Ozonolysis of 3-carene in the atmosphere. Formation mechanism of hydroxyl radical and secondary ozonides

Literature Information

Publication Date 2019-03-18
DOI 10.1039/C8CP07195K
Impact Factor 3.676
Authors

Lingyu Wang, Yuhong Liu


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Abstract

The gas-phase ozonolysis mechanism of 3-carene is investigated using high level quantum chemistry and kinetic calculations. The reaction follows the Criegee mechanism with an initial addition of O3 to the CC bond, followed by a chain of unimolecular isomerizations, as 3-carene + O3 → POZs (primary ozonides) → CIs (Criegee intermediates, 4 conformers) → Ps (products). In the course of the reaction, a large excess of energy retained in the POZs* lead to the prompt unimolecular processes in POZs*, CIs*, and Ps*, and only ∼4% of CIs* could be stabilized by collision at 298 K and 760 Torr. From RRKM-ME calculations, the VHPs* could further dissociate to vinoxy-type radical and OH radical, the SOZs* could isomerize to 3-caronic acid, and DIOs* could be stabilized via collision. The fractional yield of OH radical, in the range of 0.56 to 0.59, agrees reasonably well with the previously measured value of 1.06 (with an uncertainty factor of 1.5).

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

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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