Abstract
The cross-luminescence (CRL) resulting from radiative electronic transitions from the mainly anion-related valence band to the uppermost cation core band has been studied in a number of complex halides containing CsCl, RbF, KF, and BaF2. The energy of the CRL photons is determined by the energy difference of the two bands, and the shapes of the spectra reflect the grouping of the molecular orbitals in the clusters involving cations with a hole in the core shell and nearest-neighbour halide ions. For crystals with more than one type of cation, the spectrum reveals information about the 'active' cation which contains the core hole and also about the other cations. Correlations have been established between the local symmetry of the clusters in different crystals and the number and position of the subbands in the CRL spectra.
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