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Title: The mechanism and rate constants for oxidation of indenyl radical C 9H 7 with molecular oxygen O 2: a theoretical study

Abstract

Ab initio G3(MP2,CC)//B3LYP/6-311G(d,p) calculations have been carried out in this work to map out the C 9H 7O 2 potential energy surface in relation to the reaction of the 1-indenyl radical with molecular oxygen. The resulting energetics and molecular parameters of the species involved in the reaction have been then utilized in Rice–Ramsperger–Kassel–Marcus master equation calculations of temperature- and pressure-dependent reaction rate constants and product branching ratios. The results demonstrate that, while the reaction is insignificant at low temperatures, at higher temperatures, above 800 K or higher depending on the pressure, the prevailing reaction channel leads to the formation of the 1- H-inden-1-one + OH products via a 1,3-H shift from C to O in the initial association complex W1 accompanied by OH elimination through a high barrier of 25.6 kcal mol ₋1. The branching ratio of 1- H-inden-1-one + OH increases from ~61% to ~80% with temperature, whereas c-C 6H 4-CH 2CHO + CO (32–12%) and coumarin + H (7–6%) are significant minor products. The total rate constant of the indenyl + O 2 reaction leading to the bimolecular products is independent of pressure and exceeds 1.0 × 10 ₋15 cm 3 molecule ₋1 s ₋1 only at temperaturesmore » above 2000 K, reaching 6.7 × 10 ₋15 cm 3 molecule ₋1 s ₋1 at 2500 K. The indenyl + O 2 reaction is concluded to be too slow to play a substantial role in oxidation of the five-member ring in indenyl and the present results corroborate the assertion that molecular oxygen is not an efficient oxidizer of five-member-ring radicals.« less

Authors:
 [1];  [1];  [1]; ORCiD logo [2]
  1. Samara Univ. (Russia); Lebedev Physical Inst., Samara (Russia)
  2. Samara Univ. (Russia); ; Florida International Univ., Miami, FL (United States)
Publication Date:
Research Org.:
Florida International Univ., Miami, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Ministry of Education and Science of the Russian Federation
OSTI Identifier:
1594769
Alternate Identifier(s):
OSTI ID: 1507167
Grant/Contract Number:  
FG02-04ER15570; 14.Y26.31.0020
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 21; Journal Issue: 17; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ghildina, A. R., Porfiriev, D. P., Azyazov, V. N., and Mebel, A. M. The mechanism and rate constants for oxidation of indenyl radical C9H7 with molecular oxygen O2: a theoretical study. United States: N. p., 2019. Web. doi:10.1039/c9cp01122f.
Ghildina, A. R., Porfiriev, D. P., Azyazov, V. N., & Mebel, A. M. The mechanism and rate constants for oxidation of indenyl radical C9H7 with molecular oxygen O2: a theoretical study. United States. doi:10.1039/c9cp01122f.
Ghildina, A. R., Porfiriev, D. P., Azyazov, V. N., and Mebel, A. M. Wed . "The mechanism and rate constants for oxidation of indenyl radical C9H7 with molecular oxygen O2: a theoretical study". United States. doi:10.1039/c9cp01122f.
@article{osti_1594769,
title = {The mechanism and rate constants for oxidation of indenyl radical C9H7 with molecular oxygen O2: a theoretical study},
author = {Ghildina, A. R. and Porfiriev, D. P. and Azyazov, V. N. and Mebel, A. M.},
abstractNote = {Ab initio G3(MP2,CC)//B3LYP/6-311G(d,p) calculations have been carried out in this work to map out the C9H7O2 potential energy surface in relation to the reaction of the 1-indenyl radical with molecular oxygen. The resulting energetics and molecular parameters of the species involved in the reaction have been then utilized in Rice–Ramsperger–Kassel–Marcus master equation calculations of temperature- and pressure-dependent reaction rate constants and product branching ratios. The results demonstrate that, while the reaction is insignificant at low temperatures, at higher temperatures, above 800 K or higher depending on the pressure, the prevailing reaction channel leads to the formation of the 1-H-inden-1-one + OH products via a 1,3-H shift from C to O in the initial association complex W1 accompanied by OH elimination through a high barrier of 25.6 kcal mol₋1. The branching ratio of 1-H-inden-1-one + OH increases from ~61% to ~80% with temperature, whereas c-C6H4-CH2CHO + CO (32–12%) and coumarin + H (7–6%) are significant minor products. The total rate constant of the indenyl + O2 reaction leading to the bimolecular products is independent of pressure and exceeds 1.0 × 10₋15 cm3 molecule₋1 s₋1 only at temperatures above 2000 K, reaching 6.7 × 10₋15 cm3 molecule₋1 s₋1 at 2500 K. The indenyl + O2 reaction is concluded to be too slow to play a substantial role in oxidation of the five-member ring in indenyl and the present results corroborate the assertion that molecular oxygen is not an efficient oxidizer of five-member-ring radicals.},
doi = {10.1039/c9cp01122f},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 17,
volume = 21,
place = {United States},
year = {2019},
month = {4}
}

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