Ab Initio Investigation of the Na3[Ln(ODA)3]·2NaClO4·6H2O (Ln = Ce–Yb; ODA = Oxydiacetate) Series

In this work, the Na 3 [Ln(ODA) 3 ]·2NaClO 4 ·6H 2 O (Ln = Ce–Yb; ODA = oxydiacetate) series was analyzed with the ab initio ligand field theory (AILFT) module of the ORCA computational suite. The results were discussed within the framework of the angular overlap model (AOM) and compared to literature data. We find that the structural changes observed across the series exemplifies the effects of the lanthanide contraction also manifesting in the value of the AOM parameters. It is also shown that the complete active space self-consistent field (CASSCF) methodology is sufficient to describe the ligand field interactions in mononuclear lanthanide complexes, and the effects of dynamic correlation, through n -electron valence state perturbation theory (NEVPT2), are discussed. The calculated ligand field parameters of the present work are compared to the experimentally derived values from the literature.