Unraveling Conformer-Specific Sources of Hydroxyl Radical Production from an Isoprene-Derived Criegee Intermediate by Deuteration.

Abstract

Ozonolysis of isoprene, the most abundant volatile organic compounds emitted into the Earth's troposphere after methane, yields three distinct Criegee intermediates. Among these, methyl vinyl ketone oxide (MVK-oxide) is predicted to be the major source of atmospheric hydroxyl radicals (OH) from isoprene ozonolysis. Previously, Barber et al. [ J. Am. Chem. Soc., 2018, 140, pp 10866-10880] demonstrated that syn-MVK-oxide conformers undergo unimolecular decay via 1,4-hydrogen (H) transfer from the methyl group to the adjacent terminal oxygen atom, followed by the prompt release of OH radical products. Here, we selectively deuterate the methyl group of MVK-oxide (d3-MVK-oxide) and record its IR action spectrum in the vinyl CH stretch overtone (2νCH) region. The resultant time-dependent appearance of OD radical products, detected by laser-induced fluorescence, demonstrates that a unimolecular decay of d3-MVK-oxide proceeds by an analogous 1,4-deuterium (D) atom transfer mechanism anticipated for syn conformers. The experimental spectral and temporal results are compared with the calculated IR absorption spectrum and unimolecular decay rates predicted by the Rice-Ramsperger-Kassel-Marcus (RRKM) theory for syn-d3-MVK-oxide, as well as the prior study on syn-MVK-oxide. The d3-MVK-oxide IR action spectrum is similar to that for MVK-oxide, yet exhibits notable changes as the overtone and combination transitions involving CD stretch shift to a lower frequency. The unimolecular decay rate for d3-MVK-oxide is predicted to be a factor of 40 times slower than that for MVK-oxide in the 2νCH region. Experimentally, the temporal profile of the OD products reflects the slower unimolecular decay of d3-MVK-oxide compared to that for MVK-oxide to OH products as well as experimental factors. Both experiment and theory demonstrate that quantum mechanical tunneling plays a very important role in the 1,4-H/D-transfer processes at energies in the vicinity of the transition-state barrier. The similarities of the IR action spectra and changes in the unimolecular decay dynamics upon deuteration indicate that syn conformers make the main contribution to the IR action spectra of MVK-oxide and d3-MVK-oxide.