We have calculated rate constants and reaction energies for addition reactions of the acryloyl (C3H3O●) and butadienyl (C4H5●) radicals each with triplet O2, triplet O atom, and singlet O atom. These hydrocarbon radicals each correspond to two isomers separated by little or no barrier, where the less stable 1,3-dienyl radicals lead to more stable products than the 1,2-allyl radicals. Optimized geometries and molecular orbitals were calculated at the MCSCF level using correlation consistent basis sets. Multi-reference CI calculations were then performed to obtain more accurate single-point energies. Analysis based on the Eyring kinetic model predicts that a significant mixture of products will be formed at combustion temperatures. These thermodynamic and kinetic data will help quantify the relative amounts of these products in a high-temperature flame or engine.

<i>Ab initio</i> kinetic analysis of acryloyl and butadienyl radicals with atomic and molecular oxygen

251st National Meeting (2016)

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Ab initio kinetic analysis of acryloyl and butadienyl radicals with atomic and molecular oxygen