Dynamical coupling in the differential equations approach to atom-diatom exchange reactions |
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| Authors: | Paul McGuire David A. Micha |
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| Affiliation: | 1. Quantum Theory Project and Department of Chemistry , University of Florida , Gainesville, Florida, 32601;2. Quantum Theory Project and Department of Physics , University of Florida , Gainesville, Florida, 32601;3. Max-Planck-Institut für Str?mungsforschung , 3400, G?ttingen, B?ttingerstr. 6/8, West Germany |
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| Abstract: | The atomic exchange reaction A + BC → AB + C is investigated quantum mechanically employing a coupled differential equations approach. The relative motion in reactant and product channels is described in the common coordinate R 3 (the AC nuclear separation) and is developed in three-dimensional space. The total wave functions of the system are expressed as a superposition of valence bond electronic states of the initial (A, BC) and final (AB, C) configurations, with the coefficients describing the relative and internal (vibrational, rotational) nuclear motions. Choosing convenient trial functions with the appropriate boundary conditions and using the Kohn variational principle, a set of differential (rather than the usual integro-differential) equations is obtained for the relative motion wave functions in R 3. The potential matrix elements turn out to be dynamical in that they depend on the initial k 1 and final k 2 wave vectors. Two-state coupled channel calculations of the differential and integral cross sections for the isotopic species D + H2, H + H2 and D + D2 are presented for collision energies up to 0·8 eV. |
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