Chemical Physics Letters, Vol.391, No.1-3, 195-199, 2004
An ab initio study on the mechanism of the F+O-3 -> FO+O-2 reaction: comparative reactivity study along the isoelectronic NH2, OH and F radicals series
The title reaction has been theoretically studied by using MP2, QCISD, QCISD(T), CCSD(T), CASSCF, and CASPT2 methods with various basis sets. At single-reference MP2 and QCISD levels of theory, the potential energy hypersurface (HPES) shows a two-step reaction mechanism through two transition states (TS1 and TS2) and an intermediate (Int). However, the multiconfigurational CASSCF HPES shows a one-step reaction mechanism, as was previously found for the NH2 + O-3 and OH + O-3 reactions. The results show that the reactivity of the isoelectronic series of NH2, OH, and F radicals increases from the amino radical to the fluorine atom. (C) 2004 Elsevier B.V. All rights reserved.