Limonene: A scented and versatile tropospheric free radical deactivator

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Abstract

The reactions of limonene with various free radicals (OCH3, OBr, SH, OOH, and OOCH3) were investigated along the 273.15–312.15 K temperature range. To that purpose the density functional theory was used, at the M06-2X/6–311+g(d,p) level. Two reaction mechanisms, hydrogen atom transfer (HAT) and radical adduct formation (RAF) were considered. It was found that the relative reactivity of the studied radicals toward limonene is: SH > OBr > OCH3 > OOH > OOCH3. HAT was identified as the dominant mechanism for OOH and OOCH3, while RAF contributes the most to the reactions involving OCH3, OBr, and SH. The obtained Arrhenius expressions are: k(OCH3) = 1.58 × 10−13 e−1.59/RT, k(OBr) = 3.55 × 10−12 e+1.82/RT, k(SH) = 3.30 × 10−11 e+0.79/RT, k(OOH) = 1.33 × 10−15 e−5.99/RT, and k(OOCH3) = 5.88 × 10−17 e−6.26/RT. According to them, the reactions of OBr and SH become slower as temperature rises from 273.15 to 312.15 K, while for the other radicals the reactions rate increases with temperature. The subsequent tropospheric fate of the most abundant OBr adduct was also investigated in the same temperature range, considering O2 addition to this radical (step 2) and the reaction of the peroxyl radical yielded in this step 2 with NO. The latter is predicted to take place in two steps: the NO addition (3a) and the NO2 elimination (3b). The corresponding Arrhenius expression are k2 = 3.56 × 10−15 e+1.43/RT and k3b = 1.35 × 1014 e−31.65/RT. Step 3a was found to be barrierless. To our best knowledge, all the data provided here is reported for the first time. Thus, it would hopefully contribute to enhance the knowledge necessary for the full understanding (and accurate modeling) of the troposphere.

Original languageEnglish
Article numbere27103
JournalInternational Journal of Quantum Chemistry
Volume123
Issue number24
DOIs
StatePublished - 15 Dec 2023

Keywords

  • activation energy
  • atmosphere
  • kinetics
  • product distribution
  • reaction mechanism
  • temperature dependence
  • troposphere

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