502 Ch.

9 The Gutzwiller Vaxiational Method

Our picture of the correlated, paramagnetic ground state is that

“switching on” U > 0 does not change the overall appearance of the
ground state, it just diminishes the density of doubly occupied sites n d
(and then, because of (9.7), also n,). Fig. 9.l.b depicts an intermedi-
ate situation between the extremes of the uncorrelated Fermi sea, and
full localization. For each U / W , n d has to be chosen optimally. We
achieve this by devising a trial ground state in which n d is controlled by
a variational parameter. The procedure is sometimes described as deter-
mining the optimum degree of “polarity fluctuations”. To understand
the phrase, we have to recall some of the early history of the subject.

9.1.1 Digression: The Early History

It was realized already in the 1930s that the independent-electron de-
scription may break down completely, as it does for the insulating oxides
NiO, COO and Fe3Od. Later it was recognized that it may be inade-
quate even for certain metals such as Ni. Here we follow an insightful
and highly influential discussion given in 1953 by Van Vleck [423]. Van
Vleck’s arguments were critically re-examined and much elaborated by
Herring [ 1631.
Accepting5 that the band filling in Ni can be given as 3d9.44s0.6,
it is clear that a “snapshot” of metallic nickel should consist mainly
of 3d9 and 3d” sites (for the purposes of the present discussion, the
whereabouts of the 4s electrons are immaterial). However, if - in the
spirit of band theory - we neglect the correlations between electrons
with different spin and orbital quantum numbers, we would predict
a fair concentration of 3d8, 3d7, .,. sites as well. Let us estimate the
concentration of 3d7 sites! Consider an arbitrary lattice site, with ten 3d
spin-orbitals. According to independent-particle theory, the probability
of finding any of these spin-orbitals occupied is 0.94, independentlg of the
occupation of the other spin-orbitals. Thus the probability of finding
seven specified spin-orbitals occupied, and the other three empty, is
0.947 x 0.063. However, there are C:’ = 120 ways to pick the seven

5The value n d M 9.4 appears in many solid-state texts, e.g., in [209]. Since the
present argument serves merely to illustrate an idea, we are not worried by the fact
that some contemporary electronic structure calculations give a rather different value.