The low-temperature electronic spectra of Pr3+ at an octahedral site of sym
metry in the PrCl63- moiety, in crystals of Cs2NaPrCl6, Cs2LiPrCl6, and Cs2
NaMCl6:Pr(M = Gd, Y) have been measured and interpreted. Together with the
results from d-f emission spectra and resonance electronic Raman spectra, t
hese new data permitted the assignment of symmetry representations of up to
39 out the possible 40 crystal field levels of the 4f(2) configuration. Th
e inclusion of configuration interaction with the next highest even parity
configuration, 4f6p, into the energy level parametrization reduced the mean
deviation of the energy level fit using the single 4f(2) configuration mod
el alone, by a factor of 2.9 (i.e., from 32.7 to 11.6 cm(-1)). In particula
r, the interaction mechanism for the "anomalous" multiplets D-1(2) and (1)G
(4) was shown to arise from crystal field mixing with 4f6p states. This lea
ds to the inclusion of up to about 0.5% of fp-orbital character for these 4
f(2) eigenvectors. In the 4f(2) single-configuration fits to triplet levels
alone, the fourth-degree crystal field parameter turned out to be larger t
han in the fits to singlet terms, which is the reverse of the expected orde
r if correlation crystal field effects are important. (C) 2001 American Ins
titute of Physics.