504 Ch.

9 The Gutzwiller Vaxiational Method

energy between any two electrons on the same site is the same Hubbard
Udd. Between 9 electrons there are Cg = 36 pairwise interactions, so
the on-site energy of a 3 8 site is

E(3d9) = 9Ed + 36Udd (9.14)

where Ed is the atomic d-level. Determining the energies of the 3d8 and
3d1° configurations similarly, the energy expenditure of the hopping
event (9.13) is found to be

+ +
(E(3d8) E(3d10))- (E(3d9) E ( 3 d 9 ) ) = (9.15)
( 8 ~ df 28Udd -k 1OEd -k 45Udd) - 2 ( 9 -k~ 36udd) = udd.

Creating also 3d7, etc. sites would require additional energy investments
of Udd. Hence, consideration of the electron+lectron interaction shows
that hopping processes leading to large fluctuations of local charge must
be hampered by energy barriers, and the concentration of species like
3d8, 3d7, will be quite a bit lower than the independent-electron esti-
mate (9.10). The mechanism responsible for this suppression of charge
fluctuations is that the hopping amplitudes must be dependent on the
occupation numbers of the d-orbitals. To include this feature, we must
go beyond the independent-particle picture, and incorporate local corre-
lation eflects.
For very strong Udd (i.e., for u d d >> W , the d-bandwidth), the aver-
age band filling 3d9*44s0.6is realized by 40% of the sites being 3d10, and
60% 3 8 . For non-integer filling, even Udd + 00 leaves us with a residue,
an unavoidable minumum, of charge fluctuations: in Van Vleck’s classic
work6, this was referred to as the “model of minimum polarity”. By
“polarity” we should understand the deviation of the local charge from
its mean value. We will often refer to them as polarity fluctuations:
these are just the entities which can carry electric current.- Referring
to Sec. 1.3, we now realize that by restricting the charge states of iron
to Fe++ and Fef++, we were introducing a minimum polarity model
of magnetite. Similarly, in Sec. 8.5.3 we used the minimum polarity
picture for Lal-,(Sr/Ca),MnOs.
‘Actually, Van Vleck credits H. Hurwitz with having introduced the idea in his
unpublished Thesis work in 1941.