STATIONARY-STATE SCATTERING-THEORY FOR DISSOCIATIVE PHOTODETACHMENT ON NONADIABATICALLY COUPLED POTENTIAL SURFACES AS A PROBE OF TRANSITION-STATES

We develop a stationary-state scattering theory of dissociative photod etachment in a transition-state region for a system in which two or mo re potential surfaces are mutually coupled through the nonadiabatic in teraction in dissociative channels. Since the present phenomenon invol ves electron detachment and molecular dissociation dynamics, it is a d oubly half collision in a three-body problem. We perform an asymptotic analysis for the dissociative wave functions, which formally gives a closed form of the transition amplitude in which the pulse shape and p olarization of a pumping laser, the kinetic energy distribution of a d etached electron, and the product distribution are all correlated. The present formal theory thus provides a unified basis for the analyses in the experimental and numerical studies. We revisit the mathematical role of the so-called in-going state for general dissociation dynamic s and, in particular, argue that the traditional interpretation of the ingoing wave function due to Breit and Bethe is not necessarily valid .