Abstract
The complex doublet potential-energy surface for the reaction of CCO with NO2, including 8 minimum isomers and 17 transition states, is explored theoretically using the coupled cluster and density functional theory. The association of CCO with NO2 was found to be a barrierless process forming an energy-rich adduct a (OCCNO2) followed by oxygen shift to give b (O2CCNO). Our results show that the product P1 (CO2 + CNO) is the major product with absolute yield, while the product P4 (2CO + NO) is the minor product with less abundance. The other products may be undetectable. The product P1 (CO2 + CNO) can be obtained through R →a → b → P1 (CO 2 + CNO), whereas the product P4 (2CO + NO) can be obtained through two channels R → a → b → c→ (d, g) → P2 (OCNO + CO) → P4 (2CO + NO) and R → a →b → f →P3 (c-OCC- O + NO) → P4 (2CO + NO). Because the intermediates and transition states involved in the above three channels are all lower than the reactants in energy, the CCO + NO2 reaction is expected to be rapid, which is consistent with the experimental measurement in quality. The present study may be helpful for further experimental investigation of the title reaction.
Original language | English |
---|---|
Pages (from-to) | 6503-6508 |
Number of pages | 6 |
Journal | Journal of Physical Chemistry A |
Volume | 109 |
Issue number | 29 |
DOIs | |
Publication status | Published - 28 Jul 2005 |
Externally published | Yes |