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Computational quantum chemistry applied to nitrogen oxide chemistry and new fire-resistant polymers
Computational quantum chemistry was used as a tool to predict needed thermochemistry and kinetics for two classes of problems: formation and destruction of NOx pollutants and development of new fire-resistant polymers. Of the latter, polycarbodiimides and polyhydroxyamides (PHA's) were studied. Different methods were used: HF/6-31 G(d), BAC-MP4 (bond-additivity corrections to UMP4 energies and HF vibrational frequencies), PM3 semi-empirical, and combinations. On the NOx problem, work focused on using theory to generate improved kinetics in H2/O2/NOx combustion. The results were a set of thermochemical data and highpressure-limit kinetics for NOx formation and destruction. Hartree-Fock structures and frequencies and fourth-order Moeller-Plesset energies were used for reactions of H/N/O-species involving H1N1O1 , N1O2, N2O1, H1N 2O1, and N2O2 surfaces, including NH + NO ↔ N2O + H, N2O + O ↔ NO + NO, N + OH ↔ NO + H, N + O2 ↔ NO + O, and N + NO ↔ N2 + O. Thermochemical results were discussed in the form of potential energy surfaces. In general, BAC-MP4 heats of formation compared consistently well to literature data. The results generated from this work allowed evaluation of pressure-dependent kinetics and, ultimately, a refined group of reactions for the NOx mechanism. Strengths of particular bonds and bonding combinations in polycarbodiimides were calculated. Work focused on effects of R groups, chain size and stereoregularity on bond dissociation energies (BDE). Specifically, five polycarbodiimide systems were studied: (1) R=R′=H, (2) R=R′ =CH3, (3) R=R′=CH2CH 3, (4) R=CH(CH3)(Phenyl), R′=H, and (5) R=CH(CH3)(phenyl), R′=CH 3. Methyl- and ethyl-substituted polycarbodiimides decreased the bond strength of the central C-N bond. Ligands on the amine (backbone) nitrogen weakened its chain C-N bond dramatically. However, a lower barrier reaction has also been identified. Results imply rapid, concerted unzipping of this polymer, a result consistent with experiment. For the polyhydroxyamide (PHA) system, a model cyclization reaction of PHA to polybenzoxazole (PBO) was evaluated. PHA cyclization to PBO has been studied experimentally, but a detailed theoretical reaction surface has never been evaluated. Moreover, a plausible mechanism by which PHA arrives at PBO had not been previously determined. The calculated overall heat of reaction was thermoneutral, and decomposition was determined to occur at 212°C, compared to the 215°C experimental value. The hydrogen-transfer reaction and a four-center concerted transition-state reaction were found to be the limiting steps.
Rotem, Karin, "Computational quantum chemistry applied to nitrogen oxide chemistry and new fire-resistant polymers" (1999). Doctoral Dissertations Available from Proquest. AAI9920647.