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@ARTICLE{Vereecken:838697,
author = {Vereecken, Luc},
title = {{T}he reaction of {C}riegee intermediates with acids and
enols},
journal = {Physical chemistry, chemical physics},
volume = {19},
number = {42},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2017-07258},
pages = {28630-28640},
year = {2017},
abstract = {The reaction of CH2OO, the smallest carbonyl oxide (Criegee
intermediate, CI), with several acids was investigated using
the CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ quantum chemical
method, as well as microvariational transition state theory
and RRKM master equation theoretical kinetic methodologies.
For oxoacids HNO3 and HCOOH, a 1,4-insertion mechanism
allows for barrierless reactions with high rate
coefficients, in agreement with literature experimental
data. This mechanism relies on the presence of a double bond
in the α-position to the acidic OH group. We predict that
reactions of CI with enols will likewise have high rate
coefficients, proceeding through a similar mechanism. The
hydracid HCl was found to react through a less favorable
1,2-insertion reaction, leading to lower rate coefficients,
again in good agreement with the literature. We conclude
that the reaction mechanism is the main indicator for the
reaction rate for CH2OO + acid reactions, with acidity only
of secondary influence. At room temperature and 1 atm the
main product for all reactions was found to be the
thermalized hydroperoxide initial adduct, with minor yields
of fragmentation products. One of the product channels
characterized is a novel reaction path involving
intramolecular H-abstraction after a roaming reaction in the
OH + product radical complex formed by the dissociation of
the hydroperoxide adduct; this channel is the lowest
fragmentation route for some of the reactions studied.},
cin = {IEK-8},
ddc = {540},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {243 - Tropospheric trace substances and their
transformation processes (POF3-243)},
pid = {G:(DE-HGF)POF3-243},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:29057418},
UT = {WOS:000414243300016},
doi = {10.1039/C7CP05132H},
url = {https://juser.fz-juelich.de/record/838697},
}