The H₂O critical point defines the parabolic vertex of the p(T) vaporization boundary and, as a geometric consequence, a positive vertical asymptote for first partial derivatives of the equation of state. Convergence of these derivatives, isothermal compressibility and isobaric expansivity, to the critical asymptote effectively controls thermodynamic, electrostatic, and transport properties of fluid H₂O and dependent transport and chemical processes in hydrothermal systems. The equation of state for fluid H₂O developed by Levelt Sengers et a1. (1983a) from modern theories of revised and extended scaling affords accurate prediction of state and thermodynamic properties in the critical region. This formulation has been used together with the virial equation of state proposed by Haar et a1. (1984) and predictive equations for the static dielectric constant (Uematsu and Franck, 1980), thermal conductivity (Sengers et a1., 1984), and dynamic viscosity (Sengers and Kamgar-Parsi, 1984) to present a comprehensive summary of fluid H₂O properties within and near the critical region. Specifically, predictive formulations and computed values for twenty-one properties are presented as a series of equations, three-dimensional P-T surfaces, isothermal and isobaric crosssections, and skeleton tables from 350°-475°C and 200-450 bar. The properties considered are density, isothermal compressibility, isobaric expansivity, Helmholtz and Gibbs free energies, internal energy, enthalpy, entropy, isochoric and isobaric heat capacities, the static dielectric constant, Z, Y, and Q Born functions (Helgeson and Kirkham, 1974a), dynamic and kinematic viscosity, thermal conductivity, thermal diffusivity, the Prandtl number, the isochoric expansivity-compressibility coefficient, and sound velocity. The equations and surfaces are analyzed with particular emphasis on functional form in the near-critical region and resultant extrema that persist well beyond the critical region. Such extrema in isobaric expansivity, isobaric heat capacity, and kinematic viscosity delineate state conditions that define local maxima in fluid and convective heat fluxes in hydrothermal systems; at the critical point, these fluxes are infinite in permeable media. Extrema in the Q and Y Born functions delineate state conditions that define local minima in the standard partial molal volumes and enthalpies of aqueous ions and complexes; at the critical point, these properties are negative infinite. Because these fluxes and thermodynamic properties converge to vertical asymptotes at the critical point, seemingly trivial variations in near-critical state conditions cause large variations in fluid mass and thermal energy transfer rates and in the state of chemical equilibrium.

The oscillatory de Haas-van Alphen (DHVA) magnetization has been studied in Pt crystals containing more than 100 ppm vacancies. Magnetic fields as high as 75 kG were used. The oscillations were observed at temperatures as low as 0.45 k, and found to be strongly attenuated by the vacancies in this concentration range. The emphasis of this work is on the measurement of this attenuation for the purpose of studying conduction electron scattering due to single vacancies. Dingle (scattering) temperatures due to vacancies are reported for four cyclotron orbits with the field in a (110) plane, along with a new measurement of the cyclotron effective mass (m* = 2.31 ± 0.03) for the electron orbit 33° away from <100>. Vacancies were generated by quenching Pt single crystals from temperatures as high as 1730 °C in air, using a technique which minimizes the induced strain. The vacancy contribution to the electron scattering rate was separated by measuring the Dingle temperature in both quenched and annealed specimens which had been subjected to the same quenching process. The results suggest that there is only a moderate variation in this scattering rate over the s-p-like electron sheet of the Fermi surface. However, the scattering rate for the d-like open hole sheet, which contacts the Brillouin zone, is about 49% larger than that for the electron sheet. This anisotropy is attributed mainly to the lattice distortion around a vacancy and to the difference between the hole and electron wave-function symmetries.

This work involves the synthesis of two types of electro-optic monomers and their corresponding polymers. The first type of monomers contain the p-oxy-α-cyanocinnamate structure and were synthesized from ω-hydroxyalkoxy-substituted benzaldehydes and methyl cyanoacetate. These ω-hydroxy-α-cyanoester monomers show a high degree of electron delocalization. Copolyesters were synthesized by copolymerization of these monomers with methyl 12-hydroxydodecanoate by the standard two-stage, high-temperature polyesterification procedure. The copolyesters, incorporating dipolar units all pointing in the same direction, are soluble and solution- and melt-processable. Second harmonic generation (SHG) measurements on chloroform solutions of the copolymers showed enhancements of χ² as large as 20 relative to the dipolar monomers. These are the first known readily soluble main chain polymers that exhibit SHG behavior. The second type of monomers were acrylates containing substituted phenyl esters of benzoic acid as mesogenic (pendant) groups. Specifically, the mesogenic group contained an oxy-aryl-carboxy-aryl-carboxy-alkyl structure separated from the acrylate carbon-carbon double bond by a spacer group, which had a carboxyethyl-carboxyhexyl structure. A synthetic route was established by synthesizing a model monomer containing a 2-methylpropyl group as the alkyl group at the end of the mesogenic group. The model monomer was polymerized free radically and the resulting polymer found to possess a smectic liquid crystalline phase that became isotropic at 103° C. With the synthetic route established, an optically active monomer containing a (S)-2-methyl-1-butyl group as the alkyl group at the end of the mesogenic group was synthesized and polymerized. The optically active polymer was already in a smectic liquid crystalline phase at room temperature (≈25° C) and the phase persisted up to 72.6° C. These results indicate that it is possible to design polymers containing thermotropic liquid crystalline phases by fixing low molecular weight liquid crystalline molecules to a polymer main chain.

