title: 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.
authors.affiliation: The Center for Computational Quantum Chemistry, The University of Georgia, GA, USA.
authors.forename: David S
authors.initials: DS
authors.lastname: Hollman
authors.forename: Andrew C
authors.initials: AC
authors.lastname: Simmonett
authors.forename: Henry F
authors.initials: HF
authors.lastname: Schaefer
mesh_terms: D001554:Benzene / Q000737:chemistry*; D003198:Computer Simulation; D006859:Hydrogen / Q000737:chemistry*; D017665:Hydroxyl Radical / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D013499:Surface Properties; D013816:Thermodynamics
chemical_list: D017665:Hydroxyl Radical; D006859:Hydrogen; D001554:Benzene