Ab initio kinetics predictions for the role of pre-reaction complexes in hydrogen abstraction from 2-butanone by OH radicals.

The existence of pre- and post-reaction complexes has been proposed to influence hydrogen abstraction reaction kinetics, but the significance still remains controversial. A theoretical study is presented to discuss the effects of complexes on hydrogen abstraction from 2-butanone by OH radicals based on the detailed PESs at the DLPNO-CCSD(T)/aug-cc-pVTZ//M06-2x-D3/may-cc-pVTZ level with five pre-reaction complexes at the entrance of the channels and four post-reaction complexes at the exit. The hydrogen bond interactions, steric effects, and contributions to the bonding orbital of the OH radical species and 2-butanone species in the complex structures were visualized and investigated by wavefunction analyses. Three kinds of mechanisms-the general bimolecular reaction, the reaction with the complexes considered, and the well-skipping reaction-were compared based on high-pressure-limit rate constants, predicted branching ratios, and fractional populations of reactants and products in the temperature range of 250-2000 K. The existence of complexes was proved to be crucial in the kinetics and mechanisms of the hydrogen abstraction from 2-butanone molecules by OH radicals.