| Autor: |
Ghildina AR; Lebedev Physical Institute, Samara 443011, Russia., Zavershinskiy IP; Samara University, Samara 443086, Russia., Mebel AM; Samara University, Samara 443086, Russia.; Department of Chemistry and Biochemistry, Florida International University, Miami, Florida 33199, United States., Vinogradov KY; Samara University, Samara 443086, Russia., Bulanova AV; Samara University, Samara 443086, Russia., Zhu H; Institute of Modern Catalysis, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China. |
| Jazyk: |
angličtina |
| Zdroj: |
The journal of physical chemistry. A [J Phys Chem A] 2021 Aug 12; Vol. 125 (31), pp. 6796-6804. Date of Electronic Publication: 2021 Jul 29. |
| DOI: |
10.1021/acs.jpca.1c05421 |
| Abstrakt: |
Electronic structure/Rice-Ramsperger-Kassel-Marcus Master equation calculations were applied to unravel the oxidation mechanism and kinetics of the cyclopenta[ a ]naphthalenyl radical with molecular oxygen. The reaction has been shown to proceed through the addition of O 2 in the ortho- position in the five-membered ring of C 13 H 9 . At low temperatures, the reaction yields a collisionally stabilized C 13 H 9 O 2 complex, which rapidly decomposes back to the reactants. In the high-temperature regime, above 800, 900, 1125, and 1375 K at pressures of 0.03, 1, 10, and 100 atm, respectively, the reaction forms bimolecular products including 3 H -/1 H -cyclopenta[ a ]naphthalen-3-one + OH as the prevailing product together with 1-ethanol-substituted 2-naphthyl radical + CO and 3 H -benzo[ f ]chromen-3-one + H as minor ones, with the branching ratio of the OH elimination channel growing with temperature and the rate constants for the individual bimolecular channels being independent of pressure. The calculated rate constants and product branching for cyclopenta[ a ]naphthalenyl + O 2 closely agree with those reported earlier for the indenyl + O 2 reaction and are recommended for the combustion kinetic models for the oxidation reactions of five-membered rings on free edges of larger polycyclic aromatic hydrocarbon molecules. The results also confirm that the oxidation of a π radical located on a five-membered ring with molecular oxygen is very slow. |
| Databáze: |
MEDLINE |
| Externí odkaz: |
|
