wide Web.