The contributions of particular protonated forms into the overall rate constants of thermolysis were estimated using the DFT calculated Gibbs free energies Δ(r)⁰G of C-ON bond homolysis reactions.  The computations revealed that the observed rate constants of thermolysis of the two species at several pH values are dominated by decomposition reactions of two or even three protonated forms.  A linear correlation between the sum of radical stabilization energies (RSEs) of products of thermolysis and the calculated Gibbs free energies of reactions was found for various protonated forms of the species studied. 
THERM