Theoretical Considerations of Potential Energy Surfaces for Ion-Molecule Reactions,
JOHNS HOPKINS UNIV BALTIMORE MD DEPT OF CHEMISTRY
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A general formulation for potential energy surfaces for ion-molecule reactions is presented in terms of the symmetry and spin restrictions for permitted intermediates from reactants and for what electronic states of the products such intermediates can dissociate to. Large scale ab-initio configuration interaction calculations of the O N2 to NO N reaction convincingly confirmed the mechanism postulated on the basis of the symmetry and spin restrictions. This treatment was generalized successfully to the case of molecular decompositions and confirmed calculationally. Further examples of ab-initio configuration interaction calculations are presented for the C H2 system and for the excited states of H3O. The symmetry and spin formulation of potential energy surfaces is completely general and applicable to all reactive and non-reactive collisions including electronically or vibrationally excited chemical lasers, atmospheric phenomena, hot atom chemistry and chemical kinetics.
- Physical Chemistry