R.D. Haun. / "January 18, 1957." Based on a thesis, M.I.T. Dept. of Physics, January 7, 1957. / Bibliography: p. 63. / Army Signal Corps Contract DA36-039-sc-64637. Dept. of the Army Task 3-99-06-108 and Project 3-99-00-100.

M.W.P. Strandberg. / "September 25, 1948." / Includes bibliographical footnotes. / Army Signal Corps Contract No. W-36-039-sc-32037 Project No. 102B. Dept. of the Army Project No. 3-99-10-022.

Thesis (Ph. D.)--University of Florida, 1982. / Description based on print version record. Typescript. Vita. Includes bibliographical references (leaves 72-74).

Semiconductor nanowires have attracted considerable attention as possible source for lasers and optical storage media. We report the fabrication and optical characterization of ZnO and CdS nanowires. The former are produced by electrochemical deposition of Zn inside nanoporous alumina films containing regimented arrays of 10nm, 25nm and 50 nm diameter pores, followed by room temperature chemical oxidization. Fluorescence spectroscopy shows different characteristics associated with different sample diameter. The 50 nm ZnO nanowires show an exciton recombination peak and an additional peak related to the deep trap levels. 25 nm ZnO nanowires show a only the exciton recombination peak, which is red shifted, possibly due to quantum confined Stark effect associated with built in charges in the alumina. This feature can be exploited to produce light emitting devices whose frequency can be modulated with an external electric field. Such devices could be novel ultra-violet frequency modulators for optical communication and solar blind materials. In addition, we have investigated fluorescence spectra of 10-, 25- and 50-nm diameter CdS nanowires (relative dielectric constant = 5.4) self assembled in a porous alumina matrix (relative dielectric constant = 8-10). The spectra reveal peaks associated with free electron-hole recombination. The 10-nm wire spectra show an additional lower energy peak due to exciton recombination. In spite of dielectric de-confinement caused by the insulator having a higher dielectric constant than the semiconductor, the exciton binding energy increases almost 8-fold from its bulk value in the 10 nm wires. This increase is most likely due to quantum confinement accruing from the fact that the exciton Bohr radius (~5 nm) is comparable to or larger than the wire radius, especially if side depletion is taken into account. Such an increase in the binding energy could be exploited to make efficient room temperature luminescent devices in the visible range.

Approved for public release, distribution is unlimited / In this thesis, the performance of a step quantum well infrared photodetector (QWIP), which was designed to detect a laser spot at 1.05 m æ and IR radiation between 9.5 m æ to 10.5 m æ, was evaluated. In the far infrared (FIR), the maximum responsivity of the test detector at 10 K was measured at 1.02 A/W with a peak wavelength of 10.3 æm under a negative bias of 0.83 V. The D* at background limited infrared performance (BLIP) was measured at 9 8.0 10 cm Hz /W with 180o field of view. The BLIP temperature was found to be about 55 K. In addition, the FIR detection wavelength found shift with the amount of bias across the device. The amount of shift observed was 0.21 meV/KVcm-1 which is due to linear Stark effect associated with the step quantum well. The quantum well infrared detectors made of square quantum wells found to have an order of magnitude lower Stark shift originated from second order effects. This suggests that the step well infrared detector can have applications in tunable wavelength infrared detectors. / Major, Republic of Singapore Navy

Cette thèse de doctorat concerne deux problèmes mathématiques issus de la mécanique quantique. On considère une particule quantique, non relativiste et sans spin, astreinte à se mouvoir sur une surface bidimensionnelle $\cal S$, plongée dans un champ magnétique homogène qui lui est perpendiculaire. Dans un premier problème, $(\cal S)=\R\times \mathbb(S)_L^1$, qui est un cylindre infini de circonférence $L$, ce qui correspond à des conditions aux bords periodiques. Dans le deuxième cas, $(\cal S)=\R^2$. En fonction du problème étudié, on ajoute un potentiel convenable. On est ainsi amené à étudier deux opérateurs de Schrödinger. Le premier opérateur analysé génère la dynamique d'une particule soumise à un potentiel aléatoire de type Anderson ainsi qu'un potentiel non aléatoire dont le but est de confiner la particule le long de l'axe du cylindre, sur une longueur $L$. Dans ce cas, on localise le spectre et on le classifie par le courant quantique porté par les fonctions propres correspondantes. On montre qu'il y a des régions spectrales où n'existent que des valeurs propres avec courant d'ordre un par rapport à $L$, et des régions spectrales où sont mélangées valeurs propres avec courant d'ordre un et valeurs propres avec courant infinitésimal par rapport à $L$. Ces resultats on un intétet physique dans le cadre de l'effect Hall entier. Le deuxième opérateur de Schrödinger étudié, correspond à la situation physique où le potentiel est donné par la somme d'un potentiel ``local'' et d'un potentiel dû à un petit champ électrique $F$ constant. Dans ce cas on montre que les états résonants induits par le champ électrique décroissent exponentiellement avec un taux donné par la partie imaginaire des valeurs propres d'un certain opérateur non auto-adjoint. On montre de plus que cette partie imaginaire possède une borne supérieure de l'ordre de $\exp(-1/F^2)$, pour $F$ tendant vers zéro. Ainsi, le temps de vie de l'état résonant en question est au moins de l'ordre de $\exp(1/F^2)$.

