Density Functional and Basis Set Dependence of Hydrated Ln(III) Properties

Abstract

Benchmark studies of Ln(H2O)1,8-9(3+) (Ln = La, Lu) have been performed to assess the calculated properties obtained with local density approximation, generalized gradient approximation (GGA), meta-GGA, and hybrid functionals, when used with small- and large-core relativistic effective core potentials and their associated bases. Basis set dependence and the importance of specific functions to adequately describe the Ln atomic orbitals have been determined. The lanthanide contraction has been found to be an insufficient metric for characterizing the quality of a method/basis set combination due to cancellation of the errors. The electrostatic description obtained by natural population analysis has been examined, and an alternative partitioning of the valence space, which includes the 6s6p5d4f natural atomic orbitals, has been proposed.