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Title:Theoretical and Kinetic Study of the Hydrogen Atom Abstraction Reactions of Esters with HO2 Radicals
Authors:J. Mendes, C.-W. Zhou, H. J. Curran, 2013
Abstract: This work details an ab-initio and chemical kinetic study of the hydrogen atom abstraction reactions by the hydroperoxyl radical (HO2) on the following esters: methyl ethanoate, methyl propanoate, methyl butanoate, methyl pentanoate, methyl iso-butyrate, ethyl ethanoate, propyl ethanoate and iso-propyl ethanoate. Geometry optimization and frequency calculation of all of the species involved, as well as the hindrance potential description for reactants and transition states, has been performed with the Møller–Plesset (MP2) method using the 6-311G(d,p) basis set. Validation of all of the connections between transition states and local minima was performed by intrinsic reaction coordinate calculations. Electronic energies for all of the species are reported at the CCSD(T)/cc-pVTZ level of theory in kcal mol−1 with the zero-point energy corrections. The CCSD(T)/CBS (extrapolated from CCSD(T)/cc-pVXZ, in which X = D, T, Q) was used for the reactions of methyl ethanoate + HO2 radicals as a benchmark in the electronic energy calculations. High-pressure limit rate constants, in the temperature range 500–2000 K, have been calculated for all of the reaction channels using conventional transition state theory with asymmetric Eckart tunneling corrections. The 1-D hindered rotor approximation has been used for the low frequency torsional modes in both reactants and transition states. The calculated individual and total rate constants are reported for all of the reaction channels in every reaction system. A branching ratio analysis for every reaction site has also been investigated for all of the esters studied in this work.
ICHEC Project:Computational Quantum Chemistry and Kinetics of the Interaction of OH and HO2 Radicals with Biofuels
Publication:The Journal of Physical Chemistry A (2013) 10.1021/jp409133x
URL: http://pubs.acs.org/doi/abs/10.1021/jp409133x
Status: Accepted

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