published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Mechanical Engineering / Master / Master of Philosophy

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No description available.

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The UV-visible absorption spectrum of carbon vapor trapped in solid argon at low temperature contains many intense features, but only those of C₂ and C₃ have been identified. For this work, graphite vapor was produced under high vacuum conditions and condensed with argon onto a cold (∼10K) substrate. The resulting matrix-isolated carbon molecules were analyzed with both UV-visible and infrared absorption spectroscopy. Slight warming of the sample allowed formation of larger molecules and subsequent spectra traced the growth of their absorption features. The experiment associated infrared features to particular UV-visible features via their growth curves. The most reliable correlations are listed below. Theoretical calculations of equilibrium geometries and IR vibrational frequencies were performed on linear and nearly linear carbon chain molecules from C₃ to C₉ at the HF/SCF level of theory and from C₃ to C₇ at the MP2 level of theory, both using the 6-31G* basis set. Tentative assignment of the UV-visible features to molecules was made based on these considerations and on the following: the experimental IR/UV-visible correlations, previous experimental IR work, and modeling of the growth of the UV-visible features during matrix annealing. (UNFORMATTED TABLE FOLLOWS:) Molecule, UV-visible Feature (Å), IR Feature (cm⁻¹), Correlation Coefficient. C₃ (linear), 4100, 2040, .98. C₈ (linear), 3075, 1998, .97. C₈ (cyclic), 3900, 1804, .90. C₆ (linear), 2465, 1952, .86. C₇, 3480. C₉, 4480.

Optical properties of carbon are studied in bulk state from λ ∿ 0.05 to 100 μm for graphite, and from λ ∿ 0.05 to 1000 μm for glassy carbon; in small particle state, the optical studies cover the spectral range going from λ ∿ 0.1 to 100 μm for all the materials. A Kramers-Kronig analysis of near normal reflectance data and/or a reflectance data fit to a Drude-Lorentz model gave bulk optical constants. These optical constants are used in theoretical calculations of extinction and the results compared with experimental results obtained from measurements of a variety of carbon particles. It is inferred that the high experimentally observed extinction is mainly due to a shape effect.

The expansion of mesquite (Prosopis velutina) in southeastern Arizona and attempts to control or remove mesquite have been well documented. However, removal of woody plants may affect the distribution and quantities of nutrient resources within soil including changes in carbon (C) and nitrogen (N) cycling and changes in the amounts of C and N sequestered in these soils. We hypothesized that mechanical mesquite removal would alter soil microclimate and nutrient inputs, leading to changes in soil C and N cycling and microbial communities and activities.This study was conducted at two separate semi-arid grassland sites south of Tucson, AZ during a three-year period. There were six study plots at each site, three plots from which mature mesquite trees had been mechanically removed and three plots where mature mesquite trees were left intact. We measured the soil temperature and moisture, C and N pools, N2O and CO2 fluxes, N mineralization rate, and microbial resistance and resilience to determine if short term changes in any of these parameters were taking place.No significant differences in N mineralization rate or microbial resistance or resilience were found between the soils under intact mesquite and from plots where mesquite had been mechanically removed. Soil temperature was not statistically analyzed because temperature was taken in only one plot per treatment and without within-treatment replicates, t-tests could not be performed. Statistically significant differences in soil moisture, total soil C and N, microbial biomass C and N, heterotrophic plate counts, and CO2 and N2O fluxes were found between treatments on different dates throughout the experiment. Despite this finding of some significant differences between treatments for some parameters measured, no recognizable pattern of changes was observed during this study. Over the course of the experiment, the data did not support our overall hypothesis, that short term changes in microclimate following mesquite removal would alter soil C and N cycling and microbial communities and activities.