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

Literature Information

Publication Date 2007-08-02
DOI 10.1039/B708023A
Impact Factor 3.676
Authors

L. Vereecken, J.-F. Müller, J. Peeters


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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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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