An Explanation for Symmetry-Induced Isotopic Fractionation in Ozone

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Science  22 Nov 1996:
Vol. 274, Issue 5291, pp. 1344-1346
DOI: 10.1126/science.274.5291.1344


Application of a theory of nuclear symmetry-based reaction restrictions to the O2 + O → O3 reaction provides a potential explanation for the symmetry-induced isotopic enrichment observed for laboratory and atmospherically produced O3. Within this theory, the rate of formation of O3 from collisions of O and isotopically homonuclear O2 depends on whether the O2 molecule is in an f (allowed) or an e (restricted) parity label state. The restriction can be relaxed by various potential energy surface coupling terms, and the assumption that approximately 78 percent of the restricted O2(e) levels produce O3 with the same efficiency as the allowed O2(f) levels can account for laboratory-observed isotopic fractionation. In particular, the theory explains the special enhanced formation of the completely asymmetric isotopomer 16O17O18O.

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