40 Ch.

2 Atoms, Ions, and Molecules

the L-S coupling scheme breaks down for heavy elements. This is indeed
the case: for large 2, J and J z are the only relevant quantum numbers,
and the mixing of states with different ( L ,S) values becomes noticeable.
However, one really never gets to the extreme case of the so-called J-J
coupling where the spin-orbit interaction would be much stronger than
the energy differences between the terms. Heavy atoms can rather be
characterized as intermediate-coupling cases. This manifests itself in,
say, 10%-like deviations from the Land6 interval rule. For our purposes,
it will be good enough to use the results of the L-5' coupling even for
heavy atoms, and point out numerical inaccuracies when the need arises.

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We should have a rough idea of the numerical values. The A0 appear-

-
ing in (2.69) or in (2.70) is: 3.7. 10-3eV for C ( 2 = 6); 6 . 10-2eV
for Co (2 = 27); 0.125eV for Rh (2 = 45); and 1.25eV for Bi
(2 = 83). An extensive list can be found in [465]. (Remember that the
X figuring in (2.71) may be only 1/5th of the corresponding Xo).
Problem 2.3. Determine the possible ( L ,S) value pairs a) for a p2 configu-
ration, and b) for a d2 configuration!

2.3.1 Coupling to the Magnetic Field

We repeat the argument which led from (2.7) to (2.13) in the single-
electron case. The classical Hamiltonian is now

1 N
Xf1(rl,.. . , r ~ ; p 1 .,.., P N ) = - +V(rl,. . . ,rN)
2 M 7.= 1 (pj -
C

(2.73)
where V is the sum of the potential and electron-electron interaction
energies. (2.73) is quantized following the rules Em,r,] = (h/i)Jmn.
Assuming a constant field and using the gauge (2.10), we find that, in
first order, the magnetic field couples to

C(l2+ 2 4 =L +2s
where L is the total orbital angular momentum, and S is the total spin.
The full expression of %!field is given by the sum of the Zeeman term and