The 4f5d→4f2 emission spectra of Cs2MPrCl6 (M = Na,Li) and CS2NaYCl6:Pr3+ have been recorded at temperatures down to 10 K. The spectra of Pr3+ in the cubic host Cs2NaYCl6 are the most clearly resolved, and 15 transitions to terminal crystal field levels of symmetry representations Γ5g and Γ4g have been observed and assigned, thereby inferring that the symmetry representation of the lowest 4f5d crystal field level is Γ3u. Each transition is characterized by strong progressions in two totally symmetric vibrational modes. The relative displacement of the potential energy curves for the 4f2 and 4f5d crystal field levels, along the α1g internal mode coordinate, is small, being only about 5 pm. The 10-K ultraviolet absorption spectra of CS2NaYCl6:Pr3+ are assigned to transitions from the [3H4] Γ1g electronic ground state to terminal Γ4u crystal field levels of 4f5d. Nontotally symmetric gerade vibrational modes only provide minor intensity contributions. The large energy gap between the d-f emission and f-d absorption spectra of Pr3+ in the cubic elpasolite host is rationalized. The 8-K excitation spectra of Cs2NaPrCl6 and Cs2NaYCl6:Pr3+, excited by synchrotron radiation, show that the transitions to 4f5d fall into two groups. The energy levels and wave vectors of the (independent) 4f2 and 4f5d configurations of Pr3+ have been calculated using a model which includes spin-orbit coupling and crystal field and Coulomb interactions, as well as the configuration interaction of 4f2 with 4f6p. Using the eigenvector of the predominantly high-spin, lowest excited crystal field level of 4f5d, the emission intensities are reasonably well simulated. However, the refinement of the 4f2→4f5d absorption intensities requires a more detailed knowledge of the crystal field energy level scheme of 4f5d. The configuration interaction of 4f5d with 4f6s and 4f5g is discussed.

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