Studies of the Potential-Curve-Crossing Problem. II. General Theory and a Model for Close Crossings

Abstract

A unified formal treatment of the two-state potential-curve-crossing problem in atomic collision theory is presented, and the case of close crossings analyzed in detail. A complete solution for this case, including necessary computations, is given using a suitable generalization of the linear model originally suggested by Landau, Zener, and Stueckelberg. Our solution is based upon a hierarchy of approximations concerned with (i) choice of a discrete basis set for electronic coordinates, (ii) semiclassical treatment of the nuclear motion, (iii) an appropriate model for the two-state electronic Hamiltonian, and (iv) a complete solution to that model.