EXCHANGE INTERACTION
Magnetism can be divided into two groups, group A and group B. In group A there is no interaction between the individual moments and each moment acts independently of the others. Diamagnets and paramagnets belong to this group.
Group B consists
of the magnetic materials most people are familiar with, like iron or nickel.
Magnetism occurs in these materials because the magnetic moments couple to one
another and form magnetically ordered states. The coupling, which is quantum
mechanical in nature, is known as the exchange interaction and is rooted in the
overlap of electrons in conjunction with Pauli's exclusion principle. Whether
it is a ferromagnet, antiferromagnet of ferrimagnet the exchange interaction
between the neighboring magnetic ions will force the individual moments into
parallel (ferromagnetic) or antiparallel (antiferromagnetic) alignment with
their neighbours. The three types of exchange which are currently believed to
exist are, a) direct exchange, b) indirect exchange and c) superexchange.
A. Direct exchange
Direct exchange operates between moments,
which are close enough to have sufficient overlap of their wavefunctions. It
gives a strong but short range coupling which decreases rapidly as the ions are
separated. An initial simple way of understanding direct exchange is to look at
two atoms with one electron each. When the atoms are very close together the
Coulomb interaction is minimal when the electrons spend most of their time in
between the nuclei. Since the electrons are then required to be at the same
place in space at the same time, Pauli's exclusion principle requires that they
possess opposite spins. According to Bethe and Slater the electrons spend most
of their time in between neighboring atoms when the interatomic distance is
small. This gives rise to antiparallel alignment and therefore negative
exchange. (antiferromagnetic), Fig. 1.
Fig. 1. Antiparallel
alignment for small interatomic distances.
If the atoms are far apart the electrons
spend their time away from each other in order to minimize the
electron-electron repulsion. This gives rise to parallel alignment or positive
exchange (ferromagnetism), Fig. 2.
Fig. 2. Parallel alignment
for large interatomic distances.
For direct
inter-atomic exchange j can be positive or negative depending on the balance
between the Coulomb and kinetic energies. The Bethe-Slater curve represents the
magnitude of direct exchange as a function of interatomic distance. Cobalt is
situated near the peak of this curve, while chromium and manganese are on the
side of negative exchange. Iron, with its sign depending on the crystal
structures probably around the zero-crossing point of the curve, Fig. 3.
Fig. 3. The Bethe-Slater curve.
B. Indirect
exchange
Indirect exchange couples moments over
relatively large distances. It is the dominant exchange interaction in metals,
where there is little or no direct overlap between neighboring electrons. It
therefore acts through an intermediary, which in metals are the conduction
electrons (itinerant electrons). This type of exchange is better known as the
RKKY interaction named after Ruderman, Kittel, Kasuya and Yoshida. The RKKY
exchange coefficient j oscillates from positive to negative as the separation
of the ion changes and has the damped oscillatory nature shown in Fig. 4.
Therefore depending on the separation between a pair of ions their magnetic
coupling can be ferromagnetic or antiferromagnetic. A magnetic ion induces a
spin polarization in the conduction electrons in its neighborhood. This spin
polarization in the itinerant electrons is felt by the moments of other
magnetic ions within the range leading to an indirect coupling.
In rare-earth
metals, whose magnetic electrons in the 4f shell are shielded by the 5s and 5p electrons,
direct exchange is rather and indirect exchange via the conduction electrons
gives rise to magnetic order in these materials.
Fig. 4. The coefficient of indirect (RKKY) exchange versus the
interatomic spacing a.
C. Superexchange
Superexchange describes the
interaction between moments on ions too far apart to be connected by direct
exchange, but coupled over a relatively long distance through a non-magnetic
material. We take as an example the coupling between the moments on a pair of
metal cations separated by a diatomic anion as illustrated in Fig.5. The ferric
ion has a half filled 3d shell and so has a spherically symmetric charge
distribution (S state ion). The triply rare-earth ion is not symmetric and has
a strong spin-orbit coupling; its charge distribution is coupled to its moment.
The ion's moments are coupled via superexchange, so turning the Fe moment
alters the overlap of the R cation in the molecule. This changes the magnitude
of both the Coulomb and exchange interactions between the cations, leading to a
coupling, which depends on the moment's orientation.
Fig. 5. Superexchange in ferric-rare earth interaction in a garnet.
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