CH 2 OO Criegee intermediate UV absorption cross-sections and kinetics of CH 2 OO + CH 2 OO and CH 2 OO + I as a function of pressure

The UV absorption cross-sections of the Criegee intermediate CH OO, and kinetics of the CH OO self-reaction and the reaction of CH OO with I are reported as a function of pressure at 298 K. Measurements were made using pulsed laser flash photolysis of CH I /O /N gas mixtures coupled with time-resolv...

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Veröffentlicht in:Physical chemistry chemical physics : PCCP 2020-05, Vol.22 (17), p.9448-9459
Hauptverfasser: Mir, Zara S, Lewis, Thomas R, Onel, Lavinia, Blitz, Mark A, Seakins, Paul W, Stone, Daniel
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Sprache:eng
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Zusammenfassung:The UV absorption cross-sections of the Criegee intermediate CH OO, and kinetics of the CH OO self-reaction and the reaction of CH OO with I are reported as a function of pressure at 298 K. Measurements were made using pulsed laser flash photolysis of CH I /O /N gas mixtures coupled with time-resolved broadband UV absorption spectroscopy at pressures between 6 and 300 Torr. Results give a peak absorption cross-section of (1.37 ± 0.29) × 10 cm at ∼340 nm and a rate coefficient for the CH OO self-reaction of (8.0 ± 1.1) × 10 cm s , with no significant pressure dependence of the absorption cross-sections or the self-reaction kinetics over the range investigated. The rate coefficient for the reaction between CH OO and I demonstrates pressure dependence over the range investigated, with a Lindemann fit giving k = (4.4 ± 1.0) × 10 cm s and k = (6.7 ± 0.6) × 10 cm s . The origins of IO in the system have been investigated, the implications of which are discussed.
ISSN:1463-9076
1463-9084
DOI:10.1039/D0CP00988A