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@ARTICLE{Alarcn:154645,
      author       = {Alarcón, Paulo and Bohn, Birger and Zetzsch, Cornelius and
                      Rayez, Marie-Thérèse and Rayez, Jean-Claude},
      title        = {{R}eversible addition of the {OH} radical to p-cymene in
                      the gas phase: multiple adduct formation. {P}art 2},
      journal      = {Physical chemistry, chemical physics},
      volume       = {16},
      issn         = {1463-9084},
      address      = {Cambridge},
      publisher    = {RSC Publ.},
      reportid     = {FZJ-2014-03929},
      pages        = {17315-17326},
      year         = {2014},
      abstract     = {A flash photolysis-resonance fluorescence (FP-RF) system
                      was used to study the p-cymene (PC) + OHreaction at
                      temperatures between 299 and 349 K in helium. Triexponential
                      functions were fitted to groups ofobserved OH decay curves
                      according to a model considering a reversible addition to
                      form two adducts asthermolabile reservoirs of OH. Compared
                      to Part 1 of this paper, consideration of a second adduct
                      stronglyimproved the fits to our measurements, and the rate
                      constants for the major pathways were optimizedbetween 299
                      and 349 K. The Arrhenius expression for the rate constant of
                      the sum of OH addition andH-atom abstraction pathways was
                      found to be kOH = 1.9 1012 exp[(610 210) K/T] cm3 s1.
                      Rateconstants of unimolecular decomposition reactions of the
                      adducts were similar to other aromaticcompounds with the
                      following Arrhenius expressions: 1 1012 exp[(7600 800) K/T]
                      s1 for adduct1 and 4 1011 exp[(8000 300) K/T] s1 for adduct
                      2. Adduct yields increased and decreased withtemperature for
                      adduct 1 and 2, respectively, but were similar (B0.4) around
                      room temperature.Equilibrium constants yielded values for
                      reaction enthalpies and entropies of adduct formations.
                      Whilefor one adduct reasonable agreement was obtained with
                      theoretical predictions, there were significantdeviations
                      for the other adduct. This indicates the presence of more
                      than two adduct isomers that werenot accounted for in the
                      reaction model. Quantum chemical calculations (DFT
                      M06-2X/6-31G(d,p)) andRRKM kinetics were employed with the
                      aim of clarifying the mechanism of the OH addition to
                      PC.These calculations show that formation of adducts with OH
                      in ortho positions to the isopropyl andmethyl substituents
                      is predominant $(55\%$ and $24\%)$ to those with OH in ipso
                      positions $(21\%$ and $3\%).A$ large fraction $(490\%)$ of
                      the ipso-C3H7 adduct is predicted to react by dealkylation
                      forming p-cresol(in the absence of oxygen) and isopropyl
                      radicals. These theoretical results agree well with the
                      interpretationof the experimental results showing that the
                      two ortho adducts (which appeared as OHreservoirs in the
                      experiment) have been observed.},
      cin          = {IEK-8},
      ddc          = {540},
      cid          = {I:(DE-Juel1)IEK-8-20101013},
      pnm          = {233 - Trace gas and aerosol processes in the troposphere
                      (POF2-233)},
      pid          = {G:(DE-HGF)POF2-233},
      typ          = {PUB:(DE-HGF)16},
      UT           = {WOS:000340353000047},
      doi          = {10.1039/C4CP02073A},
      url          = {https://juser.fz-juelich.de/record/154645},
}