The diversity of transition metal complexes allows for a wide range of chemical processes to be mediated by the metal, from catalysis to surface chemistry. Investigations into the structure and electronic configuration of transition metal complexes allow for tuning of desired species by modifications to the ligands and/or metals to achieve more efficient thermodynamics and kinetics for the process of interest. Transition metals, often used in catalysts for a number of important processes, require detailed descriptions of intermediates, transition states and products to fully characterize a reaction mechanism(s) in order to design more active and efficient catalysts. Computational investigations into inorganic catalysts are explored with the aim of understanding the activity of each species and how modifications of supporting ligands, co-ligands and metals vary the interaction along the reaction pathway. Reported results give important insight into the development of the most active complexes in addition to determining the least active complexes to aid experimental development. This report first investigates the mechanisms of two unique transfer reactions: 1) formation of low coordinate nickel-nitrene ((P~P)Ni=NR; P~P = 1,2-bis(dihydrophosphino)-ethane or 1,2-bis(difluoromethylphosphino)-ethane) complexes as catalysts for nitrogen atom transfer and 2) oxidation of a triphosphorus niobium complex, [(η2-P3SnPh3)Nb(OMe)3], for the transfer of the phosphorus …

The design and fabrication of a novel soft landing instrument Soft Landing Ion Mobility (SLIM) is described here. Topics covered include history of soft landing, gas phase mobility theory, the design and fabrication of SLIM, as well as applications pertaining to soft landing. Principle applications devised for this instrument involved the gas phase separation and selection of an ionized component from a multicomponent gas phase mixture as combing technique to optimize coatings, catalyst, and a variety of alternative application in the sciences.

Copper(I) complexes have been studied through both experimental and computational means in the presented work. Overall, the work focuses on photophysical and photochemical properties of copper(I) complexes. Photophysical and photochemical properties are found to be dependent on the geometries of the copper(I) complexes. One of the geometric properties that are important for both photochemical and photophysical properties is coordination number. Coordination numbers have been observed to be dependent on both ligand size and recrystallization conditions. The complexes geometric structure, as well as the electronic effects of the coordination ligands, is shown both computationally as well as experimentally to affect the emission energies. Two-coordinate complexes are seen to have only weak emission at liquid nitrogen temperature (77 K), while at room temperature (298 K) the two-coordinate complexes are not observed to be luminescent. Three-coordinate complexes are observed to be luminescent at liquid nitrogen temperature as well as at room temperature. The three-coordinate complexes have a Y-shaped ground (S0) state that distorts towards a T-shape upon photoexcitation to the lowest lying phosphorescent state (T1). The geometric distortion is tunable by size of the coordinating ligand. Luminescence is controllable by limiting the amount of non-radiative emission. One manner by which non-radiative emission is …

The efforts of my research have led to the successful construction of several instruments that have helped expand the field of microwave spectroscopy. The classic Balle-Flygare spectrometer has been modified to include two different sets of antenna to operate in the frequency ranges 6-18 GHz and 18-26 GHz, allowing it to function for a large range without having to break vacuum. This modified FTMW instrument houses two low noise amplifiers in the vacuum chamber to allow for the LNAs to be as close to the antenna as physically possible, improving sensitivity. A new innovative Balle-Flygare type spectrometer, the efficient low frequency FTMW, was conceived and built to operate at frequencies as low as 500 MHz through the use of highly curved mirrors. This is new for FTMW techniques that normally operate at 4 GHz or higher with only a few exceptions around 2 GHz. The chirped pulse FTMW spectrometer uses horn antennas to observe spectra that span 2 GHz versus the standard 1 MHz of a cavity technique. This instrument decreases the amount of time to obtain a large spectral region of relative correct intensity molecular transitions. A Nd:YAG laser ablation apparatus was attached to the classic Balle-Flygare and chirped …

