The reaction of O 2 with HOCO has been studied by using an ab initio direct dynamics method based on the UB3PW91 density functional theory. Results show that the reaction can occur via two mechanisms: direct hydrogen abstraction and an addition reaction through a short-lived HOC(O)O 2 intermediate. The lifetime of the intermediate is predicted to be 660 ±30 fs. Although it is an activated reaction, the activation energy is only 0.71 kcal/mol. At room temperature, the obtained thermal rate coefficient is 2.1 × 10 -12 cm 3 molecule -1 s -1, which is in good agreement with the experimental results.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry