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Published October 7, 2009 | Supplemental Material
Journal Article Open

Hyperthermal O-Atom Exchange Reaction O_2 + CO_2 through a CO_4 Intermediate


O_2 and CO_2 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 O_2 and CO_2 at elevated collision energies (~160 kcal mol^(−1)) from crossed-molecular-beam experiments. CCSD(T)/aug-cc-pVTZ calculations demonstrate that isotope exchange can occur on the ground triplet potential energy surface through a short-lived CO_4 intermediate that isomerizes via a symmetric CO_4 transition state containing a bridging oxygen atom. We propose a plausible adiabatic mechanism for this reaction supported by additional spin-density calculations.

Additional Information

Copyright © 2009 American Chemical Society. Received May 14, 2009; Publication Date (Web): September 10, 2009. We thank G. B. Ellison, S. L. Mielke, and J. E. Wulff for insightful discussions. This work was supported by the Missile Defense Agency under cooperative agreement HQ0006-05-2-0001. L.Y.Y. was supported by the Davidow Fund, and G.C.S. was supported by AFOSR Grant FA955D-07-1-0095.

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August 19, 2023
October 19, 2023