Ab Initio Reaction Kinetics of CH3OC(=O) and CH2OC(=O)H Radicals

Ting Tan, Xueliang Yang, Yiguang Ju, Emily A. Carter

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44 Scopus citations


The dissociation and isomerization kinetics of the methyl ester combustion intermediates methoxycarbonyl radical (CH3OC(=O)) and (formyloxy)methyl radical (CH2OC(=O)H) are investigated theoretically using high-level ab initio methods and Rice-Ramsperger-Kassel-Marcus (RRKM)/master equation (ME) theory. Geometries obtained at the hybrid density functional theory (DFT) and coupled cluster singles and doubles with perturbative triples correction (CCSD(T)) levels of theory are found to be similar. We employ high-level ab initio wave function methods to refine the potential energy surface: CCSD(T), multireference singles and doubles configuration interaction (MRSDCI) with the Davidson-Silver (DS) correction, and multireference averaged coupled-pair functional (MRACPF2) theory. MRSDCI+DS and MRACPF2 capture the multiconfigurational character of transition states (TSs) and predict lower barrier heights than CCSD(T). The temperature- and pressure-dependent rate coefficients are computed using RRKM/ME theory in the temperature range 300-2500 K and a pressure range of 0.01 atm to the high-pressure limit, which are then fitted to modified Arrhenius expressions. Dissociation of CH3OC(=O) to CH3 and CO2 is predicted to be much faster than dissociating to CH3O and CO, consistent with its greater exothermicity. Isomerization between CH3OC(=O) and CH2OC(=O)H is predicted to be the slowest among the studied reactions and rarely happens even at high temperature and high pressure, suggesting the decomposition pathways of the two radicals are not strongly coupled. The predicted rate coefficients and branching fractions at finite pressures differ significantly from the corresponding high-pressure-limit results, especially at relatively high temperatures. Finally, because it is one of the most important CH3O removal mechanisms under atmospheric conditions, the reaction kinetics of CH3O + CO was also studied along the PES of CH3OC(=O); the resulting kinetics predictions are in remarkable agreement with experiments.

Original languageEnglish (US)
Pages (from-to)1590-1600
Number of pages11
JournalJournal of Physical Chemistry B
Issue number8
StatePublished - Mar 3 2016
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Materials Chemistry
  • Surfaces, Coatings and Films
  • Physical and Theoretical Chemistry


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