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

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. ^[2]; Azyazov, V. N. ^[2]; ^[3]

Samara Univ. (Russia); Lebedev Physical Inst., Samara (Russia); Florida International University
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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: Ministry of Education and Science of the Russian Federation; Ministry of Education and Science of the Russian Federation; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: FG02-04ER15570

OSTI ID:: 1594769

Alternate ID(s):: OSTI ID: 1507167

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

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (54)

Indene Formation under Single-Collision Conditions from the Reaction of Phenyl Radicals with Allene and Methylacetylene-A Crossed Molecular Beam and Ab Initio Study Parker, Dr Dorian S. N.; Zhang, Dr Fangtong; Kaiser, Dr Ralf I. Chemistry - An Asian Journal, Vol. 6, Issue 11 https://doi.org/10.1002/asia.201100535	journal	September 2011
Formation of soot from polycyclic aromatic hydrocarbons as well as fullerenes and carbon nanotubes in the combustion of hydrocarbon Mansurov, Z. A. Journal of Engineering Physics and Thermophysics, Vol. 84, Issue 1 https://doi.org/10.1007/s10891-011-0459-y	journal	January 2011
Soot formation Haynes, B. S.; Wagner, H. Gg. Progress in Energy and Combustion Science, Vol. 7, Issue 4 https://doi.org/10.1016/0360-1285(81)90001-0	journal	January 1981
Gaussian-3 theory using coupled cluster energies Curtiss, Larry A.; Raghavachari, Krishnan; Redfern, Paul C. Chemical Physics Letters, Vol. 314, Issue 1-2 https://doi.org/10.1016/S0009-2614(99)01126-4	journal	November 1999
Soot surface oxidation in hydrocarbon/air diffusion flames at atmospheric pressure Xu, F. Combustion and Flame, Vol. 132, Issue 1-2 https://doi.org/10.1016/S0010-2180(02)00459-5	journal	January 2003
Formation of polycyclic aromatic hydrocarbons and their growth to soot—a review of chemical reaction pathways Richter, H.; Howard, J. B. Progress in Energy and Combustion Science, Vol. 26, Issue 4-6 https://doi.org/10.1016/S0360-1285(00)00009-5	journal	August 2000
Internal structure of soot particles in a diffusion flame Botero, Maria L.; Sheng, Yuan; Akroyd, Jethro Carbon, Vol. 141 https://doi.org/10.1016/j.carbon.2018.09.063	journal	January 2019
The growth mechanism of polycyclic aromatic hydrocarbons from the reactions of anthracene and phenanthrene with cyclopentadienyl and indenyl Zhu, Ledong; Shi, Xiangli; Sun, Yanhui Chemosphere, Vol. 189 https://doi.org/10.1016/j.chemosphere.2017.09.004	journal	December 2017
Reaction mechanism, rate constants, and product yields for the oxidation of embedded five-member ring radicals with atomic oxygen Galimova, G. R.; Azyazov, V. N.; Porfiriev, D. P. Chemical Physics, Vol. 519 https://doi.org/10.1016/j.chemphys.2018.12.006	journal	March 2019
Soot surface growth and oxidation in laminar diffusion flames at pressures of 0.1–1.0 atm Kim, C. H.; El-Leathy, A. M.; Xu, F. Combustion and Flame, Vol. 136, Issue 1-2 https://doi.org/10.1016/j.combustflame.2003.09.017	journal	January 2004
Soot surface growth and oxidation at pressures up to 8.0 atm in laminar nonpremixed and partially premixed flames Kim, C. H.; Xu, F.; Faeth, G. M. Combustion and Flame, Vol. 152, Issue 3 https://doi.org/10.1016/j.combustflame.2007.10.016	journal	February 2008
