3.

1 Crystal Fields 77

Figure 3.1: Left: Schematic representation of the local environment of transition

metal ions in the undistorted perovskite structure, and in related structures such as
the KzNiF4 structure. In LaTiOJ, a Ti ion (filled circle) is sitting in the octahedral
environment of surrounding oxygen ions (empty circles); in LazCuOc, the black circle
is a Cu ion. Right: the horizontal plane through the octahedron centers is the
characteristic Cu02 plane of the cuprates.

what is the ground state of the 3d1 configuration? If the Ti3+ ion were
alone in vacuum, and if we neglected the spin-orbit coupling (which is
indeed small for Ti), the electron could be in any of the five 3d orbital
states, and its ground state would be tenfold degenerate (counting also
the spin degeneracy). If we included the spin-orbit interaction, Hund's
third rule would tell us that the ground state is the fourfold degenerate
J = 3/2 level.
The essential point, though, is that the motion of the d-electron is
governed not only by the potential of the Ti3+ ion core, which we include
in the ionic Hamiltonian ?ifTi), but also by the electrostatic potential
of the surrounding six oxygen ions
6
3t3d(r) = ?dTi)(r) + V(O"Y)(r- Rj).
j=1

The very notion of a 3d-state derives from the eigenvalue problem

of the spherically symmetrical 3t(Ti).If the anisotropic field produced
by the oxygen ions were very strong, we should start the solution of
the Schrodinger equation from scratch. Fortunately, it is an acceptable