A series of ab initio calculations has been performed in the Born-Oppenheimer approximation for some electronic states of OH. Wavefunctions and energies are calculated variationally. The form chosen for the wave-function is a finite linear superposition of configurations. Molecular orbitals are formed by Schmidt-orthogonalizing the atomic orbitals, each of which is represented by a single Slater-type orbital. The variational parameters are the coefficients in the linear expansion of the wave-function, and the non-linear parameters [character omitted] of the Slater-type orbitals. Wavefunctions and potential energy curves are given for some of the lower-lying ²Σˉ and ²Σˉ and ²Πstates. One result of note is that the lowest ²Σˉ state is bound. This disagrees with an earlier calculation (Harris and Michels, 1969), but it is in accord with a recent interpretation of the spectrum (Pryce, 1971). / Science, Faculty of / Physics and Astronomy, Department of / Graduate

Thesis (Ph. D.)--Ohio State University, 2007. / Title from first page of PDF file. Includes bibliographical references (p. 338-365).

For many years there has been a great interest among the scientific community in the study of the hydroxyl radical, HO. This interest stems from the fundamental role played by this molecule in the photochemistry of the atmosphere, mainly as a cleansing agent of environmental pollutants. Knowing the concentration of the radical would enable scientists to corroborate current atmospheric models and to predict future trends in the atmosphere. Even though there is a great interest in the determination of atmospheric concentrations of this molecule, the task has been very difficult. This is mainly due to the lack of a method sensitive enough to detect concentrations around 106 molecules per cubic centimeter. The most accurate method presently available is the method of laser induced fluorescence using the fluorescence assay with gas expansion technique (LIF-FAGE). This method involves low pressure excitation of HO from its ground state to its lowest electronic excited state and observing the consequent fluorescence around 309 nm. The procedure is done at a pressure of 5 Torr to maximize the fluorescence lifetime of the radical and to minimize the interference of photolytic species. Background determination is achieved by chemical modulation using isobutane in a second channel of the same cell which removes the HO signal. In this study an assessment of the level of ozone interference in LIFF AGE has been done by calculating the relative population distribution of HO among its rotational levels and from this, determining its temperature. When the laser passes through the excitation detection cell it photolyses the ozone present producing in this way the highly reactive 0 1(D). When this molecule reacts with water or with isobutane it produces HO, and this is the source of interference in the actual measurements. In the determination of the relative population distributions of the different HO species, it was found that the naturally occurring HO has a thermal distribution with a temperature of about 300 K. The HO molecules produced from the reaction of 0 1(D) with isobutane also showed a thermal distribution with a temperature of about 230 K. On the other hand, the HO produced from the reaction of 0 1(D) with water did not show a thermal distribution. Two distinct temperatures were observed for this case: one around 200 K for values of K = 1 to 4, and the second one around 3000 K for values of K = 5 to 6. These values agree with previous experimental results for LIF methods by other authors except for the fact that the deviation from the first temperature determined by other authors starts at K = 6 or 7.

