Research Article

Strange and Unconventional Isotope Effects in Ozone Formation

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Science  13 Jul 2001:
Vol. 293, Issue 5528, pp. 259-263
DOI: 10.1126/science.1058528

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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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