154 Ch.

4 Mott Transition and Hubbard Model

Figure 4.2: Left: a snapshot of the Fermi sea ground state. Right: schematic
representation of the half-filled 3s band. The average energy of the filled part of the
band lies a distance atss below the centre of the band.

where Q is a number of order unity, and it is determined by the shape

of the band. (4.8) expresses that the average kinetic energy gain due to
delocalization into Bloch states is of order t33 (see the right-hand side
of Fig. 4.2).
The total energy density corresponding to the uncorrelated band
ground state is thus

By increasing the lattice constant a, the ratio U33/t3s increases

steeplyg. In doing so, it passes through the critical value (U33/t39)cr =
4a,where the Coulomb energy cost of charge fluctuations begins to ex-
ceed the kinetic energy gain arising from occupying the lower half of a
band. In other words, the Fermi sea ground state energy is predicted
to exceed the energy of an assembly of L neutral Na atoms, which is
just ~ 5 ~ Consequently,
3 ~ . the formation of the band, i.e., of an itiner-
ant ground state, is no longer favourable: it is energetically better to
localize exactly one electron at each lattice site. If we allow only these
two extremes for the ground state: either the uncorrelated JFS), or a
Heitler-London-type state of fully localized electrons, then we axe led to
'U3, remains relatively unaffected but t3s which behaves like the overlap integral
between atomic orbitals centered at nearest-neighbour sites, falls off exponentially.