Mechanistic study of the reaction of methyl peroxy radical (CH3O2) with formaldehyde (CH2O)

Abstract

ABSTRACTA direct dynamic study on the reactions of CH3O2 + CH2O was carried out over the temperature range of 300–1500 K. All stationary points were calculated with the M06-2X/6-311++G(d,p) level of theory and identified for local minimum. The energetic parameters were refined at QCISD (T)/cc-pVTZ and CCSD (T)/cc-pVTZ levels of theory. Three channels were explored and a reaction of hydrogen abstraction from CH2O by CH3O2 was identified as dominant channel which involves the formation of a prereactive complex in the entrance channel. The rate coefficient of the dominant channel was calculated with TST and TST/Eck and the Eckart tunnelling effect is only important over the lower temperature region. The calculated rate coefficient of the dominant channel has positive temperature dependence and agrees reasonably with the available literature data.