Predissociation and the Crossing of Molecular Potential Energy Curves

Abstract

The calculation of the width and shape of a line which is broadened because of predissociation has been extended so as to include perturbations of intermediate size. By ``perturbations of intermediate size'' we mean perturbations which are not so great that lines (of given rotational quantum number) belonging to two adjacent vibrational levels are broadened so as to overlap appreciably; they may be any size up to that limit. These calculations have been applied with certain simplifying assumptions to the case where a potential curve giving molecule formation is intersected by a repulsive curve, the curves which cross defining the unperturbed energy levels and wave functions. It is found that the discrete lines are not only broadened, but they are shifted in position, slightly distorted in shape, and there is present a series of subsidiary maxima of the absorption coefficient. The exact amount of broadening of a line depends very greatly upon its energy relative to the energy at which the potential curves cross, and in general a line which is much broadened will also be much shifted in position. In molecules we may expect to have isolated groups of rotational levels in which the central level is sharp, and the rotational levels on either side become more and more diffuse, finally fading out. The predissociation phenomena in iodine chloride are discussed on the basis of the above theory. In particular, two groups of sharp and diffuse levels, such as described, are considered and are respectively ascribed to the isotopic molecules, ICI³⁵ and ICI³⁷. There is some difficulty in describing the phenomena in iodine chloride quantitatively, but qualitatively the experimental results appear to accord with the theory.