Assessing the lanthanide pseudopotential datasets in terms of Slater-Condon spectral parameters

We analyze data of the pseudopotential files and successive plane-wave calculations, determining the SlaterCondon parameters related to the 4f and 5d shells of the lanthanide atoms. The selected pseudopotentials belong to the PAW (projected augmented wave) technique. The outlined procedures are generally applicable to other cases and classes of pseudopotentials. The extracted Slater-Condon parameters are reproducing the atomic spectral terms emerging from configurations with incomplete occupation of the shells of the atoms considered. The purpose of this study is to use the obtained Slater-Condon parameters for the study of lanthanide luminescence due to fn -> fn-1d orbital promotions. The intra-shell Fkff (k = 0,2,4,6) and inter-shell Fkfd (k = 0,2,4) or Gkfd(k= 1,3,5) Slater-Condon parameters are discussed in free neutral lanthanide atoms, free Ln3+ ions and ionic bodies in LnF3 lattices. Furthermore, the d-type intra-shell parameters, Fkdd (k = 0,2,4), are considered in the same conditions. The methodology applied here consists in the decomposition into Slater-Type Orbital (STO) primitives, followed by the analytic evaluation of the Slater-Condon integrals. The ff intra-shell parameters are affected to a little extent by the condition of the whole atomic body, while the fd inter-shell parameters, as well as the intra-shell dd ones, are undergoing a significant increase in Ln0 -> Ln3+ ionization. These parameters undergo a strong reduction (below the neutral atom values) for the ions in LnF3 lattices, probing then the socalled nephelauxetic effect. The actual calculations yield parameters slightly overestimated, in comparison with the available experimental data. However, they can be used in semiquantitative simulations of spectral features, with potential applications in modeling lanthanide-based phosphors.