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Issue 38, 2007
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Low-volatility poly-oxygenates in the OH-initiated atmospheric oxidation of α-pinene: impact of non-traditional peroxyl radical chemistry

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Abstract

Following new insights on non-traditional peroxyl radical chemistry, we present an update to our earlier OH-initiated α-pinene degradation mechanism (Peeters et al., Phys. Chem. Chem. Phys., 2001, 3, 5489), incorporating ring closure reactions and a fast H-shift isomerization in certain key peroxyl and oxy radical intermediates. These changes, affecting only a single branch of the comprehensive mechanism and based on extensive quantum-chemical and theoretical kinetic calculations, show significant formation, ∼20% overall, of poly-oxygenated (hydro)peroxides in atmospheric conditions. These low-volatility compounds are expected to have a significant impact on aerosol formation, and are believed to be the high-mass product compounds observed in available experimental work. The proposed changes also affect the predicted acetone yield, matching the experimental data closely.

Graphical abstract: Low-volatility poly-oxygenates in the OH-initiated atmospheric oxidation of α-pinene: impact of non-traditional peroxyl radical chemistry

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Publication details

The article was received on 29 May 2007, accepted on 23 Jul 2007 and first published on 02 Aug 2007


Article type: Paper
DOI: 10.1039/B708023A
Citation: Phys. Chem. Chem. Phys., 2007,9, 5241-5248
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    Low-volatility poly-oxygenates in the OH-initiated atmospheric oxidation of α-pinene: impact of non-traditional peroxyl radical chemistry

    L. Vereecken, J.-F. Müller and J. Peeters, Phys. Chem. Chem. Phys., 2007, 9, 5241
    DOI: 10.1039/B708023A

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