Hyperthermal o-atom exchange reaction O2 + CO2 through a CO4 intermediate

Laurence Y. Yeung, Mitchio Okumura, Jeffrey T. Paci, George C Schatz, Jianming Zhang, Timothy K. Minton

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

(Chemical Equation Presented) O2 and CO2 do not react under ordinary conditions because of the thermodynamic stability of CO 2 and the large activation energy required for multiple double-bond cleavage. We present evidence for a gas-phase O-atom exchange reaction between neutral O2 and CO2 at elevated collision energies (∼160 kcal mol-1) from crossed-molecular-beam experiments. CCSD(T)/augcc-pVTZ calculations demonstrate that isotope exchange can occur on the ground triplet potential energy surface through a short-lived CO4 intermediate that isomerizes via a symmetric CO4 transition state containing a bridging oxygen atom. We propose a plausible adiabatic mechanism for this reaction supported by additional spin-density calculations.

Original languageEnglish
Pages (from-to)13940-13942
Number of pages3
JournalJournal of the American Chemical Society
Volume131
Issue number39
DOIs
Publication statusPublished - Oct 7 2009

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Carbon Monoxide
Thermodynamics
Isotopes
Ion exchange
Gases
Oxygen
Atoms
Potential energy surfaces
Molecular beams
Thermodynamic stability
Activation energy
Experiments

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hyperthermal o-atom exchange reaction O2 + CO2 through a CO4 intermediate. / Yeung, Laurence Y.; Okumura, Mitchio; Paci, Jeffrey T.; Schatz, George C; Zhang, Jianming; Minton, Timothy K.

In: Journal of the American Chemical Society, Vol. 131, No. 39, 07.10.2009, p. 13940-13942.

Research output: Contribution to journalArticle

Yeung, Laurence Y. ; Okumura, Mitchio ; Paci, Jeffrey T. ; Schatz, George C ; Zhang, Jianming ; Minton, Timothy K. / Hyperthermal o-atom exchange reaction O2 + CO2 through a CO4 intermediate. In: Journal of the American Chemical Society. 2009 ; Vol. 131, No. 39. pp. 13940-13942.
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