Maxwell-Boltzmann distribution curves for M3+-F− interstitials in fluorite-type lattices have been calculated and compared with spectroscopic data. The dominant sites, in the order of their relative importance for low concentrations and T\u3c700 K, are the C4v(1, 0, 0), Cs(2, 1, 0), C3v(1, 1, 1), Cs(1, 2, 2), Cs(1, 1, 3), and Cs(2, 3, 0) sites. The dominant presence of the third-nearest-neighbor monoclinic Cs(2, 1, 0) pair, which has not been reported previously, is predicted by our calculations. In view of this result, the electron spin resonance data on U3+ in CaF2 reported by Mahlab, Volterra, Low, and Yariv, which these authors interpreted in terms of the fifth-nearest-neighbor site, have been shown to arise actually from the prominent presence of the third-nearest-neighbor Cs(2, 1, 0) site
