Microscopic theory (quantum-mechanical)

properties only if some of the ions remain magnetic. This may happen in the so called 'transition elements', which have unfilled inner shells. The most notable of them is the 3d shell, but Table 4.1 shows that the 4d, 4f, 5d, and 5f shells have similar properties. Taking chromium again as an example, it has a valency of two or three; hence, in a chemical bond it must lose its 4s electron [see Fig. ll.l6(b)] and one or two of its 3d electrons. The important thing is that there are a number of 3d electrons left that have identical spins, being thus responsible for the paramagnetic properties of the salt.

271

11.7.4 Antiferromagnetism
Let us now study the magnetic properties of solid chromium. From what we have said so far it would foilow that chromium is a paramagnetic solid with a susceptibiliw somewhat larger than that of other metals because free electrons contribute to it, and the lattice ions are magnetic as well. These expectations are not entirely false, and this is u'hat happens above a certain temperature, the Niel temperature (475 K for chromium). Below this temperature. however, a rather odd phenomenon occurs. The spins of the neighbouring atoms suddenly acquire an ordered structure: they become antiparallel as shown in Fig. 11.19. This is an effect olthe'exchange interaction', which is essentially just another name for Pauli's pnnciple. According to Pauli's principle, lwo electrons cannot be in the same state unless their spins are opposite. Hence, two electrons close ro each other have a tendencv to acquire opposite spins. Thus. the electron-pairs participating in cor,'alent bonds have opposite spins, and so have the eiectrons in neighbourins chromium atoms. Besides chromium, there are a number ol compounds like MnO, MnS. FeO. etc. and another element, manganese Q.{eel temperature 100 K) that have the same antiferromagnetic properties. Antiferromagnetics display an ordered structure ofspins; so in a sense, they are highly magnetic. Alas, all the magnetic moments cancel each other (in practice nearly cancel each other) and there are therefore no extemal magnetic
effects.

Louis N6el reccived the Nobel Prize in 1970.

ti

tr
(J)

11
(b)

11 .7

.5

Ferromagnetism

Leaving chromium and manganese, we come to iron, cobalt, and nickel, which are ferromagnetic. In a ferromagnetic material the spins of neighbouring atoms are parallel to each other [Fig. 11.19(b)]. Nobody quite knows why. There seems to be general agreement that the exchange interaction is responsible for the lining-up of the spins (as suggested hrst by Heisenberg in 1928) but there is no convincing solution yet. The simplest explanation (probably as good as any other) is as follows. Electrons tend to line up with their spins antiparallel. Hence, a conduction electron passing near a 3d electron ofa certain iron atom will acquire a tendency to line up antiparallel. When this conduction electron arrives at the next iron ion, it will try to make the 3d electron of that atom antiparallel to itself; that is, parallel to the 3d electron of the previous iron atom. Hence, all the spins tend to line up.

+l{
+

(c)

Fig.

11

.19

The angular momentum vector lor (a) anti ferromagnctic. ( b ) lenomagnetic and (c) lerrimagnetic materials.