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Issue 23, 2011
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Ab initio and kinetic study of the reaction of ketones with ȮH for T = 500–2000 K. Part I: hydrogen-abstraction from H3CC(O)CH3x(CH3)x, x = 0 ↦ 2

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Abstract

A theoretical study is presented of the mechanism and kinetics of the reactions of the hydroxyl radical with three ketones: dimethyl (DMK), ethylmethyl (EMK) and iso-propylmethyl (iPMK) ketones. CCSD(T) values extrapolated to the basis set limit are used to benchmark the computationally less expensive methods G3 and G3MP2BH&H, for the DMK + ȮH reaction system. These latter methods are then used in computations involving the reactions of the larger ketones. All possible abstraction channels have been modeled. A stepwise mechanism involving the formation of a reactant complex in the entrance channel and a product complex in the exit channel has been recognized in part of the abstracting processes. High-pressure limit rate constants of the title reactions have been calculated in the temperature range of 500–2000 K using the Variflex code including Eckart tunneling corrections. Variable reaction coordinate transition state theory (VRC-TST) has been used for the rate constants of the barrier-less entrance channel. Calculated total rate constants (cm3 mol−1 s−1) are reported as follows:

k(DMK) = 1.32 × 102 × T3.30exp(503/T)

k(EMK) = 3.84 × 101 × T3.51exp(1515/T)

k(iPMK) = 2.08 × 101 × T3.58exp(2161/T)

Group rate constants (on a per H atom basis) for different carbon sites in title reactions have also been provided.

Graphical abstract: Ab initio and kinetic study of the reaction of ketones with ȮH for T = 500–2000 K. Part I: hydrogen-abstraction from H3CC(O)CH3–x(CH3)x, x = 0 ↦ 2

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Publication details

The article was received on 02 Dec 2010, accepted on 12 Apr 2011 and first published on 13 May 2011


Article type: Paper
DOI: 10.1039/C0CP02754E
Citation: Phys. Chem. Chem. Phys., 2011,13, 11175-11192
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    Ab initio and kinetic study of the reaction of ketones with ȮH for T = 500–2000 K. Part I: hydrogen-abstraction from H3CC(O)CH3x(CH3)x, x = 0 ↦ 2

    C. Zhou, J. M. Simmie and H. J. Curran, Phys. Chem. Chem. Phys., 2011, 13, 11175
    DOI: 10.1039/C0CP02754E

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