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

doi:10.1021/ja903944k

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

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

17 Scopus citations

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 language	English (US)
Pages (from-to)	13940-13942
Number of pages	3
Journal	Journal of the American Chemical Society
Volume	131
Issue number	39
DOIs	https://doi.org/10.1021/ja903944k
State	Published - Oct 7 2009

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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title = "Hyperthermal o-atom exchange reaction O2 + CO2 through a CO4 intermediate",

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.",

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T1 - Hyperthermal o-atom exchange reaction O2 + CO2 through a CO4 intermediate

AU - Yeung, Laurence Y.

AU - Okumura, Mitchio

AU - Paci, Jeffrey T.

AU - Schatz, George C.

AU - Zhang, Jianming

AU - Minton, Timothy K.

PY - 2009/10/7

Y1 - 2009/10/7

N2 - (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.

AB - (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.

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JO - Journal of the American Chemical Society

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

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