Details

Autor(en) / Beteiligte

• Hollman, David S
• Simmonett, Andrew C
• Schaefer, Henry F

Titel

The benzene+OH potential energy surface: intermediates and transition statesElectronic supplementary information (ESI) available: Full Cartesian geometries; additional focal point tables; comparison of geometry optimization methods; comparison of OH frequency shifts for different methods. See DOI: 10.1039/c0cp01607a

Erscheinungsjahr

2011-01

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• 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. 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.