Abstract
The reaction of toluene (T) with ·OH produces addition products as well as the benzyl radical (TR). TR can react with ·OH or O2 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 of TR + O2 and T + ·OH +O2. For those species the experimental HFs of which are known, we obtained a good correlation between experimental and theoretical values at the G4 (r2 = 0.999) and M06/cc-pVQZ (r2 = 0.997) levels, thus showing the goodness of the methods used. Experimentally 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.
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Acknowledgements
PEDECIBA (Uy), CSIC (UdelaR, Uy) and ANII (Uy) are gratefully acknowledged for sustained funding of the theoretical atmospheric chemistry program in which the toluene project is included. Some of the calculations reported in this paper were performed in ClusterUY, a newly installed platform for high-performance scientific computing at the National Supercomputing Center, Uruguay.
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Ventura, O.N., Kieninger, M., Salta, Z. et al. 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. Theor Chem Acc 138, 115 (2019). https://doi.org/10.1007/s00214-019-2500-8
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DOI: https://doi.org/10.1007/s00214-019-2500-8