Perturbative reactive scattering within a quasiadiabatic representation: Multichannel application

Peploski, James C.; Eno, Larry
July 1991
Journal of Chemical Physics;7/15/1991, Vol. 95 Issue 2, p895
Academic Journal
Low energy reactive transition probabilities for a model multichannel collision problem, are determined within a so-called quasiadiabatic (QA) representation of the system electronic energy. The procedure involves setting up a set of coupled nonreactive surfaces (the QA representation) and then perturbatively mixing coupled-channel wave functions on the QA surfaces. It is applied to a hard-sphere-type model of the collinear A+BC reaction and for a relatively high system mass (5.0×104 a.u.). Optimization of the representation (which we have previously argued should temper maximization of the QA reactivity with a drive for balance between its diabatic and nonadiabatic components) yields results which are in very good agreement with exact ones (errors <10%) over a wide range of collision energies. At the same time, as the collision energy approaches the classical reactive threshold, we see evidence of QA failure; we trace this to difficulties with our particular optimization procedure when the diabatic contribution becomes dominant. ‘‘Conventional’’ perturbative results are generated for the same model problem and found to be poor in general (errors [bar_over_tilde:_approx._equal_to]40%–50%). It is demonstrated that the ineffectiveness of the conventional approach may be ascribed to the system’s high mass.


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