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Internal hyperfine fields in magnetic

solids
a
P. S. Allen
a
Department of Physics , The University , Nottingham, NG7 2RD
Published online: 20 Aug 2006.

To cite this article: P. S. Allen (1976) Internal hyperfine fields in magnetic solids, Contemporary
Physics, 17:4, 387-402, DOI: 10.1080/00107517608224050

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 CONTEMP. PHYS., 1976, VOL. 17, NO. 4, 387-402

Internal Hyperfine Fields in Magnetic Solids

P. S. ALLEN
Department of Physics, The University, Nottingham NG7 2RD

SUMMARY. This article is divided into three parts, the first of which contains an
introduction to the concept of an internal magnetic field and in particular to the
hyperfine field. The detailed origin of this internal field is outlined in Section 2,
where its dependence on electronic structure is emphasized. By means of typical
examples of hyperfine fields from both the iron group and the rare earth group of
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transition elements, Section 3 illustrates the way in which internal field measurement
is applied (a)to further our understanding of electronic structure in magnetic
materials and ( b )as an aid to the understanding of the statisticaltheories of magnetism.

1. Introduction
The idea of an internal magnetic field has been with us for at least one
hundred years. Yet, because it is not a piece of terminology which is uniquely
debed, it is one about which there often exists confusion. I n this intoductory
section, we shall follow the development of the internal field idea, before
emphasizing and cladying the meaning with which we shall associate it,
i.e. the internal magnetic hyperfine field at the nucleus.

1.1. Development prior to the advent of quantum mechanics

The physical scientists’ understanding of how magnetism manifests itself
within solid bodies has undergone many changes with the passage of time.
During the eighteenth century, when it was fashionable to explain complex
scientific phenomena in terms of imponderable fluids, magnetism was no
exception to the general rule. Both one and two fluid models were proposed
to account for magnetic phenomena. Coulomb himself favoured the two
fluid model and explained the absence of single magnetic poles by supposing
that each of the magnetic fluids (austral and boreal) were transfixed in equal
amounts by the molecules of the solid body.
The fluid models were discarded in the first quarter of the 19th century by
Ampere, who preferred to view magnetism in hrms of the forces between
current elements. His mutual force or ‘action at a distance’ viewpoint
stemmed from the experimental work of the early 19th century French school
on the magnetic effects of currents. This work led Ampere to regard elemental
molecular currents as the fundamental magnetic entities, rather than impon-
derable magnetic fluids, and according to his model the magnetic molecules
maintained their magnetism by virtue of their being enclosed by elemental
perpetual current loops.
Although it did not produce an alternative to amperean currents as a
mechanism for the origin of magnetism, the work of Michael Faraday had a
profound effect upon the development of magnetic concepts. From his distrust
of ‘ action at a distance’ and his conviction that magnetic force was
C.P. 20
 388 P . 8.Allen
‘transmitted’ through space, Faraday initiated the development of the magnetic
field concept. It is therefore conventional nowadays to imagine that if two
separated seats of magnetism are to affect each other, then one of them must
produce at the site of the other a magnetic field, with which the former may
interact. Such a view avoids the idea of action at a distance and only con-
siders entities to be capable of interacting if they occupy the same space
coordinates at one and the same time.
Faraday’s other contribution which was highly relevant to the developing
understandmg of internal magnetic fields was his discovery of diamagnetism
announced in 1845. By 1847 Weber had developed an explanation of this
in terms of molecular currents which postulated a radical difference between
the origins of paramagnetism and diamagnetism. Diamagnetism was thought
to be caused by the induction of currents in the molecular circuits of zero ohmic
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resistance and as such opposed the inducing magnetism. Paramagnetic

materials however, were considered to contain permanent molecular current
loops which adjusted their orientation if an external field was applied, thus
causing the pre-existing current to counteract any induced diamagnetic
currents.
These induced and permanent molecular currents bear a striking resemblance
to contemporary ideas. Indeed Weber went so far as to postulate in 1871
that the amperean currents were composed of one electric charge in orbit
around another of opposite sign, a model which was to k d favour again 35
years later in the hands of Langevin, before being adopted by Niels Bohr for
his celebrated atomic model.
Weber was also responsible for the origin of the idea which extended the
above model to include ferromagnetic materials. This idea was to imagine
that the permanent molecular current loops (which constituted the molecular
magnets) were constrained in their attempts to change orientation when under
the intluence of external magnetic fields, by the action of their neighbouring
loops. Thus the notion was introduced that the elementary magnets within a
solid experience s i g d c a n t magnetic fields due to their neighbours, in addition
to magnetic fields from outside the solid body. The internal field concept was
therefore born about 100 years ago. but at that time the details of its origin,
or indeed of how it might be measured, were not at all clear.
By extending Weber’s basic models, both Langevin and Weiss made sig-
nificant contributions to our understandug of internal magnetism at the
beginning of this century. Langevin, who produced quantitative theories of
both diamagnetism and paramagnetism, thought of Weber’s permanent current
loops in terms of their corresponding magnetic dipole moments and in order
to explain the temperature dependence of paramagnetism introduced the idea
that thermal fluctuations could produce the disordering influence which opposed
the tendency of these magnetic dipoles to align in an applied field. Pierre
Webs followed this in 1907 by proposing that it was the interaction between
neighbouring magnetic dipoles which gave rise to the spontaneous magnetiza-
tion in ferromagnetic materials. Though correct in principle, Weiss was
unable to discover the detailed nature of this interaction. He realized that
the classical dipole-dipole interaction was much too small to produce the
desired effect, and it was not until the advent of Quantum Mechanics some
20 years later that the origins of the ordering interaction became clearer.
 Internal Hyperfine Fields in Magnetic Solids 389

