Theoretical Investigation of the Radical-Radical Reaction of O(3P) + C2H3 and Comparison with Gas-Phase Crossed-Beam Experiments

Se Hee Jung, Su Chan Jang, Jin Wook Kim, Jang Woon Kim, Jong-Ho Choi

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

Herein, we present an ab initio study of the prototypal radical-radical reactions of ground-state atomic oxygen [O(3P)] with the vinyl (C2H3) radical using density functional theory and a complete basis set model. Two distinctive pathways on the lowest doublet potential energy surfaces (PESs) were predicted to be in competition: addition and abstraction. The barrierless addition of O(3P) to the hydrocarbon radicals leads to energy-rich intermediate formation followed by subsequent isomerization and decomposition to yield various products: CH2CO (ketene) + H, CO + CH3, C2HOH (acetylenol) + H, 3,1CCHOH + H, H2O + C2H, 3,1CH2 + HCO, H2CO (formaldehyde) + CH, C2H2 (acetylene) + OH, and 3,1CCH2 + OH. The competing but minor H-atom abstraction mechanisms produce C2H2 + OH and 1,3CCH2 + OH. The optimized structures of the reactants, products, intermediates, and transition states and the reaction mechanisms were obtained on the lowest doublet PESs. The major pathway was predicted to be the formation of CH2CO + H through the low-barrier, single-step cleavages of the addition intermediates. The Levine-Bernstein prior method, statistical surprisal approach, and microcanonical Rice-Ramsperger-Kassel-Marcus theory were applied to deduce the energy distributions of H atoms and OH products and quantitative rate constants. On the basis of the statistical theory and the population analysis, the predicted energy distributions were compared to the kinetic energy release of H and the preferential population of the Π(A′) component of OH products reported in recent gas-phase crossed-beam investigations (Park, M. J.; Jang, S. C.; Choi, J. H. J. Chem. Phys. 2012, 137, 204311), and their kinetic and dynamic characteristics were discussed.

Original languageEnglish
Pages (from-to)11761-11771
Number of pages11
JournalJournal of Physical Chemistry A
Volume119
Issue number49
DOIs
Publication statusPublished - 2015 Dec 10

Fingerprint

Potential energy surfaces
Gases
vapor phases
Acetylene
Atoms
Population Dynamics
Carbon Monoxide
products
Isomerization
Hydrocarbons
Kinetic energy
Ground state
Formaldehyde
Density functional theory
Rate constants
Statistical methods
energy distribution
Experiments
potential energy
vinyl radical

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Theoretical Investigation of the Radical-Radical Reaction of O(3P) + C2H3 and Comparison with Gas-Phase Crossed-Beam Experiments. / Jung, Se Hee; Jang, Su Chan; Kim, Jin Wook; Kim, Jang Woon; Choi, Jong-Ho.

In: Journal of Physical Chemistry A, Vol. 119, No. 49, 10.12.2015, p. 11761-11771.

Research output: Contribution to journalArticle

@article{55ea6be80761414786f16e1cb72e09a6,
title = "Theoretical Investigation of the Radical-Radical Reaction of O(3P) + C2H3 and Comparison with Gas-Phase Crossed-Beam Experiments",
abstract = "Herein, we present an ab initio study of the prototypal radical-radical reactions of ground-state atomic oxygen [O(3P)] with the vinyl (C2H3) radical using density functional theory and a complete basis set model. Two distinctive pathways on the lowest doublet potential energy surfaces (PESs) were predicted to be in competition: addition and abstraction. The barrierless addition of O(3P) to the hydrocarbon radicals leads to energy-rich intermediate formation followed by subsequent isomerization and decomposition to yield various products: CH2CO (ketene) + H, CO + CH3, C2HOH (acetylenol) + H, 3,1CCHOH + H, H2O + C2H, 3,1CH2 + HCO, H2CO (formaldehyde) + CH, C2H2 (acetylene) + OH, and 3,1CCH2 + OH. The competing but minor H-atom abstraction mechanisms produce C2H2 + OH and 1,3CCH2 + OH. The optimized structures of the reactants, products, intermediates, and transition states and the reaction mechanisms were obtained on the lowest doublet PESs. The major pathway was predicted to be the formation of CH2CO + H through the low-barrier, single-step cleavages of the addition intermediates. The Levine-Bernstein prior method, statistical surprisal approach, and microcanonical Rice-Ramsperger-Kassel-Marcus theory were applied to deduce the energy distributions of H atoms and OH products and quantitative rate constants. On the basis of the statistical theory and the population analysis, the predicted energy distributions were compared to the kinetic energy release of H and the preferential population of the Π(A′) component of OH products reported in recent gas-phase crossed-beam investigations (Park, M. J.; Jang, S. C.; Choi, J. H. J. Chem. Phys. 2012, 137, 204311), and their kinetic and dynamic characteristics were discussed.",
author = "Jung, {Se Hee} and Jang, {Su Chan} and Kim, {Jin Wook} and Kim, {Jang Woon} and Jong-Ho Choi",
year = "2015",
month = "12",
day = "10",
doi = "10.1021/acs.jpca.5b09191",
language = "English",
volume = "119",
pages = "11761--11771",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "49",

