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@ARTICLE{Vereecken:890523,
      author       = {Vereecken, L. and Carlsson, P. T. M. and Novelli, A. and
                      Bernard, F. and Brown, S. S. and Cho, C. and Crowley, J. N.
                      and Fuchs, H. and Mellouki, W. and Reimer, David and
                      Shenolikar, J. and Tillmann, R. and Zhou, L. and
                      Kiendler-Scharr, A. and Wahner, A.},
      title        = {{T}heoretical and experimental study of peroxy and alkoxy
                      radicals in the {NO} 3 -initiated oxidation of isoprene},
      journal      = {Physical chemistry, chemical physics},
      volume       = {23},
      number       = {9},
      issn         = {1463-9076},
      address      = {Cambridge},
      publisher    = {RSC Publ.},
      reportid     = {FZJ-2021-01010},
      pages        = {5496-5515},
      year         = {2021},
      abstract     = {The initial stages of the nitrate radical (NO3) initiated
                      oxidation of isoprene, in particular the fate of the peroxy
                      (RO2) and alkoxy (RO) radicals, are examined by an extensive
                      set of quantum chemical and theoretical kinetic
                      calculations. It is shown that the oxidation mechanism is
                      highly complex, and bears similarities to its OH-initiated
                      oxidation mechanism as studied intensively over the last
                      decade. The nascent nitrated RO2 radicals can interconvert
                      by successive O2 addition/elimination reactions, and
                      potentially have access to a wide range of unimolecular
                      reactions with rate coefficients as high as 35 s−1; the
                      contribution of this chemistry could not be ascertained
                      experimentally. The chemistry of the alkoxy radicals derived
                      from these peroxy radicals is affected by the nitrate
                      moiety, and can lead to the formation of nitrated epoxy
                      peroxy radicals in competition with isomerisation and
                      decomposition channels that terminate the organic radical
                      chain by NO2 elimination. The theoretical predictions are
                      implemented in the FZJ-NO3-isoprene mechanism for
                      NO3-initiated atmospheric oxidation of isoprene. The model
                      predictions are compared against peroxy radical (RO2) and
                      methyl vinyl ketone (MVK) measurements in a set of
                      experiments on the isoprene + NO3 reaction system performed
                      in the SAPHIR environmental chamber (IsopNO3 campaign). It
                      is shown that the formation of NO2 from the peroxy radicals
                      can prevent a large fraction of the peroxy radicals from
                      being measured by the laser-induced fluorescence (ROxLIF)
                      technique that relies on a quantitative conversion of peroxy
                      radicals to hydroxyl radicals. Accounting for the relative
                      conversion efficiency of RO2 species in the experiments, the
                      agreement between observations and the theory-based
                      FZJ-NO3-isoprene model predictions improves significantly.
                      In addition, MVK formation in the NO3-initiated oxidation
                      was found to be suppressed by the epoxidation of the
                      unsaturated RO radical intermediates, allowing the
                      model-predicted MVK concentrations to be in good agreement
                      with the measurements. The FZJ-NO3-isoprene mechanism is
                      compared against the MCM v3.3.1 and Wennberg et al. (2018)
                      mechanisms.},
      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       = {33650589},
      UT           = {WOS:000627550700037},
      doi          = {10.1039/D0CP06267G},
      url          = {https://juser.fz-juelich.de/record/890523},
}