The benzene+OH potential energy surface: intermediates and transition states

Abstract

The potential energy surface for the interaction between benzene and hydroxyl radical is studied in detail using quantum mechanical methods, with a particular focus on the hydrogen abstraction pathway. Geometric parameters are optimized using a variety of density functional methods as well as perturbation theory. Energies are refined using coupled cluster singles and doubles with perturbative triples [CCSD(T)] extrapolated to the complete basis set limit. At our most reliable level of theory, complexation energies are found to be (with zero-point corrected energies in parentheses) 3.7 (2.8) kcal/mol for the benzene–hydroxyl radical complex and 2.9 (−1.7) kcal/mol for the phenyl radical–water complex. The barrier to H abstraction lies 6.5 (4.2) kcal/mol above the infinitely separated benzene and hydroxyl radical monomers.