}

TY - JOUR

T1 - Theoretical Investigation of the Radical-Radical Reaction of O(3P) + C2H3 and Comparison with Gas-Phase Crossed-Beam Experiments

AU - Jung, Se Hee

AU - Jang, Su Chan

AU - Kim, Jin Wook

AU - Kim, Jang Woon

AU - Choi, Jong-Ho

PY - 2015/12/10

Y1 - 2015/12/10

N2 - Herein, we present an ab initio study of the prototypal radical-radical reactions of ground-state atomic oxygen [O(3P)] with the vinyl (C2H3) radical using density functional theory and a complete basis set model. Two distinctive pathways on the lowest doublet potential energy surfaces (PESs) were predicted to be in competition: addition and abstraction. The barrierless addition of O(3P) to the hydrocarbon radicals leads to energy-rich intermediate formation followed by subsequent isomerization and decomposition to yield various products: CH2CO (ketene) + H, CO + CH3, C2HOH (acetylenol) + H, 3,1CCHOH + H, H2O + C2H, 3,1CH2 + HCO, H2CO (formaldehyde) + CH, C2H2 (acetylene) + OH, and 3,1CCH2 + OH. The competing but minor H-atom abstraction mechanisms produce C2H2 + OH and 1,3CCH2 + OH. The optimized structures of the reactants, products, intermediates, and transition states and the reaction mechanisms were obtained on the lowest doublet PESs. The major pathway was predicted to be the formation of CH2CO + H through the low-barrier, single-step cleavages of the addition intermediates. The Levine-Bernstein prior method, statistical surprisal approach, and microcanonical Rice-Ramsperger-Kassel-Marcus theory were applied to deduce the energy distributions of H atoms and OH products and quantitative rate constants. On the basis of the statistical theory and the population analysis, the predicted energy distributions were compared to the kinetic energy release of H and the preferential population of the Π(A′) component of OH products reported in recent gas-phase crossed-beam investigations (Park, M. J.; Jang, S. C.; Choi, J. H. J. Chem. Phys. 2012, 137, 204311), and their kinetic and dynamic characteristics were discussed.

AB - Herein, we present an ab initio study of the prototypal radical-radical reactions of ground-state atomic oxygen [O(3P)] with the vinyl (C2H3) radical using density functional theory and a complete basis set model. Two distinctive pathways on the lowest doublet potential energy surfaces (PESs) were predicted to be in competition: addition and abstraction. The barrierless addition of O(3P) to the hydrocarbon radicals leads to energy-rich intermediate formation followed by subsequent isomerization and decomposition to yield various products: CH2CO (ketene) + H, CO + CH3, C2HOH (acetylenol) + H, 3,1CCHOH + H, H2O + C2H, 3,1CH2 + HCO, H2CO (formaldehyde) + CH, C2H2 (acetylene) + OH, and 3,1CCH2 + OH. The competing but minor H-atom abstraction mechanisms produce C2H2 + OH and 1,3CCH2 + OH. The optimized structures of the reactants, products, intermediates, and transition states and the reaction mechanisms were obtained on the lowest doublet PESs. The major pathway was predicted to be the formation of CH2CO + H through the low-barrier, single-step cleavages of the addition intermediates. The Levine-Bernstein prior method, statistical surprisal approach, and microcanonical Rice-Ramsperger-Kassel-Marcus theory were applied to deduce the energy distributions of H atoms and OH products and quantitative rate constants. On the basis of the statistical theory and the population analysis, the predicted energy distributions were compared to the kinetic energy release of H and the preferential population of the Π(A′) component of OH products reported in recent gas-phase crossed-beam investigations (Park, M. J.; Jang, S. C.; Choi, J. H. J. Chem. Phys. 2012, 137, 204311), and their kinetic and dynamic characteristics were discussed.

UR - http://www.scopus.com/inward/record.url?scp=84949023934&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84949023934&partnerID=8YFLogxK

U2 - 10.1021/acs.jpca.5b09191

DO - 10.1021/acs.jpca.5b09191

M3 - Article

VL - 119

SP - 11761

EP - 11771

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 49

ER -