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

Yeung, Laurence Y. and Okumura, Mitchio and Paci, Jeffrey T. and Schatz, George C. and Zhang, Jianming and Minton, Timothy K. (2009) Hyperthermal O-Atom Exchange Reaction O_2 + CO_2 through a CO_4 Intermediate. Journal of the American Chemical Society, 131 (39). pp. 13940-13942. ISSN 0002-7863.

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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.

Item Type:Article
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URLURL TypeDescription
Okumura, Mitchio0000-0001-6874-1137
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.
Funding AgencyGrant Number
Missile Defense AgencyHQ0006-05-2-0001
Davidow Discovery FundUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)FA955D-07-1-0095
Issue or Number:39
Record Number:CaltechAUTHORS:20091022-131306426
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Official Citation: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 Journal of the American Chemical Society 2009 131 (39), 13940-13942
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:16457
Deposited By: George Porter
Deposited On:22 Oct 2009 21:40
Last Modified:03 Oct 2019 01:12

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