jp4000413_si_001.pdf (644.25 kB)
Theoretical and Kinetic Study of the Reactions of Ketones with HȮ2 Radicals. Part I: Abstraction Reaction Channels
journal contribution
posted on 2016-02-19, 07:07 authored by Jorge Mendes, Chong-Wen Zhou, Henry
J. CurranThis 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.