This paper treats a non-intrusive method of measuring electric fields in plasmas and other sensitive or hostile environments. The method is based on the use of an atomic hydrogen beam prepared in the metastable fine structure quantum state 2s1/2. Interaction with the field that is to be measured causes Stark mixing with the closely lying 2p1/2, whose spontaneous decay rate is much higher than that of 2s1/2. As a result, the total transition rate to the ground state and consequently the intensity of the Lyman-α line (121.6nm) is increased. Observations of emitted radiation from a region in which the interaction takes place are used to draw conclusions about the electric field, effectively providing a way to measure it. In the first section, the theory behind the method is described, using time dependent perturbation theory and taking into account both Lamb shift and hyperfine structure. A description of the set-up that we have used to test the theoretical predictions follows and practical aspects related to the operation of the experiment are briefly addressed. Measurements of the dependence of the Lyman-α intensity on both electric field frequency and amplitude are presented and shown to be in agreement with theory. These measurements have been performed in vacuum and in an argon plasma, both for static and RF fields. Two mechanisms, labeled oscillatory and geometrical saturation, that decrease the emitted intensity for strong fields are identified and described, and both are of importance for the future implementation of the studied diagnostic in a fusion device or other plasma experiment. Studies of the field profiles between a pair of electrically polarized plates have been carried out and algorithms for relating measured data to actual values of electric field strength have been developed. For static fields in vacuum, collected data is compensated for geometrical saturation and the resulting profiles are compared to those calculated with a finite element method. Good correspondence is seen in many cases, and where it is not, the discrepancies are explained. Static profile measurements in a plasma show the formation of a sheath whose thickness has been studied while varying discharge current, pressure and plasma frequency. The qualitative dependence of the sheath thickness on these parameters is in accordance with well established theory. When it comes to RF fields, a possible standing wave pattern is detected in the plasma despite problems with low signal to noise ratio. In order to optimize the working conditions of the set-up, effects of charge accumulation due to ions present in the hydrogen beam have been studied as well as errors due to residual particle fluxes during the off-phase when pulsing the beam. A conceptual design suggestion for implementing the method in the edge plasma of a tokamak or another similar device, based on the collected information, is also given.

The electrostatic field created by the inward pointing dipole moments of an oriented membrane leaflet has never been measured directly, but is thought to have an important influence on membrane function. Here we present the first direct measurement of the membrane dipole field in lipid bicelles using vibrational Stark effect spectroscopy which is based on the sensitivity of a nitrile oscillator’s vibrational frequency to its local electrostatic environment. The nitrile probe was introduced as the artificial amino acid p-cyanophenylalanine (CN-Phe) in four different locations of a α-helical peptide composed of alternating alanine and leucine residues. This peptide was intercalated into bicelles composed of mixtures of the long chain lipids 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), or 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and the short chain lipid 1,2-dihexanoyl-sn-glycero-3-phosphocholine (DHPC) formed in two different sizes, 5 nm and 15 nm in radius. Formation of the bicelle above the phase transition temperature of the lipid mixture was confirmed by ³¹P NMR, and the structure of the [alpha]-helix within the bicelle was confirmed by circular dichroic spectroscopy. The absorption energy of the nitrile probe at 4 positions along the helical axis was measured by Fourier transform infrared spectroscopy, from which we estimate the magnitude of the membrane dipole electrostatic field to be -6 MV/cm. Then we successfully manipulated the dipole field in q = 0.5 DMPC/DHPC bicelles by incorporating the small molecule phloretin into the membrane and measured the corresponding ratiometric fluorescence signal of the co-intercalated voltage gated dye di-8-ANEPPS. We measured 0.7 ± 0.2 cm⁻¹ blue shift in absorption energy of the nitrile probe due to the decrease in dipole field caused by phloretin, corresponding to a dipole field of -4.2 MV/cm. This change was essentially identical to what has been estimated through ratiometric fluorescence methods, indicating that VSE spectroscopy will be useful tool for measurement of the biological effects of electrostatic fields in lipid membranes. / text

