48 Ch.

2 Atoms, Ions, and Molecules

is the effective number of Bohr magnetons.

Recalling our discussion of the Bohr-van Leeuwen theorem, it is
clear that the Langevin formula (2.91) does not really belong to classical
physics. A consequent application of classical statistics would exclude
the possibility of postulating the existence of classical dipoles with a
given magnitude 11.1. In retrospect, one might say that the success
of Langevin's theory (1905) is due to the fact that it implicitly used
quantization.
The second term in (2.89) is the T-independent Van Vleck suscep-
tibility. It results from the field-induced admixture of the higher-lying
levels of the multiplet. Its full expression can be derived from (2.77)-
(2.80) (for an application, see Problem 2.6). Here we merely note that
it has the form
(2.94)
since the spin-orbit coupling constant A gives the order of magnitude
of the energy denominators in (2.77).
We may ask whether (2.89) is applicable for the high-temperature
(paramagnetic) phase of solids. Plotting the temperature dependence
of the susceptibility, we often find that it can be fitted with the sum of
a constant and a Curie-Weiss term

(2.95)

Simple mean field theory predicts 8 = -Tc for ferromagnets and 8 = TN

for antiferromagnets [32, 2091. However, C' is not necessarily close to
the C defined in (2.90), and for many antiferromagnets, 8 is rather
different from T N . A realistic description of crystal field effects and
intersite interactions is necessary for resolving the discrepancies. Let
us, however, note that there are examples of the Curie law (2.90) being
followed with extraordinary accuracy down to quite low temperatures,
for instance for Gd(C2H5S04)3*9H20[209]. The reason is twofold: first,
the large non-magnetic molecules keep the Gd ions widely separated
which greatly reduces the ion-ion interaction. Second, according to
Hund's rules, the Gd3+ "vt 4f7 ion is a spin-only ion with S = 7/2 and
L = 0, thus spin-orbit corrections are very weak16.
"In view of the purported L = 0, we may well ask why do we have spin-orbit