2.

2 Direct Exchange 31

It is interesting to realize that the Coulomb interaction can induce tran-

sitions between different localized configurations7. There are many more
off-diagonal Coulomb processes which we will meet in the solution to
Problem 2.2.
The above results can be combined into the following expression for
the matrix of 3c

(Ea+cb) (: 1 0 0 0

0 0 0 1
:) ( +
Cab - Jab

8
0
0
Cab
-Jab
0
0
-Jab
Cab
- Jab0 Cab
0
0
0
I
(2.51)
$1 and $4 are immediately eigenstates, being the S” = *l components
of the triplet. The triplet eigenenergy is

There remains a 2 x 2 problem to solve. One of the eigenvalues is Ctr.

The other eigenvalue is

which corresponds to the non-degenerate singlet level.

Note that because of Jab > 0, the triplet is lower in energy than
the singlet. Our essential finding is that direct exchange in orthogonal
orbitals favours ferromagnetism.
There is a very simple argument to support this result. Two parallel-
spin electrons cannot be at the same point r in space because then they
would occupy the same quantum-mechanical state, and this is forbid-
den by the Pauli principle. Since the wave function has a continuous
dependence on the relative coordinate rl - r2, this means that the am-
plitude is gradually suppressed if we decrease 11. - r 2 ( , vanishing when
Irl - rzl = 0. This is called the exchange hole effect, and it says that
parallel-spin electrons tend to keep away from each other in real space.
There is no such effect for antiparallel-spin electrons whose meeting at
71f we use the spin-orbitals as the one-electron basis. Note that this property is
associated with the fact that the one-electron orbitals are extended in space and there-
fore can overlap. The Coulomb interaction is strictly diagonal in the r-representation
which usea fully localized &functions as a basis.