A phonon side-band occurs at about 490 cm -1 in the vibronic structure of 4f-5d transitions of Ce 3+ in CaF 2 . This frequency is greater than the highest vibrational frequency of the CaF 2 lattice. It is suggested that the side-band is due to a local mode arising from vibration of the eight nearest fluorine neighbours of the Ce 3+ ion, and that the high frequency is a consequence of increased force constants at the impurity site.
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Hayes et al. (1973) studied this question.
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