On the chemical kinetics of cyclopentadiene oxidation Robinson, R. K.; Lindstedt, R. P. Combustion and Flame, Vol. 158, Issue 4 https://doi.org/10.1016/j.combustflame.2010.12.001	journal	April 2011
Experimental and modeling studies of C2H4/O2/Ar, C2H4/methylal/O2/Ar and C2H4/ethylal/O2/Ar rich flames and the effect of oxygenated additives Dias, Véronique; Vandooren, Jacques Combustion and Flame, Vol. 158, Issue 5 https://doi.org/10.1016/j.combustflame.2011.01.015	journal	May 2011
Reaction mechanism, rate constants, and product yields for unimolecular and H-assisted decomposition of 2,4-cyclopentadienone and oxidation of cyclopentadienyl with atomic oxygen Ghildina, A. R.; Oleinikov, A. D.; Azyazov, V. N. Combustion and Flame, Vol. 183 https://doi.org/10.1016/j.combustflame.2017.05.015	journal	September 2017
Reaction mechanism, rate constants, and product yields for the oxidation of Cyclopentadienyl and embedded five-member ring radicals with hydroxyl Galimova, G. R.; Azyazov, V. N.; Mebel, A. M. Combustion and Flame, Vol. 187 https://doi.org/10.1016/j.combustflame.2017.09.005	journal	January 2018
Detailed, sterically-resolved modeling of soot oxidation: Role of O atoms, interplay with particle nanostructure, and emergence of inner particle burning Frenklach, Michael; Liu, Zhenyuan; Singh, Ravi I. Combustion and Flame, Vol. 188 https://doi.org/10.1016/j.combustflame.2017.10.012	journal	February 2018
Oxidation of cyclopentadienyl radical with molecular oxygen: A theoretical study Oleinikov, Artem D.; Azyazov, Valeriy N.; Mebel, Alexander M. Combustion and Flame, Vol. 191 https://doi.org/10.1016/j.combustflame.2018.01.010	journal	May 2018
The site effect on PAHs formation in HACA-based mass growth process Liu, Peng; Li, Zepeng; Bennett, Anthony Combustion and Flame, Vol. 199 https://doi.org/10.1016/j.combustflame.2018.10.010	journal	January 2019
New form for reduced modeling of soot oxidation: Accounting for multi-site kinetics and surface reactivity Frenklach, Michael Combustion and Flame, Vol. 201 https://doi.org/10.1016/j.combustflame.2018.12.023	journal	March 2019
Development of a reduced n-heptane-n-butylbenzene-polycyclic aromatic hydrocarbon (PAH) mechanism for engine combustion simulation and soot prediction Huang, Haozhong; Zhu, Jizhen; Lv, Delin Energy, Vol. 165 https://doi.org/10.1016/j.energy.2018.09.162	journal	December 2018
Cyclopentadiene combustion in a plug flow reactor near 1150K Butler, Robert G.; Glassman, Irvin Proceedings of the Combustion Institute, Vol. 32, Issue 1 https://doi.org/10.1016/j.proci.2008.05.010	journal	January 2009
Hydrogen-assisted isomerizations of fulvene to benzene and of larger cyclic aromatic hydrocarbons Jasper, Ahren W.; Hansen, Nils Proceedings of the Combustion Institute, Vol. 34, Issue 1 https://doi.org/10.1016/j.proci.2012.06.165	journal	January 2013
The growth of PAHs and soot in the post-flame region Liu, Peng; Li, Zepeng; Roberts, William L. Proceedings of the Combustion Institute, Vol. 37, Issue 1 https://doi.org/10.1016/j.proci.2018.05.047	journal	January 2019
Atmospheric chemical reactions of alternatives of polybrominated diphenyl ethers initiated by OH: A case study on triphenyl phosphate Yu, Qi; Xie, Hong-Bin; Chen, Jingwen Science of The Total Environment, Vol. 571 https://doi.org/10.1016/j.scitotenv.2016.07.105	journal	November 2016
Soot Oxidation by OH: Theory Development, Model, and Experimental Validation Ghiassi, Hossein; Lignell, David; Lighty, JoAnn S. Energy & Fuels, Vol. 31, Issue 3 https://doi.org/10.1021/acs.energyfuels.6b02193	journal	December 2016