In this work, the possibility of Cu electrodeposition on Ru-Ta alloy thin films is explored. Ru and Ta were sputter deposited on Si substrate with different composition verified by RBS. Four point probe, XRD, TEM and AFM were used to study the properties of Ru-Ta thin films such as sheet resistance, crystallinity, grain size, etc. Cyclic voltammetry is used to study the Cu electrodeposition characteristics on Ru-Ta after various surface pretreatments. The results provide insights on the removal of Ta oxide such that it enables better Cu nucleation and adhesion. Bimetallic corrosion of Cu on modified Ru-Ta surface was studied in CMP related chemicals. In Cu interconnect fabrication process, the making of trenches and vias on low-k dielectric films involves the application of fluorocarbon plasma etch gases. Cu microdots deposited on Ru and Ta substrate were treated by fluorocarbon plasma etch gases such as CF4, CF4+O2, CH2F2, C4F8 and SF6 and investigated by using x-ray photoelectron spectroscopy, contact angle measurement and electrochemical techniques. Micropattern corrosion screening technique was used to measure the corrosion rate of plasma treated Cu. XPS results revealed different surface chemistry on Cu after treating with plasma etching. The fluorine/carbon ratio of the etching gases results in …

The scope of work in this dissertation has comprised several major investigations on applications and theoretical studies of ab initio quantum mechanics and density functional theory where those techniques were applied to the following: (i) investigation of the performance of density functionals for the computations of molecular properties of 3d transition metal containing systems; (ii) guidance for experimental groups for rational design of macrometallocyclic multinuclear complexes with superior π-acidity and π-basicity that are most suitable for p- and n-type semiconductors of metal-organic molecules and nanomaterials; (iii) investigation of the metallo-aromaticity of multi-nuclear metal complexes; (iv) investigation of the kinetics and thermodynamics of copper-mediated nitrene insertion into C-H and H-H bond; and (v) accurate computations of dissociation energies of hydrogen-bonded DNA duplex moieties utilizing the resolution of identity correlation consistent composite approach (RI-ccCA).

One of the central concerns of computational chemistry is that of efficiency (i.e. the development of methodologies which will yield increased accuracy of prediction without requiring additional computational resources – RAM, disk space, computing time). Though the equations of quantum mechanics are known, the solutions to these equations often require a great deal of computing power. This dissertation primarily concerns the theme of improved computational efficiency (i.e. the achievement of greater accuracy with reduced computational cost). Improvements in the efficiency of computational chemistry are explored first in terms of the correlation consistent composite approach (ccCA). The ccCA methodology was modified and this enhanced ccCA methodology was tested against the diverse G3/05 set of 454 energetic properties. As computational efficiency improves, molecules of increasing size may be studied and this dissertation explored the issues (differential correlation and size extensivity effects) associated with obtaining chemically accurate (within 1 kcal mol-1) enthalpies of formation for hydrocarbon molecules of escalating size. Two applied projects are also described; these projects concerned the theoretical prediction of a novel rare gas compound, FKrOH, and the mechanism of human glutathione synthetase’s (hGS) negative cooperativity. The final work examined the prospect for the parameterization of the modified embedded atom …

The growth of single and multilayer BN films on several substrates was investigated. A typical atomic layer deposition (ALD) process was demonstrated on Si(111) substrate with a growth rate of 1.1 Å/cycle which showed good agreement with the literature value and a near stoichiometric B/N ratio. Boron nitride films were also deposited by ALD on Cu poly crystal and Cu(111) single crystal substrates for the first time, and a growth rate of ~1ML/ALD cycle was obtained with a B/N ratio of ~2. The realization of a h-BN/Cu heterojunction was the first step towards a graphene/h-BN/Cu structure which has potential application in gateable interconnects.

