A theoretical investigation of the gas-phase oxidation reaction of the saturated tert-butyl radical

Jong-Ho Choi, Mi J. Nam, Sung E. Youn

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The radical-radical reaction mechanisms and dynamics of ground-state atomic oxygen [O(3P)] with the saturated tert-butyl radical (t-C 4H9) are investigated using the density functional method and the complete basis set model. Two distinctive reaction pathways are predicted to be in competition: addition and abstraction. The barrierless addition of O(3P) to t-C4H9 leads to the formation of an energy-rich intermediate (OC4H9) on the lowest doublet potential energy surface, which undergoes subsequent direct elimination or isomerization-elimination leading to various products: C 3H6O + CH3, iso-C4H8O + H, C3H7O + CH2, and iso-C4H 8 + OH. The respective microscopic reaction processes examined with the aid of statistical calculations, predict that the major addition pathway is the formation of acetone (C3H6O) + CH3 through a low-barrier, single-step cleavage. For the direct, barrierless H-atom abstraction mechanism producing iso-C4H8 (isobutene) + OH, which was recently reported in gas-phase crossed-beam investigations, the reaction is described in terms of both an abstraction process (major) and a short-lived addition dynamic complex (minor).

Original languageEnglish
Pages (from-to)2526-2532
Number of pages7
JournalChemPhysChem
Volume7
Issue number12
DOIs
Publication statusPublished - 2006 Dec 11

Fingerprint

Acetone
Gases
vapor phases
Oxygen
Oxidation
Potential energy surfaces
oxidation
Isomerization
Ground state
elimination
Atoms
acetone
isomerization
cleavage
potential energy
ground state
isobutylene
oxygen
products
atoms

Keywords

  • Ab initio calculations
  • Oxidation
  • Radicals
  • Reaction mechanisms
  • Transition states

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

A theoretical investigation of the gas-phase oxidation reaction of the saturated tert-butyl radical. / Choi, Jong-Ho; Nam, Mi J.; Youn, Sung E.

In: ChemPhysChem, Vol. 7, No. 12, 11.12.2006, p. 2526-2532.

Research output: Contribution to journalArticle

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