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Theoretical Study of the Reaction of Carbonyl Oxide with Nitrogen Dioxide: CH 2 OO + NO 2
Author(s) -
Vereecken L.,
Nguyen H. M. T.
Publication year - 2017
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.21112
Subject(s) - chemistry , adduct , radical , nitrogen dioxide , reaction mechanism , photochemistry , molecule , computational chemistry , organic chemistry , catalysis
ABSTRACT The reaction mechanism of the reaction of the Criegee intermediate CH 2 OO with NO 2 was investigated using quantum chemical and theoretical kinetic methodologies. The reaction shows a rich chemistry, though the number of channels that effectively contribute at room temperature is limited. The theoretical characterization of the entrance transition states was hampered by strongly multireference wave functions. The predicted rate coefficient k (298 K) = 4.4 × 10 −12 cm 3 molecule −1 s −1 thus carries a large uncertainty, but is in agreement with literature data. We find that the CH 2 OO + NO 2 reaction reacts by adduct formation, near‐exclusively forming nitro‐peroxy radicals, • OOCH 2 NO 2 . These will react as other alkylperoxy radicals in the atmosphere, ultimately generating CH 2 O and regenerating NO 2 in most reaction conditions. The product predictions contrast with earlier experimental work showing NO 3 formation, but support other observations of adduct products.