11.

1 Lanthanides and Actinides 599

4f

Figure 11.1: Schematic representation of the atomic orbitals of a rare earth atom
(after [134]). The circles give the approximate position of the charge density maxima.
The 5s-5p orbit indicates the size of the xenon core. The lattice constant is about
ten times a~ large as the diameter of the 4f shell.

explanation of this finding is that the binding energy of the solid is

enhanced by donating a third electron to the wide 5d-6s bands.
The unique and interesting features of rare earth systems originate
from the strong intrasite correlations between 4f electrons, which seem
to be essentially unaffected by the surrounding crystal. The underlying
reason is the extraordinary compactness of the 4f shell. As shown in
Fig. 11.1, the 4f shell is lying well inside the xenon core!
Since the core electrons outside the 4f orbital shield the fields aris-
ing from neighbouring atoms very effectively, the physics of rare earth
systems is dominated by the strong intru-ionic correlations of the f -
electrons. The behaviour of a lanthanide ion in a crystal is pretty much
the same as it would be for free ions. At least, this holds for relatively
high temperatures (room temperature is, in this respect, a high tem-
perature). At sufficiently low temperatures, the effects of a weak crystal
field may become apparent. As we discussed in Ch. 3, the weakness
of the crystal field means that all three of Hund’s rules apply; but in
spite of this fact, magnetism may turn out to be largely quenched for
temperatures lower than the crystal field splittings.

gained by aligning the maximum number of spins. Thus in order to keep the half-
filled shell configuration 4f7, europium tends to give up only two electrons, while
gadolinium has three 5d-68 electrons even as a neutral atom.