The benzene+OH potential energy surface: intermediates and transition states
Literature Information
David S. Hollman, Andrew C. Simmonett, Henry F. Schaefer
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.
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Physical Chemistry Chemical Physics

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