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. https://resolver.caltech.edu/CaltechAUTHORS:20091022-131306426
![[img]](https://authors.library.caltech.edu/style/images/fileicons/application_pdf.png)
|
PDF (Newton diagrams and TOF distributions of 16O12C18O products, results of theoretical calculations, allowed product channels, and the proposed mechanism)
- Supplemental Material
See Usage Policy. 579Kb |
Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20091022-131306426
Abstract
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 | |||||||||
|---|---|---|---|---|---|---|---|---|---|---|
| Related URLs: |
| |||||||||
| ORCID: |
| |||||||||
| 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. | |||||||||
| Funders: |
| |||||||||
| Issue or Number: | 39 | |||||||||
| Record Number: | CaltechAUTHORS:20091022-131306426 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20091022-131306426 | |||||||||
| 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 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | George Porter | |||||||||
| Deposited On: | 22 Oct 2009 21:40 | |||||||||
| Last Modified: | 03 Oct 2019 01:12 |
Repository Staff Only: item control page