The first part of this dissertation highlights the contents of the electrochemical characterization of Cu and its electroplating on Ru-based substrates. The growth of Ru native oxide does diminish the efficiency of Cu plating on Ru surface. However, the electrochemical formed irreversible Ru hydrate dioxide (RuOxHy) shows better coverage of Cu UPD. The conductive Ru oxides are directly plateable liner materials as potential diffusion barriers for the IC fabrication. The part II of this dissertation demonstrates the development of a new rapid corrosion screening methodology for effective characterization Cu bimetallic corrosion in CMP and post-CMP environments. The corrosion inhibitors and antioxidants were studied in this dissertation. In part III, a new SEC methodology was developed to study the ORR catalysts. This novel SEC cell can offer cheap, rapid optical screening results, which helps the efficient development of a better ORR catalyst. Also, the SEC method is capable for identifying the poisoning of electrocatalysts. Our data show that the RuOxHy processes several outstanding properties of ORR such as high tolerance of sulfation, high kinetic current limitation and low percentage of hydrogen peroxide.

Examinations of the effects of (a.) alkyl carbon chain length and (b.) perfluorination of acyl chlorides; propionyl chloride, butyryl chloride, valeroyl chloride, and perfluorinated acyl chlorides; perfluoropropionyl chloride and perfluorobutyryl chloride, are reported and compared using CP-FTMW spectroscopy. All of these molecules are already published in various journals except for valeroyl chloride. The chapters are organized by molecule alkyl chain length and include some background theory. Conformational stability, internal rotation, helicity, and ionic character of the C-Cl bond via the nuclear electric quadrupole coupling constant (χzz) are analyzed. Results show syn, syn-anti/syn-gauche, and syn-anti-anti/syn-gauche-anti stable conformations. Internal rotation was only seen in propionyl chloride. Helicity was not observed. (χzz) was observed to be inert to alkyl chain length, ~ 60 MHz and ~ 65 MHz for the nonfluorinated and fluorinated acyl chlorides. Partial fluorination and varying functional groups are recommended.

Kinetics and thermodynamics of bismuth (Bi) underpotential deposition (UPD) on ruthenium (Ru) and on electrochemically formed Ru oxide are studied using electrochemical quartz crystal microbalance technique. The Bi UPD and Bi bulk deposition are observed both on Ru and on electrochemically formed Ru oxide electrodes. The anodic peak potential of Bi UPD shifts slightly to positive potential as the scan rate increases. The peak current ratio (IAnode/ICathode) of Bi UPD and Bi bulk increases as the scan rate increases. Bi monolayer coverage calculated from mass (MLMass) and from charge (MLCharge) with scan rates dependent are compared both in Bi UPD region and in Bi bulk region. Stability and oxidation time effects are also investigated. Bi UPD on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate independent, oxidation time dependent, and have higher plating efficiency on Ru. However, Bi bulk deposition on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate dependent, oxidation time independent, and have higher plating efficiency on electrochemically formed Ru oxide. Both Bi UPD adatoms and Bi bulk are unstable in 0.5M H2SO4.

A study was conducted to investigate the relationships between cybergaming treatment groups and the control group (N = 99: ncontrol = 8; nlogic = 29; nspatial = 30; ncombination = 32) with success in the organic chemistry I course as measured by achievement over a 10-week period. The treatment groups included logic training, spatial training, and combination logic-spatial training. Students' ability was measured by pre/post exams using the Group Assessment of Logical Thinking (GALT) to measure logic ability, Purdue Visualizations of Rotations (ROT) test to measure spatial skills, and the General-Organic-Biochemistry (GOB) Exam to measure content attainment. Finally, students' responses about participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. A second study was conducted to evaluate the relationship between the cybergaming treatment and control groups (N = 88: nexperimental = 27; ncontrol = 61) with success in the general chemistry I course as measured by achievement and final course averages and grades. The cybergaming treatment group underwent intensive combination logic-spatial training for 10 weeks. Students' progress was measured using three pre/post instruments: Group Assessment of Logical Thinking (GALT) measured logic ability, Purdue Visualizations of Rotations (ROT) Test measured spatial skills, and the California …

The kinetics of the reaction of atomic sulfur and nitrogen dioxide have been investigated over the temperature range 298 to 650 K and pressures from 14 - 405 mbar using the laser flash photolysis - resonance fluorescence technique. The overall bimolecular rate expression k (T) = (1.88 ± 0.49) x10-11 exp-(4.14 ± 0.10 kJ mol-1)/RT cm3 molecule-1 s-1 is derived. Ab initio calculations were performed at the CCSD(T)/CBS level of theory and a potential energy surface has been derived. RRKM theory calculations were performed on the system. It is found that an initially formed SNO2 is vibrationally excited and the rate of collisional stabilization is slower than the rate of dissociation to SO + NO products by a factor of 100 - 1000, under the experimental conditions.

