<p>Second harmonic generation (SHG) is a nonlinear optical effect sensitive to interfaces between materials with inversion symmetry. It is used as an effective tool for detection of the adsorption of a substance to microscopic particles, cells, liposomes, emulsions and similar structures, surface analysis and characterization of microparticles. The scattered second harmonic (SH) intensity from surfaces of suspended microparticles is characterized by its complex angular distribution dependence on the shape, size, and physical and chemical properties of the molecules making up the outer layer of the particles. In particular, the overall scattered SH intensity has been predicted to have a dramatic and nontrivial dependence on the particle size.</p><p>Results are reported for aqueous suspensions of polystyrene microspheres with different dye molecules adsorbed on their surfaces. They indicate that the scattered SH power has an oscillatory dependence on the particle size. It is also shown that adsorption of one of the dyes (malachite green) on polystyrene particles is strongly affected when SDS surfactants are added to the solution. For this system a rapid increase of the SH signal with increasing concentration of SDS was observed in the range of low SDS concentration.</p><p>Three different theoretical models are used to analyze the observed particle size dependence of SHG. The calculated angular and particle size dependences of the SH scattered power show that the models do not agree very well between each other when the size of the particles is of the order of the fundamental light wavelength, as here. One of the models - nonlinear Mie scattering - predicts oscillatory behaviour of the scattered SH power with the particle size, but fails to reproduce the position of the maxima and minima of the experimentally observed oscillations.</p><p>The obtained results on the size dependence of the SH can be used in all applications to increase the count rate by choosing particles of the size for which the SH efficiency was found to the highest. A new effect of cooperative malachite green and SDS interaction at the polystyrene surface can be employed, for example, in the areas of microbiology or biotechnology, where adsorption macromolecules, surfactants and dyes to polystyrene microparticles is widely used.</p>

Graduation date: 2005

Graduation date: 1993

Conventional step-index silica fibers do not possess a second-order optical nonlinearity due to symmetry concerns. However, through the process of poling, the generation of a frozen-in DC field $E^{DC}$, and in turn, a non-zero second-order nonlinearity $\chi^{(2)} = 3\chi^{(3)}E^{DC}$, can be created in optical fibers. In this thesis, I measure the individual $\chi^{(2)}$ tensor elements of birefringent periodically poled fiber via second-harmonic generation and sum-frequency generation experiments. The symmetry of the $\chi^{(2)}$ tensor is consistent with that of the $\chi^{(3)}$ for isotropic media. This is the first study that characterizes all the $\chi^{(2)}$ tensor elements in birefringent poled fiber. Furthermore, I investigate the intermix of the $\chi^{(2)}$ tensor elements by twisting the fiber, which results in the generation of new second-harmonic signals not observed in untwisted fiber. The conversion efficiencies and spectral positions of these new signals can be varied by twisting the fiber.

Conventional step-index silica fibers do not possess a second-order optical nonlinearity due to symmetry concerns. However, through the process of poling, the generation of a frozen-in DC field $E^{DC}$, and in turn, a non-zero second-order nonlinearity $\chi^{(2)} = 3\chi^{(3)}E^{DC}$, can be created in optical fibers. In this thesis, I measure the individual $\chi^{(2)}$ tensor elements of birefringent periodically poled fiber via second-harmonic generation and sum-frequency generation experiments. The symmetry of the $\chi^{(2)}$ tensor is consistent with that of the $\chi^{(3)}$ for isotropic media. This is the first study that characterizes all the $\chi^{(2)}$ tensor elements in birefringent poled fiber. Furthermore, I investigate the intermix of the $\chi^{(2)}$ tensor elements by twisting the fiber, which results in the generation of new second-harmonic signals not observed in untwisted fiber. The conversion efficiencies and spectral positions of these new signals can be varied by twisting the fiber.

The main contributions of this thesis to the field of ultrashort pulse measurement are a new set of experimental tools to measure the spatio-temporal fields of femtosecond pulses, and a new simplified formalism to describe such fields in the presence of distortions. More specifically, we developed an experimental technique based on scanning-wavelength digital holography and frequency-resolved optical gating that allows the complete measurement of the electric field E(x,y,t) of trains of identical femtosecond pulses. A related method, wavelength-multiplexed digital holography, is also introduced. It achieves a single-shot measurement of the three-dimensional field E(x,y,t) but at a reduced resolution using a simple experimental apparatus. Both methods can be used to measure various spatio-temporal distortions that often plague femtosecond laser systems, in particular amplified ones. Finally, to unambiguously and intuitively quantify such distortions, we introduce normalized correlation coefficients so that a common language can be used to describe the severity of these effects.

