Auger electron spectroscopy of molecules: Angular and spin correlation with photoelectrons from rotating linear molecules.

A detailed theoretical framework is developed for studying sequential emission of a photoelectron and an Auger electron from a rotating linear molecule with information on momenta and spin-polarization of the departing particles. Identical expressions, except, of course, for different dynamical amplitudes, in both the Hund’s coupling schemes (a) and (b) are obtained for the three different correlation functions considered in this paper. The use of the parity adapted wave functions for the molecular states involved results in, among other things, the presence of only a finite number of harmonics for each of the directions included in the correlation function. Several specific photon-propagation, electron-detection configurations are suggested for which the general correlation functions derived herein become particularly simple. The correlation between the Auger and the photoelectrons is shown to become, under specific conditions, completely isotropic for all bound molecular orbitals, whatever may be their symmetries, from which pair of electrons comes out. This analysis is independent of any dynamical calculations which can be performed in a hierarchy of approximations beginning from semiempirical phenomenological models to sophisticated ab initio methods. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]