Application of the density functional theory derived orbital-free embedding potential to calculate the splitting energies of lanthanide cations in chloroelpasolite crystals

• DOI: 10.1016/j.cplett.2004.09.010
• Publication Date: 2004-09-30T11:17:26Z
• Authors: Mohamed Zbiri; Mihail Atanasov; Claude Daul; Juan Maria Garcia...; Tomasz A. Wesolowski
• Keywords: info:eu-repo/classification/ddc/540; ddc:540; 02 engineering and technology; 0210 nano-technology; 01 natural sciences; 0104 chemical sciences

Ligand field splitting energies of lanthanides Ln3+ (Ln = from Ce to Yb) in octahedral environment are calculated using the Hohenberg–Kohn theorems based orbital-free embedding formalism. The lanthanide cation is described at orbital level whereas its environment is represented by means of an additional term in the Kohn–Sham-like one-electron equations expressed as an explicit functional of two electron densities: that of the cation and that of the ligands. The calculated splitting energies, which are in good agreement with the ones derived from experiment, are attributed to two main factors: (i) polarization of the electron density of the ligands, and; (ii) ion–ligand Pauli repulsion.