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<p>Atmospheric corrosion, the most common form of metal corrosion, occurs within the interfacial region between a solid, and the surrounding atmosphere. In fact three phases and two interfaces are involved: the gas, a thin liquid layer, a solid, the gas/liquid and the liquid/solid interfaces. In this thesis, the vapor/liquid and liquid/metal interfaces have been studied by the in-situ techniques vibrational sum frequency spectroscopy (VSFS), and infrared reflection/absorption spectroscopy (IRAS). The main focus has been on characterization of the corrosive organic molecules formic acid, acetic acid, and acetaldehyde, at the two interfaces. Additionally, the headgroup of sodium dodecyl sulfate (SDS) has been examined at the air/water interface.</p><p>VSFS is an inherently surface sensitive laser spectroscopy technique, which provides vibrational spectra solely of the molecules residing at the surface of for example a liquid, despite the vast excess of the same molecules in the bulk. To obtain a comprehensive molecular picture of the organic compounds at the air/liquid interface, studies have been undertaken in several spectral regions, targeting the CH, C=O, C-O, OH, and SO3 stretching vibrations. Furthermore, the surrounding water molecules have been investigated in order to study hydration phenomena. Acetaldehyde has been determined to partly form a gem-diol (CH3CH(OH)2) at the air/water interface, whereas acetic acid forms various hydrogen-bonded species, with hydrated monomers at low concentrations and centrosymmetric cyclic dimers at high concentrations. Formic acid was found to form a different complex at very high concentrations, in addition to the species observed at low concentrations. Performing experiments with different polarizations of the laser beams has enabled the determination of the orientation of the interfacial molecules. The methyl group of acetic acid was concluded to be oriented close to the surface normal throughout the concentration range, whereas the tilt angle of the CH group of formic acid was determined to be ~35°. The SDS studies revealed that the headgroup orientation is constant in a wide range of concentrations, and also in the presence of sodium chloride.</p><p>IRAS has provided information regarding the composition and kinetics of the corrosion products formed upon exposure of a zinc oxide surface to the organic compounds. The importance of the water adlayer on metal surfaces has been confirmed by the faster kinetics observed at higher relative humidities. Exposure to formic acid resulted in the formation of zinc formate, whereas both acetic acid and acetaldehyde formed zinc acetate upon reaction with the zinc oxide surface. However, the kinetics were faster for acetic acid than acetaldehyde, which was explained in terms of an acetate-induced zinc dissolution process and a more complicated reaction path involved in the acetaldehyde case to form the zinc acetate surface species. Scanning electron microscopy indicated the formation of radially growing reaction products for acetic acid and filiform corrosion for acetaldehyde.</p>

The idea of terahertz-time-domain spectroscopy (THz-TDS) is to exploit a single cycle, spectrally broad THz radiation pulse to gain insight into the response of matter. Photoconductive devices and nonlinear crystals are utilized in both the generation as well as the coherent detection of THz radiation. The relatively high cost and the complexity of commonly used titanium-sapphire lasers hinder a more widespread use of pulsed THz systems for commercial applications. Er-doped femtosecond fiber lasers operating at 1.55 μm could offer a viable alternative. In this thesis nonlinear crystals and photoconductive emitters are discussed for excitation in the near infrared (NIR) window of between 800 nm to 1550 nm. The main focus of this thesis is a detailed study of substrate materials for an interdigitated photoconductive antenna. Photoconductive antennas with microstructured electrodes provide high electric acceleration fields at moderate voltages because of small electrode separations. The scalability of these devices allows for large active areas in the mm^2 range, which are sufficient for excitation at large optical powers. In comparison with conventional emitter structures, these antennas have more favourable characteristics regarding THz power, spectral properties, and ease of handling. Depending on the utilized substrate material, photoconductive antennas can then be operated using different excitation wavelengths. By employing substrates with short carrier trapping times these antennas can be operated as THz-detectors. Moreover the design of electrode structures for generating radially and azimuthally polarized THz waves are presented. A second topic deals with the signal analysis and signal interpretation of THz pulses transmitted through several material systems. These experiments show the potential for tomographic and spectroscopic applications. The third part deals with THz emission by frequency mixing in nonlinear organic and inorganic crystals. Hereby the focus is on polaritonic phase matching in GaAs. Furthermore, indications of THz tunability by the excitation wavelength were found by utilizing waveguide structures. However, the observed tuning range is much lower then theoretically predicted. Specific reasons for this are discussed.

Thesis (Ph. D.)--University of Chicago, Department of Chemistry, 2002. / Includes bibliographical references. Also available on the Internet.