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Thermochemistry And Kinetics In Pyrolysis And Oxidation Of Oxygenated Chlorocarbons And Chlorinated Aromatics, Li Zhu

Dissertations

Thermochemical. properties, Δf_H°₂₉₈, S°₂₉₈, and Cp°(T) (5<=T/K<=6000), are determined using different ab inifio and density functional theory methods for three chloromethyl radicals, CH₂Cl, CHCl₂, CCl₃, all chlorobenzenes from monochlorobenzene to hexachlorobenzene, and all chlorophenols from ortho-, meta-, para-chlorophenol to pentachlorophenol. The B3LYP/6-31G(d,p) method is used in the structure optimization. The B3LYP/6-31G(3df,2p), QCISD(T)/6-3 I G(d,p), and CB S-Q methods are used in single point calculations of total electronic energies. Harmonic vibration frequencies are scaled for zero point energies and thermal corrections. Isodesmic reaction(s) are utilized at each calculation level to determine Δf_H°₂₉₈ of each species. Contributions to S°₂₉₈ and Cp°(T) from …