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@ARTICLE{Novelli:890512,
      author       = {Novelli, A. and Cho, C. and Fuchs, H. and Hofzumahaus, A.
                      and Rohrer, F. and Tillmann, R. and Kiendler-Scharr, A. and
                      Wahner, A. and Vereecken, L.},
      title        = {{E}xperimental and theoretical study on the impact of a
                      nitrate group on the chemistry of alkoxy radicals},
      journal      = {Physical chemistry, chemical physics},
      volume       = {23},
      issn         = {1463-9076},
      address      = {Cambridge},
      publisher    = {RSC Publ.},
      reportid     = {FZJ-2021-01003},
      pages        = {5474-5495},
      year         = {2021},
      abstract     = {The chemistry of nitrated alkoxy radicals, and its impact
                      on RO2 measurements using the laser induced fluorescence
                      (LIF) technique, is examined by a combined theoretical and
                      experimental study. Quantum chemical and theoretical kinetic
                      calculations show that the decomposition of
                      β-nitrate-alkoxy radicals is much slower than
                      β-OH-substituted alkoxy radicals, and that the spontaneous
                      fragmentation of the α-nitrate-alkyl radical product to a
                      carbonyl product + NO2 prevents other β-substituents from
                      efficiently reducing the energy barrier. The systematic
                      series of calculations is summarized as an update to the
                      structure–activity relationship (SAR) by Vereecken and
                      Peeters (2009), and shows increasing decomposition rates
                      with higher degrees of substitution, as in the series ethene
                      to 2,3-dimethyl-butene, and dominant H-migration for
                      sufficiently large alkoxy radicals such as those formed from
                      1-pentene or longer alkenes. The slow decomposition allows
                      other reactions to become competitive, including epoxidation
                      in unsaturated nitrate-alkoxy radicals; the decomposition
                      SAR is likewise updated for β-epoxy substituents. A set of
                      experiments investigating the NO3-initiated oxidation of
                      ethene, propene, cis-2-butene, 2,3-dimethyl-butene,
                      1-pentene, and trans-2-hexene, were performed in the
                      atmospheric simulation chamber SAPHIR with measurements of
                      HO2 and RO2 radicals performed with a LIF instrument.
                      Comparisons between modelled and measured HO2 radicals in
                      all experiments, performed in excess of carbon monoxide to
                      avoid OH radical chemistry, suggest that the reaction of HO2
                      with β-nitrate alkylperoxy radicals has a channel forming
                      OH and an alkoxy radical in yields of $15–65\%,$
                      compatible with earlier literature data on nitrated isoprene
                      and α-pinene radicals. Model concentrations of RO2 radicals
                      when including the results of the theoretical calculations
                      described here, agreed within $10\%$ with the measured RO2
                      radicals for all species investigated when the alkene
                      oxidation is dominated by NO3 radicals. The formation of NO2
                      in the decomposition of β-nitrate alkoxy radicals prevents
                      detection of the parent RO2 radical in a LIF instrument, as
                      it relies on formation of HO2. The implications for
                      measurements of RO2 in ambient and experimental conditions,
                      such as for the NO3-dominated chemistry during nighttime, is
                      discussed. The current results appear in disagreement with
                      an earlier indirect experimental study by Yeh et al. on
                      pentadecene.},
      cin          = {IEK-8},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {211 - Die Atmosphäre im globalen Wandel (POF4-211)},
      pid          = {G:(DE-HGF)POF4-211},
      typ          = {PUB:(DE-HGF)16},
      pubmed       = {33650597},
      UT           = {WOS:000627550700036},
      doi          = {10.1039/D0CP05555G},
      url          = {https://juser.fz-juelich.de/record/890512},
}