“…The primary reaction barrier for EC reaction with 1 O 2 is predicted to be ΔE * = 0.92 eV via a widely used hybrid DFT functional . Multireference (CASTP2) methods yield even higher barriers, at least ΔE *=1.27 eV. ,, The M11 DFT functional also predicts a high ΔE *=1.38 eV, while corrected, range-separated hybrid generalized gradient approximation DFT predicts ΔE * > 1 eV in the most favorable pathway . As before, , we estimate unimolecular reaction rates k from ΔE * using k = k 0 exp ( − β Δ E * ) where k 0 is the kinetic prefactor we have chosen to be 10 12 /s, , and β is the inverse thermal energy 1/ k B T at T = 300 K. 1 O 2 -EC reactions are bimolecular; in a pure EC solvent, the EC concentration would be ∼15 M, and to a first approximation, we adopt an effective k 0 = 10 13 /s here.…”