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The cage effect and energetic and steric requirements of elementary bimolecular reactions in condensed phases

Abstract

Caging in atom-diatom exchange reactions in rare gases was found predominantly at such high densities that the rare gas atoms themselves become caged. Even when the reactants undergo repeated collisions within the cage, reaction will not occur unless the steric and kinematic requirements for barrier crossing are satisfied. These requirements can be understood in terms of the potential energy surface of the isolated reactants.

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