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Strange and unconventional isotope effects in ozone formation
Authors:Gao Y Q  Marcus R A
Institution:Noyes Laboratory of Chemical Physics, Mail Code 127-72, California Institute of Technology, Pasadena, CA 91125, USA.
Abstract:The puzzling mass-independent isotopic enrichment in ozone formation contrasts markedly with the more recently observed large unconventional mass-dependent ratios of the individual ozone formation rate constants in certain systems. An RRKM (Rice, Ramsperger, Kassel, Marcus)-based theory is used to treat both effects. Restrictions of symmetry on how energy is shared among the rotational/vibrational states of the ozone isotopomer, together with an analysis of the competition between the transition states of its two exit channels, permit the calculation of isotope effects consistent with a wide array of experimental results.
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