Theoretical study on reaction mechanism of the ketenylidene radical with nitrogen dioxide

Jia Xu Zhang, Jing Yao Liu, Ze Sheng Li*, Chia Chung Sun

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

2 Citations (Scopus)

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 languageEnglish
Pages (from-to)6503-6508
Number of pages6
JournalJournal of Physical Chemistry A
Volume109
Issue number29
DOIs
Publication statusPublished - 28 Jul 2005
Externally publishedYes

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