Photodissociation of K2 (X 1Σ+g-B 1Πu)

A semiclassical model based on an orbital following picture to describe the dissociation dynamics of K*2 (B 1Πu) is outlined. The results of this simple model are in complete quantitative agreement with an exact quantum calculation by Dubs and Julienne based on a half-collision multichannel quantum defect analysis (accompanying paper). These theoretical works give a complete description of the process and indicate that dissociation occurs adiabatically from the Hund’s case (a) to the Hund’s case (c) basis, followed by a sudden recoupling at long range to the Hund’s case (e) basis. The experimentally observed bound–free excitation spectrum and the polarization of the atomic product fluorescence are in excellent agreement with the result of a full thermally averaged calculation based on this theoretical dynamical model.