Within this educational endeavor instrumental development was explored through the investigation of microwave induce stable electromagnetic waves within a non-linear yttrium iron garnet ferromagnetic waveguide. The resulting magnetostatic surface waves were investigated as a possible method of rapid analytical evaluation of material composition. Initial analytical results indicate that the interaction seen between wave and material electric and magnetic fields will allow phase coherence recovery andanalysis leading to enhancement of analytical value. The ferromagnetic waveguide selected for this research was a high quality monocrystalline YIG (yttrium iron garnet) film. Magnetostatic spin waves (MSW) were produced within the YIG thin waveguide. Spin waves with desired character were used to analytically scan materials within the liquid and solid phase.

Microwave spectroscopy is a gas phase technique typically geared toward measuring the rotational transitions of Molecules. The information contained in this type of spectroscopy pertains to a molecules structure, both geometric and electronic, which give insight into a molecule's chemistry. Typically this type of spectroscopy is high resolution, but narrowband ≤1 MHz in frequency. This is achieved by tuning a cavity, exciting a molecule with electromagnetic radiation in the microwave region, turning the electromagnetic radiation o, and measuring a signal from the molecular relaxation in the form of a free induction decay (FID). The FID is then Fourier transformed to give a frequency of the transition. "Fast passage" is defined as a sweeping of frequencies through a transition at a time much shorter (≤10 s) than the molecular relaxation (≈100 s). Recent advancements in technology have allowed for the creation of these fast frequency sweeps, known as "chirps", which allow for broadband capabilities. This work presents the design, construction, and implementation of one such novel, high-resolution microwave spectrometer with broadband capabilities. The manuscript also provides the theory, technique, and motivations behind building of such an instrument. In this manuscript it is demonstrated that, although a gas phase technique, solids, liquids, …

Polymeric nanoparticles were synthesized and loaded with Cu²⁺ to explore the therapeutic potential for catically active transition metal ions and complexes other than cisplatin. Two types of nanoparticles were synthesized to show the potential for polymer based vectors. Copper loading and release were characterized via inductively coupled plasma mass spectrometry (ICP MS), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and elemental analysis. Results demonstrated that Cu could be loaded to the nano-sized carriers in an aqueous environment, and that the release was pH-dependent. The toxicity of these particles was measured in HeLa cells where significant toxicity was observed in vitro via dosing of high Cu-loaded nanoparticles. No significant toxicity was observed in cells dosed with Cu-free nanoparticles.

Predictive methods have been employed to characterize chemical separation mediums including solvents and absorbents. These studies included creating Abraham solvation parameter models for room-temperature ionic liquids (RTILs) utilizing novel ion-specific and group contribution methodologies, polydimethyl siloxane (PDMS) utilizing standard methodology, and the micelles cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) utilizing a combined experimental setup methodology with indicator variables. These predictive models allows for the characterization of both standard and new chemicals for use in chemical separations including gas chromatography (GC), solid phase microextraction (SPME), and micellar electrokinetic chromatography (MEKC). Gas-to-RTIL and water-to-RTIL predictive models were created with a standard deviation of 0.112 and 0.139 log units, respectively, for the ion-specific model and with a standard deviation of 0.155 and 0.177 log units, respectively, for the group contribution fragment method. Enthalpy of solvation for solutes dissolved into ionic liquids predictive models were created with ion-specific coefficients to within standard deviations of 1.7 kJ/mol. These models allow for the characterization of studied ionic liquids as well as prediction of solute-solvent properties of previously unstudied ionic liquids. Predictive models were created for the logarithm of solute's gas-to-fiber sorption and water-to-fiber sorption coefficient for polydimethyl siloxane for wet and dry conditions. These models …