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@ARTICLE{Vereecken:877784,
author = {Vereecken, Luc and Nozière, Barbara},
title = {{H} migration in peroxy radicals under atmospheric
conditions},
journal = {Atmospheric chemistry and physics},
volume = {20},
number = {12},
issn = {1680-7324},
address = {Katlenburg-Lindau},
publisher = {EGU},
reportid = {FZJ-2020-02451},
pages = {7429 - 7458},
year = {2020},
abstract = {A large data set of rate coefficients for H migration in
peroxy radicals is presented and supplemented with
literature data to derive a structure–activity
relationship (SAR) for the title reaction class. The SAR
supports aliphatic RO2 radicals; unsaturated bonds and
β-oxo substitutions both endocyclic and exocyclic to the
transition state ring; and α-oxo (aldehyde), –OH, –OOH,
and –ONO2 substitutions, including migration of O-based
hydrogen atoms. Also discussed are –C( = O)OH and
–OR substitutions. The SAR allows predictions of rate
coefficients k(T) for a temperature range of 200 to 450 K,
with migrations spans ranging from 1,4 to 1,9-H shifts
depending on the functionalities. The performance of the SAR
reflects the uncertainty of the underlying data, reproducing
the scarce experimental data on average to a factor of 2 and
the wide range of theoretical data to a factor of 10 to 100,
depending also on the quality of the data. The SAR
evaluation discusses the performance in multi-functionalized
species. For aliphatic RO2, we also present some
experimental product identification that validates the
expected mechanisms. The proposed SAR is a valuable tool for
mechanism development and experimental design and guides
future theoretical work, which should allow for rapid
improvements of the SAR in the future. Relative
multi-conformer transition state theory (rel-MC-TST) kinetic
theory is introduced as an aid for systematic kinetic
studies.},
cin = {IEK-8},
ddc = {550},
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:000543796900002},
doi = {10.5194/acp-20-7429-2020},
url = {https://juser.fz-juelich.de/record/877784},
}