8.

5 Effbcts of Degeneracy 465

case when t and JH are more-or-less comparable (when a considerable

fraction of local configurations violates Hund’s rule), and the case of a
strong JH,
Let us consider the latter case first because it is conceptually simpler.

-
Here we wish to model systems like Lal-,Sr,MnOa and Lal-,Ca,MnO3.
In these materials, the valence states in question are Mn4+ tgg and
Mn3+ t$ei. The crystal field splitting between the t2g and eg lev-
-
els, and the fact that the t2g lobes are not directed towards the nearest
neighbour ions, help to accept the idea that it is only the “surplus” eg
electrons that can hop. Since the three parallel t 2 g electrons form a kind
of a ridig ion core, we might as well model them by an S = 3/2 core
spin which is coupled ferromagnetically to an eg electron which happens
to visit the ion. We assume that t is the smallest energy parameter:
JH>> t . Then the low-energy subspace is spanned by configurations in
which the ionic states satisfy Hund’s rule32 everywhere. If we further
simplify the problem by neglecting the twofold degeneracy of the eg or-
bital, then the inclusion of the eg-eg and eg-t2g Coulomb interactions
is unnecessary because JH/t >> 1 is sufficient to guarantee that charge
fluctuations are kept to the unavoidable minimum33, i.e., if n is lying
+
between the integers no and no 1, then there are (n- no)L ions with
+ +
no 1 electrons, and (1 no - n ) L ions with no electrons (no = 3 for
doped LaMnO3 ). The motion of the eg electrons on the background of
the t9g cores is described by the double exchange Hamiltonian

Xdex = -t +
cjgCig)
~(c~gcjb - JH sj*sj (8.38)
ij 0 j
where sj is the eg (henceforth conduction electron) spin at site j

(8.39)

321nthis section, always Hund’s first rule is meant by Hund’s rule.

33Having neglected the degeneracy of the eg (“Conductionelectron”) orbital, we
would loose Hund’s rule energy if we put two eg electrons to the same site. Here
JH = 00 has the same effect as U = 00: it keeps charge (“polarity”) fluctuations to
an unavoidable minimum. This “minimum polarity” picture is certainly not appli-
cable to the transition metals but it should be quite acceptable for the “bad metals”
obtained by doping certain transition metal compounds. - See p. 502 for the history
of the minimum polarity concept.