Theoretical and Kinetic Study of the Reactions of Ketones with HO(2) Radicals. Part I: Abstraction Reaction Channels.
Date
2013Author
Mendes, Jorge
Zhou, Chong-Wen
Curran, Henry J.
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Mendes J, Zhou CW, Curran HJ. (2013) Theoretical and Kinetic Study of the Reactions of Ketones with HO(2) Radicals. Part I: Abstraction Reaction Channels. J Phys Chem A. 2013 Apr 16. [Epub ahead of print]
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Abstract
This work presents an ab-initio and chemical kinetic study of the reaction
mechanisms of hydrogen atom abstraction by the HO2 radical on five ketones:
dimethyl, ethyl methyl, n-propyl methyl, iso-propyl methyl and iso-butyl methyl
ketones. The Moller-Plesset method with 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 co-ordinate 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 + HO2 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 Eckart tunneling
corrections and 1-D hindered rotor approximations in the temperature range
500-2000 K.