Assessment of DFT Functionals for Structural Determination of Lanthanide(III) Complexes Using Ligand Field Splitting DOI Open Access
Lucca Blois, Renaldo T. Moura, Ricardo L. Longo

et al.

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(2)

Published: Jan. 13, 2025

ABSTRACT Lanthanide (Ln 3+ ) tetrakis complexes, C[Ln(L) 4 ], are important for applications due to their high quantum yields, solubility, and stability. Their luminescent properties depend on the structure, particularly coordination polyhedron, assessment of computational methods calculating structures is paramount. Usually, this uses RMSD distances in [Ln(L) ] − complex or {LnO 8 } polyhedron between crystallographic calculated structures. However, since ligand field (LF) splitting highly geometry‐dependent, experimental LF Stark levels (RMSD‐LF) offers a more accurate measure evaluating methods. energy eigenvalues were using simple overlap model (SOM), with geometries optimized by various density functionals. M06 M06‐L functionals, def2‐SVP/MWB52(Eu)/CPCM, demonstrate best balance accuracy low cost, making them suitable modeling C[Eu(L) complexes.

Language: Английский

Assessment of DFT Functionals for Structural Determination of Lanthanide(III) Complexes Using Ligand Field Splitting DOI Open Access
Lucca Blois, Renaldo T. Moura, Ricardo L. Longo

et al.

Journal of Computational Chemistry, Journal Year: 2025, Volume and Issue: 46(2)

Published: Jan. 13, 2025

ABSTRACT Lanthanide (Ln 3+ ) tetrakis complexes, C[Ln(L) 4 ], are important for applications due to their high quantum yields, solubility, and stability. Their luminescent properties depend on the structure, particularly coordination polyhedron, assessment of computational methods calculating structures is paramount. Usually, this uses RMSD distances in [Ln(L) ] − complex or {LnO 8 } polyhedron between crystallographic calculated structures. However, since ligand field (LF) splitting highly geometry‐dependent, experimental LF Stark levels (RMSD‐LF) offers a more accurate measure evaluating methods. energy eigenvalues were using simple overlap model (SOM), with geometries optimized by various density functionals. M06 M06‐L functionals, def2‐SVP/MWB52(Eu)/CPCM, demonstrate best balance accuracy low cost, making them suitable modeling C[Eu(L) complexes.

Language: Английский

Citations

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