Journal of Chemical Physics, Vol.117, No.6, 2800-2808, 2002
Spectrum analysis, correlation crystal-field effects and f-f transition intensities of U3+ in LaCl3
High resolution polarized absorption spectra of U3+:LaCl3 single crystals were recorded in the 4000-50 000 cm(-1) range at 7 K. The experimental crystal-field energy levels of the U3+ ion were fitted to a semiempirical Hamiltonian employing free-ion, one-electron crystal-field as well as two-particle correlation crystal-field (CCF) operators. The performed analysis of the spectra enabled the determination of crystal-field parameters and reassignment of some of the observed 5f(3)-->5f(3) transitions. The effects of selected CCF operators on the splitting of some specific U3+ multiplets have been investigated. On the basis of the obtained electronic wave functions the electric-dipole intensity parameters of the total transition dipole strength were determined by fitting the calculated and experimental transition intensities. Among 67 transitions observed in the 4000-22 000 cm(-1) range 56 were sufficiently well resolved for quantitative calculations.