Derivation of Lanthanide Series Crystal Field Parameters From First Principles
Résumé
Two series of lanthanide complexes have been cho-
sen to analyze trends in the magnetic properties
and crystal field parameters (CFPs) along the se-
ries: the highly symmetric LnZn 16 (picHA) 16 series
with Ln = Tb, Dy, Ho, Er, Yb and picHA=picoline
hydroxamic, and the [Ln(DPA)3 ](C3H5N2)3·3H2O
series with DPA = 2,6-dipicolinic acid and Ln =
Ce–Yb and with approximate three-fold symmetry.
The first series presents 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 six oxy-
gen atoms. CFPs are deduced from ab initio cal-
culations using two methods: the AILFT (Ab Ini-
tio Ligand Field Theory) which determines the pa-
rameters at the orbital level, and the ITO (Irre-
ducible 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, as a
first approximation. The sign of the 2nd order pa-
rameter B02 differs in the two series reflecting the
different environments. It is shown that the use
of strength parameter S allows for an easy com-
parison between complexes. Furthermore, in both
series, the parameters are found to decrease in mag-
nitude along the series and this decrease is imputed
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