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The oxidation of cycloalkanes is important in the combustion of transportation fuels and in atmospheric secondary organic aerosol formation. A transient carbon-centered radical intermediate (•QOOH) in the oxidation of cyclohexane is identified through its infrared fingerprint and time- and energy-resolved unimolecular dissociation dynamics to hydroxyl (OH) radical and bicyclic ether products. Although the cyclohexyl ring structure leads to three nearly degenerate •QOOH isomers (β-, γ-, and δ-QOOH), their transition state (TS) barriers to OH products are predicted to differ considerably. Selective characterization of the β-QOOH isomer is achieved at excitation energies associated with the lowest TS barrier, resulting in rapid unimolecular decay to OH products that are detected. A benchmarking approach is employed for the calculation of high-accuracy stationary point energies, in particular TS barriers, for cyclohexane oxidation (C6H11O2), building on higher-level reference calculations for the smaller ethane oxidation (C2H5O2) system. The isomer-specific characterization of β-QOOH is validated by comparison of experimental OH product appearance rates with computed statistical microcanonical rates, including significant heavy-atom tunneling, at energies in the vicinity of the TS barrier. Master-equation modeling is utilized to extend the results to thermal unimolecular decay rate constants at temperatures and pressures relevant to cyclohexane combustion.
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Watching a hydroperoxyalkyl radical (•QOOH) dissociate
A prototypical hydroperoxyalkyl radical (•QOOH) intermediate, transiently formed in the oxidation of volatile organic compounds, was directly observed through its infrared fingerprint and energy-dependent unimolecular decay to hydroxyl radical and cyclic ether products. Direct time-domain measurements of •QOOH unimolecular dissociation rates over a wide range of energies were found to be in accord with those predicted theoretically using state-of-the-art electronic structure characterizations of the transition state barrier region. Unimolecular decay was enhanced by substantial heavy-atom tunneling involving O-O elongation and C-C-O angle contraction along the reaction pathway. Master equation modeling yielded a fully a priori prediction of the pressure-dependent thermal unimolecular dissociation rates for the •QOOH intermediate—again increased by heavy-atom tunneling—which are required for global models of atmospheric and combustion chemistry.
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- Award ID(s):
- 1955068
- PAR ID:
- 10284549
- Publisher / Repository:
- American Association for the Advancement of Science (AAAS)
- Date Published:
- Journal Name:
- Science
- Volume:
- 373
- Issue:
- 6555
- ISSN:
- 0036-8075
- Page Range / eLocation ID:
- p. 679-682
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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