Strange and unconventional isotope effects in ozone formation

Science. 2001 Jul 13;293(5528):259-63. doi: 10.1126/science.1058528. Epub 2001 May 31.

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.