Hd. Schulte et al., Valence-hole localization in core-valence doubly ionized states of ionic molecules and its impact on KLV Anger spectroscopy, PHYS REV A, 60(3), 1999, pp. 2047-2062
The complete spectra of core-valence dicationic states, i.e., states with o
ne vacancy in the core and one in the valence shell, of the molecules BF3,
AlF3, BCl3, and AlCl3, are investigated by the Green's-function method. An
analysis of the double-hole density in the corresponding correlated states
shows that when the core hole is on a ligand (halogen) atom, the valence ho
le is also strongly localized, either on the same ligand or on a different
ligand. As a result these states can be classified as either on-core or off
-core site states. We discuss how the localization phenomena are at the ori
gin of the chlorine KLV Auger spectra of BCl3 and AlCl3 and, in particular,
how they provide a complete and conclusive interpretation of these spectra
. Due to the intraatomic nature of the Auger process, the simulation of the
chlorine and aluminum KLV Auger spectra is done by a simple convolution of
the respective on-core site component of the computed two-hole density dis
tribution. The ligand atom spectra contain almost no information about the
molecular system, representing an indistinct self-image of the ligand atom
itself, whereas the central atom spectra render a distinct foreign image of
the molecular environment. [S1050-2947(99)07009-2].