With growing concern about both the finite nature of traditional petroleum based fuels and their relation to climate change there is a clear need to increase our understanding of how these fuels, and potential new biofuels, react under combustion and atmospheric conditions. Both processes involve the oxidation of hydrocarbons, with sequential steps leading to increasingly oxidized species. The study reported here uses n-ketoheptyl-m-peroxy radicals, where n ranges from 1-4 and m ranges from 1-7, as a model system for studying the unimolecular decomposition of these oxygenated hydrocarbons. All geometry optimizations and frequency calculations are carried out using the Gaussian 09 suite of programs. Final energy calculations were conducted using the CBS-QB3, G3 and G4 composite methods, which were selected for their reported accuracies of ~4 kJ mol<sup>-1</sup>. Rate parameters were determined using ChemRate, which includes Eckart tunneling and Pitzer and Gwinn 1D hindered rotor treatments. Initial results suggest that the location of the ketone group within the ring structure of transition state structures may increase the rate of H-migration reactions and that when the peroxy group is beta to the ketone, C-C bond scission is the dominant pathway under both atmospheric and combustion conditions.<br/>

Computational study of ketoheptylperoxy radical atmospheric decomposition and combustion

254th National Meeting (2017)

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