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Infrared (IR) action spectroscopy is utilized to characterize carbon-centered hydroperoxy-cyclohexyl radicals (·QOOH) transiently formed in cyclohexane oxidation. The oxidation pathway leads to three nearly degenerate ·QOOH isomers, β-, γ-, and δ-QOOH, which are generated in the laboratory by H-atom abstraction from the corresponding ring sites of the cyclohexyl hydroperoxide (CHHP) precursor. The IR spectral features of jet-cooled and stabilized ·QOOH radicals are observed from 3590 to 7010 cm−1 (∼10–20 kcal mol−1) at energies in the vicinity of the transition state (TS) barrier leading to OH radicals that are detected by ultraviolet laser-induced fluorescence. The experimental approach affords selective detection of β-QOOH, arising from its significantly lower TS barrier to OH products compared to γ and δ isomers, which results in rapid unimolecular decay and near unity branching to OH products. The observed IR spectrum of β-QOOH includes fundamental and overtone OH stretch transitions, overtone CH stretch transitions, and combination bands involving OH or CH stretch with lower frequency modes. The assignment of β-QOOH spectral features is guided by anharmonic frequencies and intensities computed using second-order vibrational perturbation theory. The overtone OH stretch (2νOH) of β-QOOH is shifted only a few wavenumbers from that observed for the CHHP precursor, yet they are readily distinguished by their prompt vs slow dissociation rates to OH products. 

Unimolecular decay of the formaldehyde oxide (CH2OO) Criegee intermediate proceeds via a 1,3 ring-closure pathway to dioxirane and subsequent rearrangement and/or dissociation to many products including hydroxyl (OH) radicals that are detected. Vibrational activation of jet-cooled CH2OO with two quanta of CH stretch (17-18 kcal mol-1) leads to unimolecular decay at an energy significantly below the transition state barrier of 19.46  0.25 kcal mol-1, refined utilizing a high-level electronic structure method HEAT-345(Q)Λ. The observed unimolecular decay rate of 1.6 +/- 0.4 x 106 s-1 is two orders of magnitude slower than that predicted by statistical unimolecular reaction theory using several different models for quantum mechanical tunneling. The nonstatistical behavior originates from excitation of a CH stretch vibration that is orthogonal to the heavy atom motions along the reaction coordinate and slow intramolecular vibrational energy redistribution due to the sparse density of states. 

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. 

Vibrational spectroscopy and dissociation dynamics of a prototypical cyclic hydroperoxide, cyclohexyl hydroperoxide has been studied using a combination of synthesis, spectroscopy, and theoretical methods. 

A five-carbon unsaturated Criegee intermediate, 3-penten-2-one oxide, has been identified in the laboratory using a combination of synthesis, spectroscopy, and theoretical analysis.