Quantum
Chemistry, Reaction Kinetics, and Tunneling Effects in the Reaction
of Methoxy Radicals with O<sub>2</sub>
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Abstract
The
reaction of the methoxy radical with O<sub>2</sub> is the prototype
for the reaction of a range of larger alkoxy radicals with O<sub>2</sub> in the lower atmosphere. This reaction presents major challenges
to quantum chemistry, with CCSD(T) overpredicting the barrier height
by about 7 kcal/mol in the complete basis set limit. CCSD(T) calculations
also indicate that the CH<sub>3</sub>OOO<sup>•</sup> analog
of the HOOO<sup>•</sup> radical is energetically unstable with
respect to CH<sub>3</sub>O<sup>•</sup> + O<sub>2</sub>, a finding
that seems unlikely. The previous successful prediction of the barrier
height using CCSD(T)/cc-pVTZ energies at CASSCF/6-311G(d,p) geometries
is shown to rely on the use of a metastable Hartree–Fock reference
wave function. The performance of several density functionals is explored
and B3LYP is selected to examine the role of tunneling, including
the competition between small curvature tunneling (SCT) and large
curvature tunneling (LCT). SCT is found to be sufficient to describe
tunneling, in contrast to the typical findings for bimolecular hydrogen-abstraction
reactions. The previously proposed mechanism of a cyclic transition
state yields rate constants for CH<sub>3</sub>O<sup>•</sup> + O<sub>2</sub> that faithfully reproduces the experimentally derived
Arrhenius pre-exponential term. Predictions of the branching ratios
for the competing reactions CH<sub>2</sub>DO<sup>•</sup> +
O<sub>2</sub> → CHDO + HO<sub>2</sub> (1a) and CH<sub>2</sub>DO<sup>•</sup> + O<sub>2</sub>→ CH<sub>2</sub>O + DO<sub>2</sub> (1b) are also in good agreement with experiment