Choi, Lai Sheung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2008. / Includes bibliographical references (leaves 111-115). / Abstracts in English and Chinese. / Contents --- p.i / Acknowledgements --- p.iv / Abstract --- p.v / Abbreviations --- p.viii / Chapter Chapter 1 - --- Introduction to Dendrimer / Chapter 1.1 --- Definition --- p.1 / Chapter 1.2 --- Synthetic Routes --- p.2 / Chapter 1.2.1 --- Divergent Growth --- p.2 / Chapter 1.2.2 --- Convergent Growth --- p.3 / Chapter 1.3 --- Applications --- p.4 / Chapter 1.4 --- Examples of Dendrimers --- p.6 / Chapter 1.4.1 --- Hydrocarbon Dendritic Species --- p.6 / Chapter 1.4.2 --- Aliphatic Polyether Dendritic Species --- p.8 / Chapter Chapter 2 - --- Synthesis of Novel Amphiphilic Hydrocarbon Dendrons / Chapter 2.1 --- Background - Hydrocarbon Dendrons (HCDs) --- p.11 / Chapter 2.2 --- Modification and Design of Synthetic Scheme --- p.13 / Chapter 2.3 --- Syntheses --- p.14 / Chapter 2.3.1 --- Convergent Synthesis --- p.14 / Chapter 2.3.2 --- Divergent Synthesis --- p.19 / Chapter 2.4 --- Characterizations --- p.22 / Chapter 2.4.1 --- 1H NMR Spectroscopy --- p.22 / Chapter 2.4.2 --- 13C NMR Spectroscopy --- p.25 / Chapter 2.4.3 --- Mass Spectrometry --- p.27 / Chapter 2.4.4 --- Gel Permeation Chromatography (GPC) --- p.29 / Chapter 2.4.5 --- Thin Layer Chromatography (TLC) --- p.31 / Chapter 2.4.6 --- Solubility --- p.31 / Chapter 2.5 --- Conclusions and Future Prospects --- p.33 / Chapter Chapter 3 - --- Hydrogen Bonding in Supramolecular Chemistry / Chapter 3.1 --- Background ´ؤ Supramolecular Chemistry --- p.35 / Chapter 3.1.1 --- Multiple Hydrogen Bondings --- p.37 / Chapter 3.1.2 --- Applications --- p.39 / Chapter 3.2 --- 2-Ureido-4[lH]-Pyrimidinone (UPy) --- p.40 / Chapter 3.2.1 --- Tautomerization and Dimerization Equilibria --- p.40 / Chapter 3.2.2 --- Examples of Dendronized UPy Dimers --- p.44 / Chapter 3.3 --- Effects of Substituents on the Dimerization Behavior of UPy --- p.46 / Chapter 3.4 --- Dimerization Studies on Our New UPy-Dendrons --- p.50 / Chapter Chapter 4 - --- "Synthesis, Characterizations and Dimerization Properties of Dendronized UPy Dimers" / Chapter 4.1 --- Synthesis --- p.51 / Chapter 4.2 --- Characterizations --- p.51 / Chapter 4.2.1 --- 1H NMR Spectroscopy --- p.51 / Chapter 4.2.1.1 --- Dimerization Behavior of Protected UPy Series (94-97) in CDC13 at 25 °C --- p.52 / Chapter 4.2.1.2 --- Temperature-Dependent Behavior of Protected UPy Series (94´ؤ97) in CDC13 --- p.59 / Chapter 4.2.1.3 --- Tautomeric Behavior of Protected UPy Series in (94-97) in Other Solvents --- p.60 / Chapter 4.2.1.4 --- Characterization of Deprotected UPy Series (98-101) in DMSO-d6 --- p.60 / Chapter 4.2.1.5 --- Dimerization Behavior of Deprotected UPy Series (98-101) in THF-d8 and Other Solvents --- p.63 / Chapter 4.2.1.6 --- Temperature-Dependent Behavior of Deprotected UPy Series (98´ؤ101) in THF-d8 --- p.67 / Chapter 4.2.1.7 --- Dimerization Constants of Both Protected and Deprotected UPy Series in DMSO-d6/CDCl3 Mixtures at 25 °C --- p.68 / Chapter 4.2.2 --- 13C NMR Spectroscopy --- p.71 / Chapter 4.2.3 --- Mass Spectrometry --- p.71 / Chapter 4.2.4 --- Gel Permeation Chromatography (GPC) --- p.73 / Chapter 4.2.5 --- Vapour Pressure Osmometry (VPO) --- p.74 / Chapter 4.2.6 --- Infrared Spectroscopy --- p.75 / Chapter 4.2.7 --- Polarity and Solubility --- p.76 / Chapter 4.3 --- Conclusions --- p.77 / Chapter Chapter 5 - --- Conclusions --- p.79 / Chapter Chapter 6 - --- Experimantal Procedures / Chapter 6.1 --- General Information --- p.81 / Chapter 6.2 --- Experimantal Procedures --- p.82 / References --- p.111 / Appendix 1 - Calculations of lower-limits of Kdim* in CDCI3 --- p.A-1 / Appendix 2 - Calculations of Kdim* in systems where both dimer(s) and 6[1H] monomer coexist --- p.A-4 / Appendix 3 - List of Spectra --- p.A-5

Thesis (Ph. D.)--University of Nebraska, 1937. / Bibliography: p. 20.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1958. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 178-182).

No description available.

No description available.

published_or_final_version / Chemistry / Master / Master of Philosophy

The regioselectivity of the reaction of hydroxyl radical addition to toluene and naphthalene are examined in this study over the temperature range of 25°C-45°C. Also, the relative rates of reactivity as compared to benzene are determined for toluene, naphthalene, mesitylene, and p-xylene over the same temperature range. 2-(t-Butylazo)prop-2-yl hydroperoxide was used as the hydroxyl radical source and 1,1,3,3-tetramethylisoindolin-2-yloxyl was used as radical trap. For toluene the relative rates of addition were found to be 4 times greater for the ortho position versus the meta postion and 2 times greater for the para position versus the meta position, when the number of meta and para sites are taken into account. / Department of Chemistry