Experimental and theoretical studies of the vibrational and electronic spectra of a lanthanide ion at a site of T(h) symmetry: Pr3+ in Cs2NaPr(NO2)6.

The Pr(3+) ion in Cs(2)NaPr(NO(2))(6) is situated at a site of T(h) symmetry with 12-coordination to O atoms of bidentate nitrito groups. First-principles calculations of the vibrational modes of the complex were carried out using the density functional theory with the generalized gradient approximation Perdew-Burke-Ernzerhof exchange-correlation functional. The calculations that treated the Pr(3+) 4f electrons as valence electrons showed better agreement with the experimental vibrational assignments compared with those treating the 4f electrons a part of the inner core.

Electronic spectra and crystal field analysis of energy levels of Ho3+ in HoF6(3-).

The electronic absorption spectra of single crystals of Cs(2)NaHoF(6) have been recorded in the spectral region between 4700 and 42000 cm(-1) at temperatures down to 10 K. The structure in the (5)I(8) → (5)I(J) (J = 7-4), (5)F(J) (J = 5-1), (5)S(2), (5)G(J) (J = 4-6), (3)K(J) (J = 7, 8) transitions has been analyzed and assigned. The emission spectra (5)S(2) → (5)I(J) (J = 6-8) and (5)G(4) → (5)I(J) (J = 5-7), (5)F(5) have also been recorded at 10 K for crystals of Cs(2)NaHoF(6) and partly also for samples of Cs(2)NaHoF(6):Yb(3+).

Energy levels and hypersensitivity of samarium(III) in the elpasolite Cs(2)NaSmCl(6).

Electronic absorption spectra of neat Cs(2)NaSmCl(6) between 300 and 10 K are reported for the spectral region between 900 and 40 000 cm(-1). Interpretation of the intricate vibronic structure enables 91 conclusive and 45 tentative Kramers doublet and quartet energy levels of the 4f(5) ion Sm(3+) in this system to be assigned. Configuration interaction assisted crystal field calculations employing the diagonalization of the combined 4f(5) and 4f(4)6p(1) matrices fit the energy levels better than the conventional 4f(5) crystal field calculation.

Electronic spectra of Cs2NaYbF6 and crystal field analyses of YbX6(3-) (X = F, Cl, Br).

Detailed analysis of the vibronic structure in the electronic absorption spectrum of Cs2NaYbF6 at temperatures between 10 and 300 K enables the crystal field energy level diagram of Yb3+ in this cubic host to be deduced. Ultraviolet and visible laser excitation of Cs2NaYbF6, Cs2NaY(0.9)Yb(0.

Synthesis, Structure, and Spectroscopy of Rare Earth Hypophosphites. 1. Anhydrous and Monohydrated Lanthanide Hypophosphites.

The lanthanide hypophosphite complexes Ln(H(2)PO(2))(3) (Ln = La, Pr, Nd) and Ln(H(2)PO(2))(3).H(2)O (Ln = La, Pr) crystallize in the space group P&onemacr; (No. 2), Z = 2.