A comparative assessment of the 48-h acute toxicity of aqueous nanoparticles synthesized using the same methodology, including Au, Ag, and Ag-Au bimetallic nanoparticles, was conducted to determine their ecological effect in freshwater environments through the use of Daphnia magna, using their mortality as a toxicological endpoint. D. magna are one of the standard organisms used for ecotoxicity studies due to their sensitivity to chemical toxicants. Particle suspensions used in toxicity testing were well-characterized through a combination of absorbance measurements, atomic force or electron microscopy, flame atomic absorption spectrometry, and dynamic light scattering to determine composition, aggregation state, and particle size. The toxicity of all nanoparticles tested was found to be dose and composition dependent. The concentration of Au nanoparticles that killed 50% of the test organisms (LC(50)) ranged from 65-75 mg/L. In addition, three different sized Ag nanoparticles (diameters = 36, 52, and 66 nm) were studied to analyze the toxicological effects of particle size on D. magna; however, it was found that toxicity was not a function of size and ranged from 3-4 μg/L for all three sets of Ag nanoparticles tested. This was possibly due to the large degree of aggregation when these nanoparticles were suspended in standard synthetic freshwater. Moreover, the LC(50) values for Ag-Au bimetallic nanoparticles were found to be between that of Ag and Au but much closer to that of Ag. The bimetallic particles containing 80% Ag and 20% Au were found to have a significantly lower toxicity to Daphnia (LC(50) of 15 μg/L) compared to Ag nanoparticles, while the toxicity of the nanoparticles containing 20% Ag and 80% Au was greater than expected at 12 μg/L. The comparison results confirm that Ag nanoparticles were much more toxic than Au nanoparticles, and that the introduction of gold into silver nanoparticles may lower their environmental impact by lowering the amount of Ag which is bioavailable.

The vibrational spectroscopy of C-H stretches in organic molecules is of considerable importance for the characterization of these systems and for exploration of their properties. These stretches are strongly anharmonic, and thus methods including anharmonicity have to be used. The vibrational self-consistent field (VSCF) is applied to the following organic compounds: acetone, dimethylacetylene, neopentane, toluene, ethylene, and cyclopropane. The computed spectra are compared to new experimental data, including Raman measurements of all molecules except cyclopropane and IR of acetone, neopentane, and ethylene. A high level of agreement is found for all of the molecules. The characteristic features of CH3 and CH2 groups are studied and analyzed in detail. A reliable, unambiguous assignment of vibrational modes to spectral peaks is provided. Several characteristic features of CH3 and CH2 vibrations in polyatomic molecules are clarified, providing easier assignments for different types of organic molecules.

Raman microscopy/spectroscopy measurements are presented on high purity niobium (Nb) samples, including pieces from hot spot regions of a tested superconducting rf cavity that exhibit a high density of etch pits. Measured spectra are compared with density functional theory calculations of Raman-active, vibrational modes of possible surface Nb-O and Nb-H complexes. The Raman spectra inside particularly rough pits in all Nb samples show clear differences from surrounding areas, exhibiting enhanced intensity and sharp peaks. While some of the sharp peaks are consistent with calculated NbH and NbH 2 modes, there is better overall agreement with C-H modes in chain-type hydrocarbons. Other spectra reveal two broader peaks attributed to amorphous carbon. Niobium foils annealed to >2000 C in high vacuum develop identical Raman peaks when subjected to cold working. Regions with enhanced C and O have also been found by SEM/EDX spectroscopy in the hot spot samples and cold-worked foils, corroborating the Raman results. Such regions with high concentrations of impurities are expected to suppress the local superconductivity and this may explain the correlation between hot spots in superconducting rf (SRF) cavities and the observation of a high density of surface pits. The origin of localized high carbon and hydrocarbon regions is unclear at present but it is suggested that particular processing steps in SRF cavity fabrication may be responsible.

DEDICATIONTo my friends and family who have supported me every step of the way.-RKD ii

First-principles anharmonic calculations are carried out for the CH stretching vibrations of isolated toluene and compared with the experimental infrared spectra of isotopologues of toluene in a Ne matrix at 3 K and of liquid toluene at room temperature. The calculations use the vibrational self-consistent field method and the B3LYP potential surface. In general, good agreement is found between the calculations and experiments. However, the spectrum of toluene in a Ne matrix is more complicated than that predicted theoretically. This distinction is discussed in terms of matrix-site and resonance effects. Interestingly, the strongest peak in the CH stretching spectrum has similar widths in the liquid phase and in a Ne matrix, despite the very different temperatures. Implications of this observation to the broadening mechanism are discussed. Finally, our results show that the B3LYP potential offers a good description of the anharmonic CH stretching band in toluene, but a proper description of matrix-site and resonance effects remains a challenge.