Noncovalent factors, such as shape complementarity and electrostatic driving forces, almost exclusively cause the affinity and specificity for which two or more biological macromolecules organize into a functioning complex. The human oncoprotein p21Ras (Ras) and a structurally identical but functionally distant analog, Rap1A (Rap), exhibit high selectivity and specificity when binding to downstream effector proteins that cannot be explained through structural analysis alone. Both Ras and Rap bind to Ral guanine nucleotide dissociation stimulator (RalGDS) with affinities that differ tenfold instigating diverse cellular functions; it is hypothesized that this specificity of RalGDS to discriminate between GTPases is largely electrostatic in nature. To investigate this hypothesis, electrostatic fields at the binding interface between mutants of RalGDS bound to Rap or Ras are measured using vibrational Stark effect (VSE) spectroscopy, in which spectral shifts of a probe oscillator’s energy is related directly to that probe’s local electrostatic environment and measured by Fourier transform infrared spectroscopy (FTIR). After calibration, the probe is inserted into a known position in RalGDS where it becomes a highly local, sensitive, and directional reporter of fluctuations of the protein’s electrostatic field caused by structural or chemical perturbations of the protein. The thiocyanate (SCN) vibrational spectroscopic probe was systematically incorporated throughout the binding interface of RalGDS. Changes in the absorption energy of the thiocyanate probe upon binding were directly related to the change of the strength of the local electrostatic field in the immediate vicinity of the probe, thereby creating a comprehensive library of the binding interactions between Ras-RalGDS and Rap-RalGDS. The measured SCN absorption energy on the monomeric protein was compared with solvent-accessible surface area (SASA) calculations with the results highlighting the complex structural and electrostatic nature of protein-water interface. Additional SASA studies of the nine RalGDS mutants that bind to Ras or Rap verified that experimentally measured thiocyanate absorption energies are negatively correlated with exposure to water at the protein-water interface. By changing the solvent composition, we confirmed that the cyanocysteine residues that are more exposed to solvent experienced a large difference in absorption energy. These studies reinforce the hypothesis that differences in the electrostatic environment at the binding interfaces of Ras and Rap are responsible for discriminating binding partners. / text

The functional aspects of proteins are largely dictated by highly selective protein- protein and protein-ligand interactions, even in situations of high structural homology, where electrostatic factors are the major contributors to selectivity. The vibrational Stark effect (VSE) allows us to measure electrostatic fields in complex environments, such as proteins, by the introduction of a vibrational chromophore whose vibrational absorption energy is linearly sensitive to changes in the local electrostatic field. The works presented here seek to computationally quantify electrostatic fields measured via VSE, with the eventual goal of being able to quantitatively predict electrostatic fields, and therefore Stark shifts, for any given protein-interaction. This is done using extensive molecular dynamics in the Amber03 and AMOEBA force fields to generate large ensembles the GTPase Rap1a docked to RalGDS and [superscript p]²¹Ras docked to RalGDS. We discuss how side chain orientations contribute to the differential binding of different mutations of Rap1a binding to RalGDS, where it was found that a hydrogen-bonding pocket is disrupted by the mutation of position 31 from lysine to glutamic acid. We then show that multi-dimensional umbrella sampling of the probe orientations yields a wider range of accessible structures, increasing the quality of the ensembles generated. A large variety of methods for calculating electrostatic fields are presented, with Poisson- Boltzmann electrostatics yielding the most consistent, reliable results. Finally, we explore using AMOEBA for both ensemble-generation as well as the electrostatic description of atoms for field calculations, where early results suggest that the electrostatic field due to the induce dipole moment of the probe is responsible for predicting qualitatively correct Stark shifts.