Effective core potential methods for the lanthanides

Abstract

In this paper a complete set of effective core potentials (ECPs) and valence basis sets for the lanthanides (Ce to Lu) are derived. These ECPs are consistent not only within the lanthanide series, but also with the third‐row transition metals which bracket them. A 46‐electron core was chosen to provide the best compromise between computational savings and chemical accuracy. Thus, the 5s and 5p are included as ‘‘outer’’ core while all lower energy atomic orbitals (AOs) are replaced with the ECP. Generator states were chosen from the most chemically relevant +3 and +2 oxidation states. The results of atomic calculations indicate that the greatest error vs highly accurate numerical potential/large, even‐tempered basis set calculations results from replacement of the large, even‐tempered basis sets with more compact representations. However, the agreement among atomic calculations remains excellent with both basis set sizes, for a variety of spin and oxidation states, with a significant savings in time for the optimized valence basis set. It is expected that the compact representation of the ECPs and valence basis sets will eventually encourage their use by computational chemists to further explore the bonding and reactivity of lanthanide complexes.