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@ARTICLE{Rissanen:187515,
author = {Rissanen, Matti P. and Kurtén, Theo and Sipilä, Mikko and
Thornton, Joel A. and Kangasluoma, Juha and Sarnela, Nina
and Junninen, Heikki and Jørgensen, Solvejg and Schallhart,
Simon and Kajos, Maija K. and Taipale, Risto and Springer,
Monika and Mentel, Thomas F. and Ruuskanen, Taina and
Petäjä, Tuukka and Worsnop, Douglas R. and Kjaergaard,
Henrik G. and Ehn, Mikael},
title = {{T}he {F}ormation of {H}ighly {O}xidized {M}ultifunctional
{P}roducts in the {O}zonolysis of {C}yclohexene},
journal = {Journal of the American Chemical Society},
volume = {136},
number = {44},
issn = {1520-5126},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2015-01144},
pages = {15596 - 15606},
year = {2014},
abstract = {The prompt formation of highly oxidized organic compounds
in the ozonolysis of cyclohexene (C6H10) was investigated by
means of laboratory experiments together with quantum
chemical calculations. The experiments were performed in
borosilicate glass flow tube reactors coupled to a chemical
ionization atmospheric pressure interface time-of-flight
mass spectrometer with a nitrate ion (NO3–)-based
ionization scheme. Quantum chemical calculations were
performed at the CCSD(T)-F12a/VDZ-F12//ωB97XD/aug-cc-pVTZ
level, with kinetic modeling using multiconformer transition
state theory, including Eckart tunneling corrections. The
complementary investigation methods gave a consistent
picture of a formation mechanism advancing by peroxy radical
(RO2) isomerization through intramolecular hydrogen shift
reactions, followed by sequential O2 addition steps, that
is, RO2 autoxidation, on a time scale of seconds.
Dimerization of the peroxy radicals by recombination and
cross-combination reactions is in competition with the
formation of highly oxidized monomer species and is observed
to lead to peroxides, potentially diacyl peroxides. The
molar yield of these highly oxidized products (having O/C >
1 in monomers and O/C > 0.55 in dimers) from cyclohexene
ozonolysis was determined as (4.5 ± $3.8)\%.$ Fully
deuterated cyclohexene and cis-6-nonenal ozonolysis, as well
as the influence of water addition to the system (either H2O
or D2O), were also investigated in order to strengthen the
arguments on the proposed mechanism. Deuterated cyclohexene
ozonolysis resulted in a less oxidized product distribution
with a lower yield of highly oxygenated products and
cis-6-nonenal ozonolysis generated the same monomer product
distribution, consistent with the proposed mechanism and in
agreement with quantum chemical modeling.},
cin = {IEK-8},
ddc = {540},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {233 - Trace gas and aerosol processes in the troposphere
(POF2-233)},
pid = {G:(DE-HGF)POF2-233},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000344516600029},
pubmed = {pmid:25283472},
doi = {10.1021/ja507146s},
url = {https://juser.fz-juelich.de/record/187515},
}