Mass-independent isotopic fractionation in nonadiabatic molecular collisions

Physics – Chemical Physics

Scientific paper

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Born-Oppenheimer Approximation, Isotope Effect, Molecular Collisions, Nonadiabatic Conditions, Oxygen Isotopes, Schroedinger Equation, Chemical Equilibrium, Cosmochemistry, Eigenvectors, Electron States, Stratosphere

Scientific paper

The conditions under which nonadiabatic collisions should induce mass-independent isotopic fractionation are considered, and the consequences of such fractionation are discussed. It is shown that mass-independent isotopic fractionation in the UV photolysis of ozone is but one example of a general class of such fractionations that should be associated with nonadiabatic collisions. It is demonstrated that nonadiabatic effects may be the source of the equal O-17 and O-18 isotopic enrichment in meteoritic material observed by Clayton et al. (1973) as well as the equal O-17 and O-18 enrichments produced by Heidenreich and Thiemens using electrical discharges in oxygen-containing gas samples. The effect of oxygen isotopic fractionation in the UV photolysis of ozone on the isotope distributions among oxygen-containing species in the atmosphere is considered.

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