Crystal Field in Rare-Earth Complexes: From Electrostatics to Bonding

Riccardo Alessandri, Habiburrahman Zulfikri, Jochen Autschbach, Hélène Bolvin* (Corresponding Author)

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

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The flexibility of first-principles (ab initio) calculations with the SO-CASSCF (complete active space self-consistent field theory with a treatment of the spin-orbit (SO) coupling by state interaction) method is used to quantify the electrostatic and covalent contributions to crystal field parameters. Two types of systems are chosen for illustration: 1)The ionic and experimentally well-characterized PrCl3 crystal; this study permits a revisitation of the partition of contributions proposed in the early days of crystal field theory; and 2)a series of sandwich molecules [Ln(ηn-CnHn)2]q, with Ln=Dy, Ho, Er, and Tm and n=5, 6, and 8, in which the interaction between LnIII and the aromatic ligands is more difficult to describe within an electrostatic approach. It is shown that a model with three layers of charges reproduces the electrostatic field generated by the ligands and that the covalency plays a qualitative role. The one-electron character of crystal field theory is discussed and shown to be valuable, although it is not completely quantitative. This permits a reduction of the many-electron problem to a discussion of the energy of the seven 4f orbitals.

Original languageEnglish
Pages (from-to)5538-5550
Number of pages13
JournalChemistry : a European journal
Issue number21
Publication statusPublished - 11 Apr 2018


  • UT-Hybrid-D
  • Bond theory
  • Crystal field effects
  • Lanthanides
  • Ligand effects
  • Ab initio calculations
  • n/a OA procedure


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