Theoretical and Kinetic Study of the Reactions of Ketones with HȮ2 Radicals. Part I: Abstraction Reaction Channels

This work presents an ab initio and chemical kinetic study of the reaction mechanisms of hydrogen atom abstraction by the HȮ2 radical on five ketones: dimethyl, ethyl methyl, n-propyl methyl, iso-propyl methyl, and iso-butyl methyl ketones. The Møller–Plesset method using the 6-311G­(d,p) basis set has been used in the geometry optimization and the frequency calculation for all the species involved in the reactions, as well as the hindrance potential description for reactants and transition states. Intrinsic reaction coordinate calculations were carried out to validate all the connections between transition states and local minima. Energies are reported at the CCSD­(T)/cc-pVTZ//MP2/6-311G­(d,p) level of theory. The CCSD­(T)/cc-pVXZ method (X = D, T, Q) was used for the reaction mechanism of dimethyl ketone + HȮ2 radical in order to benchmark the computationally less expensive method of CCSD­(T)/cc-pVTZ//MP2/6-311G­(d,p). High-pressure limit rate constants have been calculated for all the reaction channels by conventional transition state theory with asymmetric Eckart tunneling corrections and 1-D hindered rotor approximations in the temperature range 500–2000 K.