The Effect of Methyl Pentanoate Addition on the Structure of a Non-Premixed Counterflow n -Heptane/O ₂ Flame Knyazkov, Denis A.; Bolshova, Tatyana A.; Dmitriev, Artem M. Energy & Fuels, Vol. 32, Issue 2 https://doi.org/10.1021/acs.energyfuels.7b03185	journal	January 2018
C ₉ H ₈ Pyrolysis. o -Tolylacetylene, Indene, 1-Indenyl, and Biindenyls and the Mechanism of Indene Pyrolysis Wentrup, Curt; Winter, Hans-Wilhelm; Kvaskoff, David The Journal of Physical Chemistry A, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpca.5b03453	journal	May 2015
Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames Mebel, Alexander M.; Landera, Alexander; Kaiser, Ralf I. The Journal of Physical Chemistry A, Vol. 121, Issue 5 https://doi.org/10.1021/acs.jpca.6b09735	journal	January 2017
Insight into The Nature of Rim Bonds in Coronene Fedik, Nikita; Boldyrev, Alexander I. The Journal of Physical Chemistry A, Vol. 122, Issue 43 https://doi.org/10.1021/acs.jpca.8b07937	journal	October 2018
VUV Photoionization Study of the Formation of the Simplest Polycyclic Aromatic Hydrocarbon: Naphthalene (C ₁₀ H ₈ ) Zhao, Long; Kaiser, Ralf I.; Xu, Bo The Journal of Physical Chemistry Letters, Vol. 9, Issue 10 https://doi.org/10.1021/acs.jpclett.8b01020	journal	May 2018
Atmospheric Chemical Reactions of Monoethanolamine Initiated by OH Radical: Mechanistic and Kinetic Study Xie, Hong-Bin; Li, Chao; He, Ning Environmental Science & Technology, Vol. 48, Issue 3 https://doi.org/10.1021/es405110t	journal	January 2014
Chemical Kinetics and Mechanisms of Complex Systems: A Perspective on Recent Theoretical Advances Klippenstein, Stephen J.; Pande, Vijay S.; Truhlar, Donald G. Journal of the American Chemical Society, Vol. 136, Issue 2 https://doi.org/10.1021/ja408723a	journal	January 2014
Theoretical Unimolecular Kinetics for CH ₄ + M ⇄ CH ₃ + H + M in Eight Baths, M = He, Ne, Ar, Kr, H ₂ , N ₂ , CO, and CH ₄ Jasper, Ahren W.; Miller, James A. The Journal of Physical Chemistry A, Vol. 115, Issue 24 https://doi.org/10.1021/jp200048n	journal	June 2011
Reformulation and Solution of the Master Equation for Multiple-Well Chemical Reactions Georgievskii, Yuri; Miller, James A.; Burke, Michael P. The Journal of Physical Chemistry A, Vol. 117, Issue 46 https://doi.org/10.1021/jp4060704	journal	May 2013
Thermochemical and Kinetic Analysis of the H, OH, HO ₂ , O, and O ₂ Association Reactions with Cyclopentadienyl Radical Zhong, Xian; Bozzelli, Joseph W. The Journal of Physical Chemistry A, Vol. 102, Issue 20 https://doi.org/10.1021/jp9804446	journal	May 1998
A VUV Photoionization Study of the Formation of the Indene Molecule and Its Isomers Zhang, Fangtong; Kaiser, Ralf I.; Kislov, Vadim V. The Journal of Physical Chemistry Letters, Vol. 2, Issue 14 https://doi.org/10.1021/jz200715u	journal	June 2011
Pressure-dependent rate constants for PAH growth: formation of indene and its conversion to naphthalene Mebel, Alexander M.; Georgievskii, Yuri; Jasper, Ahren W. Faraday Discussions, Vol. 195 https://doi.org/10.1039/C6FD00111D	journal	January 2016
Reactive polycyclic aromatic hydrocarbon dimerization drives soot nucleation Kholghy, M. R.; Kelesidis, G. A.; Pratsinis, S. E. Physical Chemistry Chemical Physics, Vol. 20, Issue 16 https://doi.org/10.1039/C7CP07803J	journal	January 2018
