Unraveling the interplay of 4fn+1 and 4fn5d1 configurations in Ln2+ complexes

Ln2+complexes configurations

The electronic structure of the low-lying states of the trivalent lanthanides (Ln3+) is known to be governed by their corresponding 4fn states. However, the electronic structure of divalent lanthanides (Ln2+) is more intricate due to the apparent interplay between the 4fn+1 and 4fn5d1 configurations. Predicting the nature of the ground state in different chemical environments is still not well understood and crucial to gaining control over the electronic and magnetic properties of these key elements.

A recent study combines multiple quantum mechanical approaches including the Ligand Field DFT (LF-DFT), CASSCF, and MC-pDFT to better understand the correlation between the Ln(III-II) redox potentials and their 4fn+1 → 4fn5d1 transition energies. The study suggests that the ground states of Ln2+ in different chemical environments can be predicted based on deformation density shapes with respect to the trivalent ions and the electron repulsion with the ligands.

The proper recovery of dynamic correlation is important to more accurately predict the electronic structure of these highly correlated systems. The use of DFT-based mutiplet expansion provides a significant improvement compared to perturbatively corrected dynamic correlation, where the LF-DFT is a reasonably cost-effective alternative. 

See also: Ligand-Field DFT webinar.

Maria J. Beltran-Leiva, William N. G. Moore, Tener F. Jenkins, William J. Evans,* Thomas E. Albrecht,* and Cristian Celis-Barros, A comprehensive approach for elucidating the interplay between 4fn+1 and 4fn5d1 configurations in Ln2+ complexes, Chem. Sci.,  Advance Article (2025)

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