The Effect of Correlation on Spectra of the Lanthanides: Pr3+

The effect of correlation on the spectra of lanthanide ions has been investigated using variational methods based on multiconfiguration Dirac–Hartree–Fock (MCDHF) theory. Results from several computational models are reported for Pr3+. The first assumes an inactive Cd-like 4 d 10 core with valence electrons in 4 f 2 5 s 2 5 p 6 subshells. Additional models extend correlation to include core effects. It is shown that, with such models, the difference between computed energy levels and those from observed data increases with the energy of the level, suggesting that correlation among outer electrons should also be based on the correlated core of excited configuration state functions (CSFs). Some M1 transition probabilities are reported for the most accurate model and compared with predictions obtained from semi-empirical methods