On Molecular Origin of Mass-Independent Fractionation of Oxygen Isotopes in the Ozone Forming Recombination Reaction

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Proceedings of the National Academy of Sciences

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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.


Proceedings of the National Academy of Sciences, Vol. 110, No. 44 (October 29, 2013): 17708-17713. DOI.