This dissertation describes the study of excitonic optical nonlinearities in semiconductors and semiconductor microstructures. The main emphasis is placed on the evolution of optical nonlinearities as one goes from bulk to quantum-confined structures. Included are experimental studies of molecular-beam-epitaxially-grown bulk GaAs and ZnSe, GaAs/AlGaAs multiple-Quantum-Wells (MQW's), and finally, quantum-confined CdSe-doped glasses. The microscopic origins and magnitudes of the optical nonlinearities of bulk GaAs and ZnSe were investigated and the exciton recovery time in ZnSe was measured. A comparison with a plasma theory indicates that in GaAs, band filling and screening of the continuum-state Coulomb enhancement are the most efficient mechanisms, while in ZnSe, exciton screening and broadening are the dominating mechanism for the nonlinearity. The maximum nonlinear index per excited electron-hole pair of ZnSe at room temperature is comparable to that of bulk GaAs and the exciton recovery times are of the order of 100 ps or less. A systematic study of the dependence of the optical nonlinearities on quantum well thickness for GaAs/AlGaAs MQWs and the results of nonlinear optical switching and gain in a 58 A GaAs/AlGaAs MQW are reported and discussed. The maximum change in the refractive index is greatest for the MQWs with the smallest well size and decreases with increasing well size, reaching a minimum for bulk GaAs. The maximum index change per photoexcited carrier increases by a factor of 3 as the well size decreases from bulk to 76 A MQW. A differential energy gain of 0.2 and the contrast of 4 are measured for a 58 MQW using 3 ns laser pulses. The linear and nonlinear optical properties of CdSe semiconductor microcrystallites grown under different heat treatments in borosilicate glasses are investigated. Pump-probe spectroscopic techniques and interferometric techniques were employed to study size quantization effects in these microcrystallites (quantum dots). Nonlinear optical properties due to the transitions between quantum confined electron and hole states are reported for low temperature and room temperature. A relatively large homogeneous linewidth is observed. Single beam saturation experiments for quantum confined samples were performed to study the optical nonlinearities as a function of microcrystallite size. Results indicate that the saturation intensity is larger for smaller size quantum dots.

Optical filters and thin film optical devices play an important role in Science and Industry. Several significant applications have emerged in optics, microelectronics and computer technology. In this work, we study some aspects of their design and applications. One class of optical fibers, known as Christiansen filters, are based on scattering phenomena in suspensions of solid particles in a liquid medium. Some new scattering filters in the visible and the near UV regions and their performance characteristics are reported here. Feasibility to fabricate such optical filters in solid matrix form is established. Some applications of these scattering filters are discussed. After an introduction to the optics of homogeneous and isotropic thin films, I discuss the general design of anisotropic thin film media and a scheme implemented to calculate their performance. Optical anisotropy, produced by the growth-induced columnar microstructure in thin films and its effects on the performance of optical filters are studied. Large shifts in the peak wavelength of a typical narrow band filter are predicted. Magneto-optical (MO) thin film media of great importance to erasable optical data storage technology are studied. An approximate technique based on a 2 x 2 matrix formalism is developed to calculate the normal incidence performance of these media. To investigate anisotropic effects, to incorporate more than one magnetic film with arbitrary orientations of magnetization, and to study oblique incidence performance, a completely general 4 x 4 matrix technique is implemented in a computer program. Effects of substrate/superstrate birefringence in the read-out signal of MO media are investigated. Several optimizing design criteria, particularly, the effectiveness in employing appropriate metal or dielectric reflector layers are studied. The influence of the plasma edge of metals in enhancing the polar Kerr rotation of MO media is discussed with illustrations. A contour plot of the Kerr rotation and reflectance is developed to help in the design of these media. An explanation is given for the observation of Kerr rotation enhancement near the plasma reflection edge of the reflector layer adjacent to the active MO layer and in general, where the reflectance spectrum shows a steep gradient.

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The deformation of a mirror's optical surface due to a spacial variation of the coefficient of thermal expansion is examined. Four types of variations of the coefficient of thermal expansion are studied. These represent variations which result after typical manufacturing and/or fabrication processes. Equations describing the deformations resulting from the variations in the coefficient of thermal expansion are derived for some of the cases. Deformations due to more complex variations in the coefficient of thermal expansion are developed empirically using data generated by the finite-element method.

Graphene is a one-atom thick sheet of graphite which made of carbon atoms arranged in a hexagonal lattice. Carbon nanotubes and graphene nanoribbons can be viewed as single molecules in nanometer scale. Carbon nanotubes are usually labeled in terms of the chiral vectors which are also the directions that graphene sheets are rolled up. Due to their small scale and special structures, carbon nanotubes present interesting electrical, optical, mechanical, thermal, and toxic properties. Graphene nanoribbons can be viewed as strips cut from infinite graphene. Graphene nanoribbons can be either metallic or semiconducting depending on their edge structures. These are robust materials with excellent electrical conduction properties and have the potential for device applications. In this research project, we present a theoretical study of electrical properties of the carbon structures. Electronic band structures, density of states, and conductance are calculated. The theoretical models include a tight-binding model, a Green’s function methodology, and the Landauer formalism. We have investigated the effects of vacancy and weak disorder on the conductance of zigzag carbon nanoribbons. The resulting local density of states (LDOS) and conductance bands show that electron transport has interesting behavior in the presence of any disorder. In general, the presence of any disorder in the GNRs causes a decrease in conductance. In the presence of a vacancy at the edge site, a maximum decrease in conductance has been observed which is due to the presence of quasi-localized states. / Theory -- Band structure and density of states of carbon nanotubes -- Band structure and density of states of graphene nanoribbons -- Quantum conductance of zigzag graphene nanoribbons -- Quantum conductance of a zigzag graphene nanoribbon with defects. / Department of Physics and Astronomy