The vibronic representation for collinear atom–diatom collisions: Two-state semiclassical model

A unique semiclassical description of atom–diatom collisions is presented in which the vibrational as well as the electronic motion is treated quantum mechanically. The electronic Hamiltonian and the vibrational nuclear kinetic energy operator are diagonalized to yield vibronic potential energy curv...

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Bibliographic Details
Published in:The Journal of chemical physics 1975-07, Vol.63 (2), p.842-851
Main Authors: Laing, John R., George, Thomas F., Zimmerman, I. Harold, Lin, Ying-Wei
Format: Article
Language:English
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Summary:A unique semiclassical description of atom–diatom collisions is presented in which the vibrational as well as the electronic motion is treated quantum mechanically. The electronic Hamiltonian and the vibrational nuclear kinetic energy operator are diagonalized to yield vibronic potential energy curves, each correlating asymptotically to a specific electronic and vibrational state of the colliding species. The vibronic curves are used in Stueckelberg-like calculations to yield individual S-matrix elements. This theory is applied to a collinear nonreactive model of X+H2 collisions in which X is either F or Br. S-matrix elements are calculated for transitions between the 2P3/2 and 2P1/2 spin–orbit states of the halogen and vibrational states of H2. The results are in very good agreement with rigorous quantum results.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.431365