Nonstatistical behavior of reactive scattering in the (18)O+(32)O(2) isotope exchange reaction

The recombination of oxygen atoms with oxygen molecules to form ozone exhibits several strange chemical characteristics, including unusually large differences in formation rate coefficients when different isotopes of oxygen participate. Purely statistical chemical reaction rate theories cannot describe these isotope effects, suggesting that reaction dynamics must play an important role. We investigated the dynamics of the 18O + 32O2 --> O3(*) --> 16O + 34O2 isotope exchange reaction (which proceeds on the same potential energy surface as ozone formation) using crossed atomic and molecular beams at a collision energy of 7.3 kcal mol(-1), providing the first direct experimental evidence that the dissociation of excited ozone exhibits significant nonstatistical behavior. These results are compared with quantum statistical and quasi-classical trajectory calculations in order to gain insight into the potential energy surface and the dynamics of ozone formation.