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@ARTICLE{Vereecken:909370,
author = {Vereecken, L. and Novelli, A. and Kiendler-Scharr, A. and
Wahner, A.},
title = {{U}nimolecular and water reactions of oxygenated and
unsaturated {C}riegee intermediates under atmospheric
conditions},
journal = {Physical chemistry, chemical physics},
volume = {24},
number = {11},
issn = {1463-9076},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2022-03158},
pages = {6428 - 6443},
year = {2022},
abstract = {Ozonolysis of unsaturated hydrocarbons (VOCs) is one of the
main oxidation processes in the atmosphere. The stabilized
Criegee intermediates (SCI) formed are highly reactive
oxygenated species that potentially influence the HOx, NOx
and SOx cycles, and affect aerosol formation by yielding
low-volatility oxygenated compounds. The current knowledge
spans mostly SCI formed from primary emitted VOCs, but
little is known about the reactivity of oxygenated SCI. In
this work we present a theoretical kinetic study of a large
number of unsaturated and oxygenated SCI, covering C[double
bond, length as m-dash]C, OH, OR, OOH, OOOH, COOH, COOR, and
ONO2 functionalities at various stereo- and site-specific
substitutions relative to the SCI carbonyl oxide moiety.
Several novel reaction types are covered, the most important
of which are fast intramolecular insertion reactions in OH,
OOH and COOH groups, or secondary ozonide formation with a
COOH group, forming cyclic oxygenated species; these
reaction classes are reminiscent of the analogous
bimolecular reactions. The reaction with H2O molecules was
likewise studied, finding that these cyclisation reactions
can be catalysed, with predicted rate coefficients nearing
the collision limit. The theoretical data is used to extend
the structure–activity relationships (SARs) proposed by
Vereecken et al. (2017), predicting the dominant
unimolecular reaction class and rate, and the rates for
reaction with H2O and (H2O)2. The SARs cover over 300 SCI
categories with over 40 substituent categories. The
validation of these SARs is discussed, and an outlook is
given for further improvement. The generally short lifetime
of oxygenated SCI suggests that ozonolysis of secondary,
oxygenated VOCs is unlikely to yield ambient concentrations
of SCI exceeding 104 cm−3 but will contribute strongly to
the in situ formation of oxygenated VOCs.},
cin = {IEK-8},
ddc = {540},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {2111 - Air Quality (POF4-211)},
pid = {G:(DE-HGF)POF4-2111},
typ = {PUB:(DE-HGF)16},
pubmed = {35244104},
UT = {WOS:000764197200001},
doi = {10.1039/D1CP05877K},
url = {https://juser.fz-juelich.de/record/909370},
}