Comment on “A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states” [J. Chem. Phys. 142, 124312 (2015)]

Journal Article · Wed Oct 28 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4934801· OSTI ID:22493186

Harding, Lawrence B.; Klippenstein, Stephen J. ^[1]

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1. Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

We discuss the recent report of a roaming type mechanism for the decomposition of the Criegee intermediate. We show that the predicted barrier height for this new pathway is too low by ∼30 kcal/mol owing to an inconsistent use of spin-restricted and spin-unrestricted calculations. As a result, this new pathway is not expected to compete significantly with the well-known dioxirane pathways for the decomposition of the Criegee intermediate.

• OSTI ID: 22493186
• Journal Information: Journal of Chemical Physics, Vol. 143, Issue 16; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DECAY
DECOMPOSITION
SPIN