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Originally published in Science Express on 31 May 2001
Science 13 July 2001:
Vol. 293. no. 5528, pp. 259 - 263
DOI: 10.1126/science.1058528
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Research Articles

Strange and Unconventional Isotope Effects in Ozone Formation

Yi Qin Gao, R. A. Marcus*

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.

Noyes Laboratory of Chemical Physics, Mail Code 127-72, California Institute of Technology, Pasadena, CA 91125, USA.
*   To whom correspondence should be addressed. E-mail: ram{at}caltech.edu

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