Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen
Abstract
Oxidation mechanism of an embedded five-member ring on a surface of a carbonaceous particle with atomic oxygen has been studied employing G3(MP2,CC)//B3LYP/6-311G* potential energy surface calculations for C15H9 + O reactions. Temperature- and pressure-dependent reaction rate constants have been evaluated using the RRKM – Master Equation approach. The mechanism involves barrierless oxygen atom addition to a carbon atom on a free edge of a five-member ring followed by migration of the H atom from the attacked C atom to an ortho position followed by the five-member ring opening and elimination of the CO group, with the five-member ring being fully destroyed. When the embedded ring has three common sides with surrounding six-member rings and one free-edge carbon atom, the only product is the 4-phenanthrenyl radical. Finally, when the embedded ring has two common sides with the six-member rings and two free-edge C atoms, two different decarbonylation products possessing a phenalene core can be formed depending on the direction of the 1,2-H shift.
- Authors:
-
- Samara National Research Univ., Samara (Russia); Florida International Univ., Miami, FL (United States)
- Samara National Research Univ., Samara (Russia); Levedev Physical Inst., Samara (Russia)
- Publication Date:
- Research Org.:
- Florida International Univ. (FIU), Miami, FL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
- OSTI Identifier:
- 1594778
- Alternate Identifier(s):
- OSTI ID: 1636451
- Grant/Contract Number:
- FG02-04ER15570; 14.Y26.31.0020
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Physics
- Additional Journal Information:
- Journal Volume: 519; Journal Issue: C; Journal ID: ISSN 0301-0104
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; five-member ring; oxidation; atomic oxygen; potential energy surface; RRKM - Master Equation; rate constant
Citation Formats
Galimova, G. R., Azyazov, V. N., Porfiriev, D. P., and Mebel, A. M. Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen. United States: N. p., 2018.
Web. doi:10.1016/j.chemphys.2018.12.006.
Galimova, G. R., Azyazov, V. N., Porfiriev, D. P., & Mebel, A. M. Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen. United States. https://doi.org/10.1016/j.chemphys.2018.12.006
Galimova, G. R., Azyazov, V. N., Porfiriev, D. P., and Mebel, A. M. Mon .
"Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen". United States. https://doi.org/10.1016/j.chemphys.2018.12.006. https://www.osti.gov/servlets/purl/1594778.
@article{osti_1594778,
title = {Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen},
author = {Galimova, G. R. and Azyazov, V. N. and Porfiriev, D. P. and Mebel, A. M.},
abstractNote = {Oxidation mechanism of an embedded five-member ring on a surface of a carbonaceous particle with atomic oxygen has been studied employing G3(MP2,CC)//B3LYP/6-311G* potential energy surface calculations for C15H9 + O reactions. Temperature- and pressure-dependent reaction rate constants have been evaluated using the RRKM – Master Equation approach. The mechanism involves barrierless oxygen atom addition to a carbon atom on a free edge of a five-member ring followed by migration of the H atom from the attacked C atom to an ortho position followed by the five-member ring opening and elimination of the CO group, with the five-member ring being fully destroyed. When the embedded ring has three common sides with surrounding six-member rings and one free-edge carbon atom, the only product is the 4-phenanthrenyl radical. Finally, when the embedded ring has two common sides with the six-member rings and two free-edge C atoms, two different decarbonylation products possessing a phenalene core can be formed depending on the direction of the 1,2-H shift.},
doi = {10.1016/j.chemphys.2018.12.006},
journal = {Chemical Physics},
number = C,
volume = 519,
place = {United States},
year = {Mon Dec 17 00:00:00 EST 2018},
month = {Mon Dec 17 00:00:00 EST 2018}
}
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Works referencing / citing this record:
The mechanism and rate constants for oxidation of indenyl radical C 9 H 7 with molecular oxygen O 2 : a theoretical study
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