66 Ch.

2 Atoms, Ions, and Molecules

doing much better for the Heitler-London energy; and surely, the MO
energy could also be improved. However, the largest interaction term
is Ulsand the essential difference between the HL and MO schemes is
that Ulsgives a large contribution to the MO energy and a (pertur-
batively) small contribution to the HL energy. If we stick to the naive
estimates (2.143) and (2.144), we have to conclude that there is a ground
state transition from the molecular orbital regime to the Heitler-London
regime as Ulsis increased (Fig. 2.4.).
We know, of course, that in a small system like the hydrogen molecule
there can be no sharp transition, and the true ground state evolves con-
tinuously from t he MO limit to t h e HL limit as UlS is increased from 0
to 00 (the 6; given in (2.134) gives a pretty good idea what this con-
tinuous U/t-dependence looks like). However, molecular orbital theory
is like band theory, and the Heitler-London picture is like what we use
to describe magnetic insulators, so the interest of Fig. 2.4 is that it
gives a foretaste of the Mott-transition in certain solids. In the sense
of (2.142), the MO ground state shows strong charge fluctuations and
is thus similar to the metallic state. The Heitler-London regime is gov-
erned by the exchange Hamiltonian (2.125) which is like the Heisenberg
model of antiferromagnetic insulators.

Solutions to the Problems

+
Problem 2.1. Since N O Zrelis diagonal in the basis lj = I f 1 / 2 , j z , I), only
+
the Zeeman term ZZ = (J” S Z ) p ~ H (or more precisely, its S”-term) can
have non-diagonal matrix elements. Even this is severely restricted. Taking
the matrix elements of [L2, +
J” S”]= 0 between states derived from different
1, we get (very schematically written)
(Z“L2, J” + S”]IZ‘) = (I(Z + 1) - Z’(V + 1))(1IJZ+ S”1I’)= 0,
wherefrom the matrix element vanishes for I # 1’. Similarly, from “&,J” +
S”] = 0 it follows that there are no matrix elements of J” Sz which would +
connect states with different n. Finally, axial symmetry guarantees that J”
must be conserved. For our present case, it means that the six states derived
from 2 p states are not coupled either to the 2s-like states, or to states with
n # 2. The only non-vanishing matrix elements are between states with j ” =
1/2, and between states with j” = -1/2. Using (2.33) and (2.34)
(3/2, f 1 / 2 , llSz11/2, f 1 / 2 , 1 ) = - h / 3 (2.145)