Description: The work function of hydrogen-terminated, polycrystalline diamond was studied using ultraviolet photoelectron spectroscopy. Polycrystalline diamond films were deposited onto molybdenum substrates by electrophoresis for grain sizes ranging from 0.3 to 108 microns. The work function and electron affinity were measured using 21.2 eV photons from a helium plasma source. The films were characterized by x-ray photoelectron spectroscopy to determine elemental composition and the sp2/sp3 carbon fraction. The percentage of (111) diamond was determined by x-ray diffraction, and scanning electron microscopy was performed to determine average grain size. The measured work function has a maximum of 5.1 eV at 0.3 microns, and decreases to 3.2 eV at approximately 4 microns. Then the work function increases with increasing grain size to 4.0 eV at 15 microns and then asymptotically approaches the 4.8 eV work function of single crystal diamond at 108 microns. These results are consistent with a 3-component model in which the work function is controlled by single-crystal (111) diamond at larger grain sizes, graphitic carbon at smaller grain sizes, and by the electron affinity for the intervening grain sizes.

Description: A resonant cavity operating in TE011 mode was used to study the adsorption response of single walled carbon nanotubes (SWCNTs) and other nanomaterials for different types of gas molecules. The range of the frequency signal as a probe was chosen as geometry dependent range between 9.1 -9.8 GHz. A highly specific range can be studied for further experiments dependent on the type of molecule being investigated. It was found that for different pressures of gases and for different types of nanomaterials, there was a different response in the shifts of the probe signal for each cycle of gassing and degassing of the cavity. This dissertation suggests that microwave spectroscopy of a complex medium of gases and carbon nanotubes can be used as a highly sensitive technique to determine the complex dielectric response of different polar as well as non-polar gases when subjected to intense electromagnetic fields within the cavity. Also, as part of the experimental work, a range of other micro-porous materials was tested using the residual gas analysis (RGA) technique to determine their intrinsic absorption/adsorption characteristics when under an ultra-high vacuum environment. The scientific results obtained from this investigation, led to the development of a chemical biological sensor prototype. ...

Description: We show that the nonadditive open systems can be studied in a consistent manner by using a generalized version of S-theorem. This new generalized S-theorem can further be considered as an indication of self-organization in nonadditive open systems as prescribed by Haken. The nonadditive S-theorem is then illustrated by using the modified Van der Pol oscillator. Finally, Tsallis entropy as an equilibrium entropy is studied by using Boltzmann's method of orthodes. This part of dissertation shows that Tsallis ensemble is on equal footing with the microcanonical, canonical and grand canonical ensembles. However, the associated entropy turns out to be Renyi entropy.

Description: Computational techniques were employed to investigate pathways that would improve the properties and characteristics of transition metal (i.e., ruthenium) catalysts, and to explore their mechanisms. The studied catalytic pathways are particularly relevant to catalytic hydroarylation of olefins. These processes involved the +2 to +3 oxidation of ruthenium and its effect on ruthenium-carbon bond strengths, carbon-hydrogen bond activation by 1,2-addition/reductive elimination pathways appropriate to catalytic hydrogen/deuterium exchange, and the possible intermediacy of highly coordinatively unsaturated (e.g., 14-electron) ruthenium complexes in catalysis. The calculations indicate a significant decrease in the Ru-CH3 homolytic bond dissociation enthalpy for the oxidation of TpRu(CO)(NCMe)(Me) to its RuIII cation through both reactant destabilization and product stabilization. This oxidation can thus lead to the olefin polymerization observed by Gunnoe and coworkers, since weak RuIII-C bonds would afford quick access to alkyl radical species. Calculations support the experimental proposal of a mechanism for catalytic hydrogen/deuterium exchange by a RuII-OH catalyst. Furthermore, calculational investigations reveal a probable pathway for the activation of C-H bonds that involves phosphine loss, 1,2-addition to the Ru-OH bond and then reversal of these steps with deuterium to incorporate it into the substrate. The presented results offer the indication for the net addition of aromatic C-H ...

Description: Energy distribution measurements of sputtered neutral particles contribute to the general knowledge of sputtering, a common technique for surface analysis. In this work emphasis was placed on the measurement of energy distribution of sputtered neutral atoms from different depths. The liquid Ga-In eutectic alloy as a sample target for this study was ideal due to an extreme concentration ratio gradient between the top two monolayers. In pursuing this study, the method of sputter-initiated resonance ionization spectroscopy (SIRIS) was utilized. SIRIS employs a pulsed ion beam to initiate sputtering and tunable dye lasers for resonance ionization. Observation of the energy distribution was achieved with a position-sensitive detector. The principle behind the detector's energy resolution is time of flight (TOF) spectroscopy. For this specific detector, programmed time intervals between the sputtering pulse at the target and the ionizing laser pulse provided information leading to the energy distribution of the secondary neutral particles. This experiment contributes data for energy distributions of sputtered neutral particles to the experimental database, required by theoretical models and computer simulations for the sputtering phenomenon.