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

14 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

ASJC Scopus subject areas

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

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