Journal of Physical Chemistry, Vol.99, No.2, 600-605, 1995
Calculation of Electronic-Spectra of Hydrated Ln(III) Ions Within the Indo/S-CI Approach
We present INDO/S-CI model calculations including a spin-orbit treatment on the electronic absorption spectra of the trivalent lanthanide ions Pr3+, Nd3+, and Tm3+ in aqueous solution. With this molecular orbital based procedure both the experimental transition energies and the relative oscillator strengths of the 4f --> 4f excitations in the 8- and 9-fold coordinated complexes [Ln(H2O)(n)](3+) are well reproduced. The intensities of the transitions are due to the admixture of higher lying configurations into the 4f(n) ground state which is found already at the SCF level.
Keywords:SPIN ORBIT INTERACTION;RARE-EARTH IONS;INTENSITY PARAMETERS;INTERMEDIATE NEGLECT;LANTHANIDE COMPLEXES;TRANSITION INTENSITIES;ABINITIO CALCULATIONS;SUPERPOSITION-MODEL;PARAMETRIZATION;MONOXIDES