title: 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)].
abstract: 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.
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Lawrence B
authors.initials: LB
authors.lastname: Harding
authors.affiliation: Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne, Illinois 60439, USA.
authors.forename: Stephen J
authors.initials: SJ
authors.lastname: Klippenstein