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@ARTICLE{Decker:830354,
author = {Decker, Z. C. J. and Au, K. and Vereecken, L. and Sheps,
L.},
title = {{D}irect experimental probing and theoretical analysis of
the reaction between the simplest {C}riegee intermediate
{CH} 2 {OO} and isoprene},
journal = {Physical chemistry, chemical physics},
volume = {19},
number = {12},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2017-03918},
pages = {8541 - 8551},
year = {2017},
abstract = {Recent advances in the spectroscopy of Criegee
intermediates (CI) have enabled direct kinetic studies of
these highly reactive chemical species. The impact of CI
chemistry is currently being incorporated into atmospheric
models, including their reactions with trace organic and
inorganic compounds. Isoprene, C5H8, is a doubly-unsaturated
hydrocarbon that accounts for the largest share of all
biogenic emissions around the globe and is also a building
block of larger volatile organic compounds. We report direct
measurements of the reaction of the simplest CI (CH2OO) with
isoprene, using time-resolved cavity-enhanced UV absorption
spectroscopy. We find the reaction to be
pressure-independent between 15–100 Torr, with a rate
coefficient that varies from (1.5 ± 0.1) × 10−15 cm3
molecule−1 s−1 at room temperature to (23 ± 2) ×
10−15 cm3 molecule−1 s−1 at 540 K. Quantum chemical
and transition-state theory calculations of 16 unique
channels for CH2OO + isoprene somewhat underpredict the
observed T-dependence of the total reaction rate
coefficient, but are overall in good agreement with the
experimental measurements. This reaction is broadly similar
to those with smaller alkenes, proceeding by 1,3-dipolar
cycloaddition to one of the two conjugated double bonds of
isoprene.},
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},
UT = {WOS:000397860900046},
pubmed = {pmid:28288212},
doi = {10.1039/C6CP08602K},
url = {https://juser.fz-juelich.de/record/830354},
}