42 Ch.

2 Atoms, Ions, and MoJecules

I(JJ”LS13-lzlJ- 1,J”LS)12
+ (2.77)
E(0)( J ) - E(0)( J - 1)
For the sake of future applications, we quote the matrix element [465]
1
-(JJ”LS13lzlJ
PBH
+
1, J” L S ) = fl(J,L , S ) f i ( J , J Z ) (2.78)

where

fdJ, L , S ) =
+ + + +
[ ( J 1)2 - (S - A ) 2 ] ( J 2 s L ) ( - J + s +L)
+ +
4(J 1)2(2J 1)(2J 3) +
(2.79)
and
( J + 1 - P ) ( J + 1 + J”) . (2.80)
The quadratic terms in (2.77) describe the second-order Zeeman effect.

Digression: The Bohr-Van Leeuwen Theorem

Let us return to the classical Hamiltonian (2.73). The corresponding
partition function is

(2.81)
It is clear that for each of the p-integrations, the replacement p +
p - (Q/c)A can be made and then the magnetic field no longer appears
in the expression of the classical free energy

It follows that the magnetization

(2.82)
vanishes identically. Classical physics cannot explain either the sponta-
neous magnetization of materials like iron, or the field-induced magne-
tization of non-magnetic substances. This remarkable result is known
as the Bohr-Van Leeuwen theorem13.
13Apparently,it was first derived by N. Bohr in a Thesis work (Copenhagen, 1911).
J.H. Van Leeuwen rediscovered and thoroughly discussed it in her Thesis work (Lei-
den, 1919). The theorem became widely known only when Van Vleck re-examined
and carefully explained it in his book ([423] was first published in 1932).