Diabatic and Adiabatic Representations for Atomic Collision Problems

Abstract

The equations of the general Born-Oppenheimer separation into electronic and heavy-particle coordinates are re-examined, and the coupled equations that result for the heavy-particle motion are expressed in a particularly simple form. This is accomplished by introducing a generalized matrix operator for the effective momentum associated with the heavy particles; the matrix portion of this operator represents a coupling of the nuclear momentum with the electronic motion. The commutator between the momentum and potential matrices is a force matrix, which provides an alternative means of evaluating the momentum matrix. The momentum coupling has both radial and angular parts; the angular momentum coupling agrees with Thorson's expression. In the usual adiabatic molecular representation, the potential energy matrix is diagonalized, and all the coupling is thrown into the radial and angular momentum matrices. For collision problems it is often more important to diagonalize the radial momentum matrix, putting the radial off-diagonal coupling into the potential matrix; this generates a family of diabatic representations, the most important of which dissociates to unique separated atom states. This standard diabatic representations has the properties called for by Lichten, is uniquely defined even with the inclusion of configuration interaction, and leads immediately to the Landau-Zener-Stueckelberg limiting case under appropriate conditions.