Absolute photodissociation cross sections of thermalized methyl vinyl ketone oxide and methacrolein oxide

Abstract

Methyl vinyl ketone oxide (MVKO) and methacrolein oxide (MACRO) are resonance-stabilized Criegee intermediates which are formed in the ozonolysis reaction of isoprene, the most abundant unsaturated hydrocarbon in the atmosphere. The absolute photodissociation cross sections of MVKO and MACRO were determined by measuring their laser depletion fraction at 352 nm, which was deduced from their time-resolved UV-visible absorption spectra. After calibrating the 352 nm laser fluence with the photodissociation of NO₂, for which the absorption cross section and photodissociation quantum yield are well known, the photodissociation cross sections of thermalized (299 K) MVKO and MACRO at 352 nm were determined to be (3.02 ± 0.60) × 10⁻¹⁷ cm² and (1.53 ± 0.29) × 10⁻¹⁷ cm², respectively. Using their reported spectra and photodissociation quantum yields, their peak absorption cross sections were deduced to be (3.70 ± 0.74) × 10⁻¹⁷ cm² (at 371 nm, MVKO) and (3.04 ± 0.58) × 10⁻¹⁷ cm² (at 397 nm, MACRO). These values agree fairly with our theoretical predictions and are substantially larger than those of smaller, alkyl-substituted Criegee intermediates (CH₂OO, syn-CH₃CHOO, (CH₃)₂COO), revealing the effect of extended conjugation. With their cross sections, we also quantified the synthesis yields of MVKO and MACRO in the present experiment to be 0.22 ± 0.10 (at 299 K and 30–700 torr) and 0.043 ± 0.019 (at 299 K and 500 torr), respectively, relative to their photolyzed precursors. The lower yield of MACRO can be related to the high endothermicity of its formation channel.