Thesis (Ph.D.)--McMaster University, 2003. / Advisor: Johan K. Terlouw. Includes bibliographical references. Also available via World Wide Web.

Thesis (Ph. D.)--University of Washington, 2000. / Vita. Includes bibliographical references (leaves 65-72).

No description available.

This paper proposes and compares some statistical methods for the analysis of chemical reaction rate data. / Master of Science

Yim Wai-leung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (leaves 73-77). / Abstracts in English and Chinese. / THESIS COMMITTEE --- p.ii / ABSTRACT (English version) --- p.iii / ABSTRACT (Chinese version) --- p.v / ACKNOWLEDGEMENTS --- p.vi / TABLE OF CONTENTS --- p.vii / LIST OF FIGURES --- p.ix / LIST OF TABLES --- p.xi / Chapter CHAPTER 1. --- General Introduction / Chapter Section 1.1 --- Introduction --- p.1 / Chapter Section 1.2 --- Electronic Structure Calculation / Chapter 1.2.1 --- Density Functional Theory --- p.2 / Chapter 1.2.2 --- "Exchange, Correlation and the Local Density Approximation" --- p.4 / Chapter 1.2.3 --- Bloch's Theorem and Plane Wave Basis Set --- p.6 / Chapter 1.2.4 --- The Pseudopotential Approximation --- p.10 / Chapter Section 1.3 --- Molecular Dynamics / Chapter 1.3.1 --- Molecular Dynamics --- p.12 / Chapter 1.3.2 --- Nose Thermostat / Chapter 1.3.2.1 --- Introduction --- p.14 / Chapter 1.3.2.2 --- Feedback Method --- p.15 / Chapter Section 1.4 --- Case Studies / Chapter 1.4.1 --- Thermal properties of small silver clusters --- p.18 / Chapter 1.4.2 --- Thermal decomposition channels of NTO --- p.20 / Chapter CHAPTER 2. --- Ab Initio Molecular Dynamics Study on Agn (n=4-6) / Chapter Section 2.1 --- Introduction --- p.22 / Chapter Section 2.2 --- Computational Method --- p.24 / Chapter Section 2.3 --- Results and Discussion / Chapter 2.3.1 --- Ag2 --- p.26 / Chapter 2.3.2 --- Ag4 --- p.30 / Chapter 2.3.3 --- Ag5 --- p.36 / Chapter 2.3.4 --- Ag6 --- p.45 / Chapter Section 2.4 --- Summary --- p.49 / Chapter CHAPTER 3. --- Ab Initio Molecular Dynamics Study on Thermal Decomposition of NTO / Chapter Section 3.1 --- Introduction --- p.52 / Chapter Section 3.2 --- Computation Details --- p.55 / Chapter Section 3.3 --- Results and Discussion / Chapter 3.3.1 --- Comparison of the Quantum Calculations by VASP and Gaussian98 --- p.56 / Chapter 3.3.2 --- Exploring the Reaction Channels --- p.62 / Chapter 3.3.2.1 --- Hydrogen-transfer Activation --- p.62 / Chapter 3.3.2.2 --- Homolytic Cleavage of C-N02 Bond --- p.63 / Chapter 3.3.2.3 --- Nitro-nitrite Rearrangement --- p.64 / Chapter 3.3.2.4 --- Direct Ring Rupture --- p.64 / Chapter 3.3.3 --- Energetic Consideration --- p.65 / Chapter 3.3.4 --- Activation Barriers --- p.70 / Chapter 3.3.5 --- Summary --- p.72 / REFERENCES --- p.73

Record high CO2 emissions in the atmosphere and the need to find alternative energy sources to fossil fuels are major global challenges. Conversion of CO2 into useful fuels like methanol and methane can in principle tackle both these environment and energy concerns. One of the routes to convert CO2 into useful fuels is by using supported metal catalyst. Specifically, metal atoms or clusters (few atoms large in size) supported on oxide materials are promising catalysts. Experiments have successfully converted CO2 to products like methanol, using TiO2 supported Cu atoms or clusters. How this catalyst works and how CO2 conversion could be improved is an area of much research. We used a quantum mechanical tool called density functional theory (DFT) to obtain atomic and electronic level insights in the CO2 reduction processes on TiO2 supported metal atoms and clusters. We modeled small Cu clusters on TiO2 surface, which are experimentally synthesizable. Our results show that the interfacial sites in TiO2 supported Cu are able to activate CO2 into a bent configuration that can be further reduced. The Cu dimer was found to be the most reactive for CO2 activation but were unstable catalysts. Following Cu, we also identified other potential metal atoms that can activate CO2. Compared to expensive and rare elements like Pt, Au, and Ir, we found several early and mid transition metals to be potentially active catalysts for CO2 reduction. Because the supported metal atom or cluster is a reactive catalyst, under reaction conditions they tend to undergo aggregation and/or oxidation to form larger less active catalysts. We chose Co, Ni, and Cu group elements to study their catalyst stability under oxidizing reaction conditions. Based on the thermodynamics of Cu oxidation and kinetics of O2 dissociation, we found that TiO2 supported Cu atom or a larger Cu tetramer cluster were the likely species observed in experiments. Our work provides valuable atomic-level insights into improving the CO2 reduction activities and predicts potential catalysts for CO2 reduction to valuable fuels.

The kinetics and mechanism of the reactions of (tmpa)W-(CO)^ and (tmen)W(CO)^ (tmpa = N,N,N',N'-tetramethy1-1,3-diaminopropane and tmen = N,N,N1,N1-tetramethylethylenediamine) with four phosphorus donor ligands (triisopropyl phosphite, triphenyl phosphite, triphenylphosphine and "constrained phosphite", 4-methyl-2,6,7-trioxa-l-phosphabicylo[2.2.2]octane) in xylene have been investigated in detail. These reactions were found to take place by the ring-opening of the bidentate ligand in a reversible step which leads to the formation of a five-coordinate intermediate of the type [(h^-tmpa)W(CO)or [(h^-tmen)W(CO). The intermediate then reacts with one molecule of phosphorus ligand, L, to form a six-coordinate intermediate, which can either expel the bidentate ligand and react with another molecule of L leading to the formation of a new disubstituted tungsten tetracarbonyl or go through a ring-reclosure step to form a seven-coordinate activated com-2 2plex or intermediate of the type [(h -tmpa)W(CO)^(L)] or [(h - tmen)W(CO)^(L)] which then regenerates the substrate through the expulstion of the L molecule. This mechanism is consistent with the observed rate behavior in these systems. For the reaction of (tmpa)W(CO)^ with the "constrained phosphite", an intermediate of the type [(h1-tmpa)W(CO)4P(OCH2)3CCH3] was isolated and identified.

Thesis (Ph. D.)--University of California, San Diego and San Diego State University, 2002. / Vita. Includes bibliographical references.

Thesis (Ph.D.) -- McMaster University, 2001. / Includes bibliographical references. Also available via World Wide Web.

Thesis (Ph.D.)--McMaster University, 2003. / Advisor: N. Werstiuk. Includes bibliographical references (leaves 148-156). Also available via World Wide Web.