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

2019 ◽  
Vol 138 (10) ◽  
Author(s):  
Oscar N. Ventura ◽  
Martina Kieninger ◽  
Zoi Salta ◽  
Agnie M. Kosmas ◽  
Vincenzo Barone
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Hydroxyl Radical ◽  
Related Species ◽  
Energy Surface ◽  
Enthalpies Of Formation

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

2019 ◽  
Author(s):  
Oscar Ventura ◽  
Martina Kieninger ◽  
Zoi Salta ◽  
Agnie M. Kosmas ◽  
Vincenzo Barone
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Hydroxyl Radical ◽  
Related Species ◽  
Energy Surface ◽  
Closed Shell ◽  
Experimental Information ◽  
Enthalpies Of Formation ◽  
Isodesmic Reactions ◽  
Benzyl 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>

scholarly journals 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

2019 ◽  
Author(s):  
Oscar Ventura ◽  
Martina Kieninger ◽  
Zoi Salta ◽  
Agnie M. Kosmas ◽  
Vincenzo Barone
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Hydroxyl Radical ◽  
Related Species ◽  
Energy Surface ◽  
Closed Shell ◽  
Experimental Information ◽  
Enthalpies Of Formation ◽  
Isodesmic Reactions ◽  
Benzyl 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>

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