Derivation of Lanthanide Series Crystal Field Parameters From First Principles.
Two series of lanthanide complexes were chosen to analyze the trends of the magnetic properties along the series: the highly symmetric LnZn 16 (picHA) 16 series with Ln = Tb, Dy, Ho, Er, Yb and picHA=picoline hydroxamic, and the [Ln(DPA) 3 ](C 3 H 5 N 2 ) 3 · 3H 2 O series with DPA = 2,6-dipicolinic acid and Ln = Ce–Yb and the approximate threefold symmetry. The first series present a compressed coordination sphere of 8 oxygen atoms environment while in the 2nd series, the coordination sphere is formed by an elongated coordination sphere formed by 6 oxygen atoms. Crystal field parameters (CFPs) are deduced from ab initio calculations using two methods: the AILFT (Ab Initio Ligand Field Theory) which determines the parameters at the orbital level, and the ITO (Irreducible Technique Operator) decomposition which treats the problem at the many-electron level. It is shown that the CFPs are transferable from one derivative to the other, within a given series. The sign of the 2nd order parameter $B_0^2$ differs in the two series reflecting the difference of environment. It is shown that the use of strength parameter $S$ permits a easy comparison between complexes. Furthermore, in both cases, the parameters are found to decrease in magnitude along the series and this decrease is imputed to covalent effects.