Enthalpies of formation of the benzyloxyl, benzylperoxyl, hydroxyphenyl radicals and related species on the potential energy surface for the reaction of toluene with the hydroxyl radical

<p></p><p>The reaction of toluene (T) with OH<sup>●</sup> produces addition products as well as the benzyl radical (TR). TR can react with OH<sup>●</sup> or O<sub>2</sub> to produce oxygenated species, for many of which there is no experimental information available. We present here theoretically determined heats of formation (HFs) of 17 such species using the non-isodesmic reactions on the potential energy surface (PES) of TR+O<sub>2</sub> and T+OH<sup>●</sup>+O<sub>2</sub>. For those species the experimental HFs of which are known, we obtained a good correlation between experimental and theoretical values at the G4 (r<sup>2</sup>=0.999) and M06/cc-pVQZ (r<sup>2</sup>=0.997) levels, thus showing the goodness of the methods used. Previously unknown HFs of other radicals (benzyloxyl, spiro [1,2-dioxetane benzyl], hydroxyphenyl, and benzylperoxyl) and closed shell species (salicylic alcohol, benzo[b]oxetane and p-hydroxy cyclohexa-2,5-dienone) were later determined using those methods.<b></b></p><br><p></p>