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

Zbiri, Mohamed; Atanasov, Mihail; Daul, Claude; Garcia-Lastra, Juan Maria; Wesolowski, Tomasz A.

doi:10.1016/j.cplett.2004.09.010

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Journal article

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

Zbiri, Mohamed Inorganic Chemistry Department, University of Fribourg, Switzerland
Atanasov, Mihail Inorganic Chemistry Department, University of Fribourg, Switzerland - Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Sofia, Bulgaria
Daul, Claude Inorganic Chemistry Department, University of Fribourg, Switzerland
Garcia-Lastra, Juan Maria Departamento de Fisica Moderna, Universidad de Cantabria – Facultad de Ciencias, Santander, Spain
Wesolowski, Tomasz A. Département de Chimie, Université de Genève, Switzerland

28.09.2004

Published in:

Chemical Physics Letters. - 2004, vol. 397(4-6), p. 441-446

English 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.

Faculty

Faculté des sciences et de médecine

Department

Département de Chimie

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