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dc.contributor.authorMendes, Jorge
dc.contributor.authorZhou, Chong-Wen
dc.contributor.authorCurran, Henry J.
dc.identifier.citationMendes, Jorge, Zhou, Chong-Wen, & Curran, Henry J. (2013). Theoretical and Kinetic Study of the Hydrogen Atom Abstraction Reactions of Esters with HȮ2 Radicals. The Journal of Physical Chemistry A, 117(51), 14006-14018. doi: 10.1021/jp409133xen_IE
dc.description.abstractThis 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 isobutyrate, ethyl ethanoate, propyl ethanoate, and isopropyl ethanoate. Geometry optimizations and frequency calculations of all of the species involved, as well as the hindrance potential descriptions for reactants and transition states, have been performed with the Moller-Plesset (MP2) method using the 6-311G(d,p) basis set. A 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 each reaction system. A branching ratio analysis for each reaction site has also been investigated for all of the esters studied in this work.en_IE
dc.description.sponsorshipThis work was supported by Science Foundation Ireland under grant number [08/IN1./I2055].en_IE
dc.publisherAmerican Chemical Societyen_IE
dc.relation.ispartofJournal Of Physical Chemistry Aen
dc.rightsAttribution-NonCommercial-NoDerivs 3.0 Ireland
dc.subjectQuadratic configuration interactionen_IE
dc.subjectVariational transition stateen_IE
dc.subjectReaction channelsen_IE
dc.subjectCoupled clusteren_IE
dc.subjectBarrier heighten_IE
dc.subjectRate constantsen_IE
dc.titleTheoretical and kinetic study of the hydrogen atom abstraction reactions of esters with HO2 radicalsen_IE
dc.local.contactHenry Curran, Dept Of Chemistry, Room 215, Arts/Science Building, Nui Galway. 3856 Email:

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