Nitrogen matters: the difference between PANH and PAH formation Bouwman, Jordy; Bodi, Andras; Hemberger, Patrick Physical Chemistry Chemical Physics, Vol. 20, Issue 47 https://doi.org/10.1039/C8CP05830J	journal	January 2018
Reaction mechanism of soot formation in flames Frenklach, Michael Physical Chemistry Chemical Physics, Vol. 4, Issue 11 https://doi.org/10.1039/b110045a	journal	February 2002
Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation Troe, J. The Journal of Chemical Physics, Vol. 66, Issue 11 https://doi.org/10.1063/1.433837	journal	June 1977
Density‐functional thermochemistry. III. The role of exact exchange Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652 https://doi.org/10.1063/1.464913	journal	April 1993
Gaussian-3 theory using density functional geometries and zero-point energies Baboul, Anwar G.; Curtiss, Larry A.; Redfern, Paul C. The Journal of Chemical Physics, Vol. 110, Issue 16 https://doi.org/10.1063/1.478676	journal	April 1999
Slow photoelectron velocity-map imaging spectroscopy of the C ₉ H ₇ (indenyl) and C ₁₃ H ₉ (fluorenyl) anions Kim, Jongjin B.; Weichman, Marissa L.; Yacovitch, Tara I. The Journal of Chemical Physics, Vol. 139, Issue 10 https://doi.org/10.1063/1.4820138	journal	September 2013
Photoionization Mass Spectrometric and Kinetic Modeling of Low‐pressure Pyrolysis of Benzene Yang, Jiu‐zhong; Zhao, Long; Cai, Jiang‐huai Chinese Journal of Chemical Physics, Vol. 26, Issue 3 https://doi.org/10.1063/1674-0068/26/03/245-251	journal	June 2013
The Role of Methyl Radical in Soot Formation Eremin, Alexander; Mikheyeva, Ekaterina Combustion Science and Technology, Vol. 191, Issue 12 https://doi.org/10.1080/00102202.2018.1551892	journal	December 2018
Surface Growth and Soot Particle Reactivity Harris, Stephen J. Combustion Science and Technology, Vol. 72, Issue 1-3 https://doi.org/10.1080/00102209008951640	journal	July 1990
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Lee, Chengteh; Yang, Weitao; Parr, Robert G. Physical Review B, Vol. 37, Issue 2 https://doi.org/10.1103/PhysRevB.37.785	journal	January 1988
Predictive a priori pressure-dependent kinetics Jasper, Ahren W.; Pelzer, Kenley M.; Miller, James A. Science, Vol. 346, Issue 6214 https://doi.org/10.1126/science.1260856	journal	December 2014
Quantum-Chemical Calculations of the Primary Reactions of Thermal Decomposition of Cyclopentadienone Ghildina, A. R.; Mebel, A. M.; Medvedkov, I. A. Combustion, Explosion, and Shock Waves, Vol. 54, Issue 1 https://doi.org/10.1134/S0010508218010021	journal	January 2018
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density Robert, Parr,; Chengteh, Lee,; Weitao, Yang, The University of North Carolina at Chapel Hill University Libraries https://doi.org/10.17615/zrp0-ry04	text	January 1988
Oxidation of Cyclopentadienyl Radical with Molecular Oxygen: a Theoretical Study Oleinikov, A. D.; Azyazov, V. N.; Mebel, A. M. 8th International Symposium on Nonequilibrium Processes, Plasma, Combustion, and Atmospheric Phenomena held Том. Volum 1. Kinetics and plasma https://doi.org/10.30826/nepcap2018-1-28	conference	April 2020
Potential Energy Surface for Oxidation of Indenyl C9H7 Ghildina, A. R.; Mebel, A. M.; Azyazov, V. N. Bulletin of the Lebedev Physics Institute, Vol. 45, Issue 10 https://doi.org/10.3103/S1068335618100019	journal	October 2018
The Role of Methyl Radical in Soot Formation Eremin, Alexander; Mikheyeva, Ekaterina Taylor & Francis https://doi.org/10.6084/m9.figshare.7492229.v1	text	January 2018

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