The mechanism and rate constants for oxidation of indenyl radical C9H7 with molecular oxygen O2: a theoretical study

Ghildina, A. R.; Porfiriev, D. P.; Azyazov, V. N.; Mebel, A. M.

doi:10.1039/c9cp01122f

Title: The mechanism and rate constants for oxidation of indenyl radical C₉H₇ with molecular oxygen O₂: a theoretical study

Journal Article · Wed Apr 03 00:00:00 EDT 2019 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c9cp01122f· OSTI ID:1594769

Ghildina, A. R. ^[1]; Porfiriev, D. P. ^[1]; Azyazov, V. N. ^[1];

^[2]

Samara Univ. (Russia); Lebedev Physical Inst., Samara (Russia)
Samara Univ. (Russia); ; Florida International Univ., Miami, FL (United States)

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.

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Research Organization:: Florida International Univ. (FIU), Miami, FL (United States)

Sponsoring Organization:: Ministry of Education and Science of the Russian Federation; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-04ER15570; 14.Y26.31.0020

OSTI ID:: 1594769

Alternate ID(s):: OSTI ID: 1507167

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 21, Issue 17; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 14 works

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Title: The mechanism and rate constants for oxidation of indenyl radical C₉H₇ with molecular oxygen O₂: a theoretical study