title: On molecular origin of mass-independent fractionation of oxygen isotopes in the ozone forming recombination reaction.
abstract: Theoretical treatment of ozone forming reaction is developed within the framework of mixed quantum/classical dynamics. Formation and stabilization steps of the energy transfer mechanism are both studied, which allows simultaneous capture of the delta zero-point energy effect and η-effect and identification of the molecular level origin of mass-independent isotope fractionation. The central role belongs to scattering resonances; dependence of their lifetimes on rotational excitation, asymmetry; and connection of their vibrational wave functions to two different reaction channels. Calculations, performed within the dimensionally reduced model of ozone, are in semiquantitative agreement with experiment.
authors: Chemistry Department, Marquette University, Milwaukee, WI 53201-1881.
authors: Mikhail V
authors: MV
authors: Ivanov
authors: Dmitri
authors: D
authors: Babikov
mesh_terms: D001272:Atmosphere / Q000032:analysis*; D007700:Kinetics; D008956:Models, Chemical; D010103:Oxygen Isotopes / Q000737:chemistry*; D010126:Ozone / Q000138:chemical synthesis*
chemical_list: D010103:Oxygen Isotopes; D010126:Ozone
keywords: collisional energy transfer; isotope effect; quantum resonance; recombination rate constant; width of resonant states