Hydrogen abstraction from biphenyl, acenaphthylene, naphthalene and phenanthrene by atomic hydrogen and methyl radical: DFT and G3(MP2)-RAD data

We provide reaction and activation energies for 28 hydrogen abstraction reactions. Hydrogens are abstracted from biphenyl, acenaphthylene, naphthalene and phenanthrene by methyl radical and hydrogen radical. We compute reaction energies and activation energies using eight functionals, three non-hybrid (BP86, TPSS and PBE) and five hybrid (B3LYP, B3PW91, TPSSh, PBE0 and HCTH407). These DFT data are compared to the energies obtained by means of the composite method G3(MP2)-RAD, which was designed to handle radical species with a high accuracy. A classification of four abstraction sites is done based on topological and energetics criteria. Furthermore, we show that PBE0 is the functional of choice when one considers hydrogen abstraction from PAH by H or CH3.