Journal
ATMOSPHERIC ENVIRONMENT
Volume 187, Issue -, Pages 218-229Publisher
PERGAMON-ELSEVIER SCIENCE LTD
DOI: 10.1016/j.atmosenv.2018.06.001
Keywords
Isoprene ozonolysis; Criegee intermediates; Oligomerization reactions; Reaction mechanisms; Rate coefficients
Funding
- National Key Research and Development Program of China [2016YFA0203000]
- National Science Foundation of China [41401567, 41573138, 21473108]
- Key Project of International Coperation of the Chinese Academy of Sciences [GJHZ1543]
- Research Grants Council of Hong Kong [PolyU 152083/14E]
- Open foundation of State Key Laboratory of Loess and Quaternary Geology [SKLLQG1627]
- Shaanxi Province Postdoctoral Science Foundation [2017BSHEDZZ62]
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Secondary organic aerosols (SOA) have significant effects on atmospheric chemistry, human health and climate forcing, but their formation mechanisms via Criegee chemistry are still poorly understood. Here we present a comprehensive theoretical investigation on the oligomerization reaction of stabilized Criegee intermediates (SCIs) with organic acid/peroxy radical by using ab initio quantum-chemical methodologies. Our results show that the ozonolysis of isoprene easily leads to a series of C3 and C4 stable CIs due to its larger exothermicity and spontaneity. The formed SCIs have two isomers: syn- and anti-, and anti- is more stable in energy than that of synby about 2-5 kcal mol(-1). The barrier heights of oligomerization reactions are very sensitive to the size and structure of functional groups near the central carbon atom site, indicating they can be tuned by the substitutions. Reaction between SCIs and peroxy radical contributes significantly to the formation of oligomer which is the dominant component of SOA. However, the reaction between SCIs and organic acid plays an important role in aerosol nucleation in some regions where high SCI and low H2O concentrations occur such as in terrestrial equatorial area. Such knowledge should be useful for understanding the mechanism of SOA formation from alkenes ozonolysis and for developing atmospheric chemistry models.
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