24 Ch.

2 Atoms, Ions, and Molecules

One might say that a fine structure appeared in the level scheme, the

-
scale of which is controlled by the fine structure constant a. The level
splittings (2.26) are of the order ( 2 ~ t ) ~ R. Note
y that increasing the
ionic charge 2 leads to a rapid increase of relativistic corrections.
(2.26) is in itself not relevant because it is merely one of the con-
tributions to the fine structure. Before discussing the result, we must
consider the contribution arising from the spin-orbit coupling.

Spin-Orbit Coupling
The nature of the spin-orbit coupling can be understood by the following
argument: the electric field of the nucleus is E = -V4 = -(r/r)dr$/dr.
As seen by the electron, the nucleus is orbiting around it with velocity
v, creating a magnetic field Hnucl= -(l/c)v x E. The electron spin
couples to this magnetic field in the form given in (2.19)

1 d4 = --Sefi2 . L--
1d4 .
2 p ~ *SHnucl1 --eii S (v x r)-- (2.27)
mc2 r dr m2c2 r dr
The simple reasoning led to almost the right result. A careful argument
shows that the correct expression for the spin-orbit coupling differs by
a factor of 2. Inserting the Coulomb potential appearing in (2.1), for
the hydrogen problem we find

h2 Ze2
zflso = --s .L . (2.28)
2m2c2 r3
(Remember that in the above equation, S and L are dimensionless op-
erators).
Once Nflso is introduced, S and L are no longer separately conserved
quantities. Rotational invariance guarantees merely the conservation of
+
the total angular momentum J = L S. It is often useful to rewrite
%so as
%!so = -(J
A 2 -L 2 - S2) (2.29)
2
where X can be identified from (2.28). Note that X > 0.
Low-order perturbation theory shows that combining the result (2.26)
with that coming from spin-orbit coupling, the shifts of the hydrogenic