1.2. The internal Jield in quantum mechanicid terms

Intimately linked with any discussion of magnetism is the quantum
mechanical concept of spin. It is unfortunate from a pedagogical point of
view that spin angular momentum does not really have a classical analogue.
The magnetic moment of the electron which derives from its intrinsic spin
angular momentum is a relativistic quantum effect, which is properly explained
by means of relativistic quantum mechanics through the Dirac equation.
Nevertheless, for the purposes of solid state physics it is usually possible to take
refuge in the non-relativistic quantum mechanics of Schrodinger and Heisen-
berg, once it has been suitably modified to account for spin. To bring about
these modifications the electron is no longer represented simply by a wave
function which depends only on space and time coordinates, but by the product
of that function and another function which depends only on the spin state of
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the electron. The product nature of the wave function will be referred to
later when we introduce the idea of exchange. Furthermore it is also necessary
to include in the hierarchy of operators, one which accounts for the magnetic
effects of electron spin. Within this framework and for the purposes of this
article it is probably only necessary to remember that the electron exhibits
an intrinsic spin angular momentum, by virtue of which it possesses a magnetic
moment of one Bohr magneton, which in turn may interact with external
magnetic fields or with other magnetic moments in a way which is often very
similar to the classical interactions of magnetic dipoles. It is nevertheless as
well toremember that this spin magnetic moment behaves as though it originates
from a circulating ourrent or solenoidal source rather than a two magnetic
pole dipole source. I n addition to its spin angular momentum, the electron
possesses another source of magnetic moment. This is its orbital angular
momentum, which gives rise to a magnetic moment whose magnitude can be
explained on classical grounds, but again in terms of a circulating current.
It is remarkable therefore that the contemporary view, having utilized both
relativity and quantum mechanics, still bears such a strong resemblance to
the ideas of Ampere and Weber.
Armed with the concept of spin, non-relativistic quantum mechanics is
able to answer two of the fundamental questions raised but not answered by
the development outlined in Section 1.1. The &st of these questions enquires
as to which atoms exhibit permanent magnetic moments and the second seeks
to discover the nature of the interaction between these atomic magnets which
causes spontaneous ordering. To answer the first question it is necessary to
recall that the possession of a magnetic moment requires the existence of a
net electronic angular momentum. The resultant electronic angular momen-
tum of an atom or ion is the vector sum of the individual angular momenta of
its electrons. In adding together these individual angular momenta, it is
convenient to note that quantum mechanics divides atomic electrons into shells
of constant energy and that if an electronic shell is completely Hied then the
resultant orbital and spin angular momenta of that shell are both zero. The
linear relationship between angular momentum and magnetic moment therefore
tells us that no magnetic moment will arise from a completely filled shell.
If however the atom or ion in question possesses a shell which is not completely
filled, then a finite angular momentum can result from this shell, which in
turn gives rise to a net magnetic moment. The atoms with magnetic moments
 3 90 P.S . Allen
are therefore usually the atoms of transition elements and the magnitude of
this moment will obviously depend strongly on the particular electronic
configuration of that element. A recent Contemporary Physics article by
Bates and Wood (1975) discusses the magnetic moments of transition metal
ions in insulating crystals.
The second question, relating to the origin of the spontaneous ordering
interaction between atomic magnets, also requires quantum mechanics for an
answer. Through the work of Heisenberg and Dirac in the late twenties,
it became clear that the ordering effects arise because of restrictions placed on
the overall electronic wave-functions by P a d ’ s exclusion principle. For
example, for pair of electrons these restrictions require that the overall
wave-function be antisymmetric with respect to exchange of the two particles.
This is a requirement which necessitates a very oareful matching between the
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space part and the spin part of the overall wave-function. Because of this
matching, a particular relative spin orientation can only couple to a certain
space orbital and as a result the energy eigenvalues, which are primarily
determined by the orbital part of the wave-function, carry with them a
correspondmg relative orientation of the spins. The system will therefore
have a ground state in which the spins may have only one relative orientation.
This might be parallel (ferromagnetic) or it might be antiparallel (antiferro-
magnetic). The alternative relative orientation, corresponding to the next
higher energy eigenvalue, can only be obtained if there is enough thermal
energy available to excite a transition between them. The separation in
energy between the two eigenvalues is c d e d the exchange interaction energy,
which we shall denote by Wex, and its sign determines which of the two
relative orientations has the lower energy.
Bemuse the exchange interaction affects the alignment of neighbowing
spins and as a consequence also of the atomic or ionic magnetic moments, it is
physically appeahg to replace it by a fictitious internal effective magnetic
field, Be=, acting on those moments, where
We,= -pion * Bex
Though Be, is an internal field, i t is not the one upon which we shall focus
attention in this article. It must also be remembered that it is fictitious in the
sense that it does not arise from a magnetic interaction. Nevertheless it
corresponds to the sort of field which Webs postulated as the source of spon-
taneous ordering and is therefore often referred to as the Weiss molecular
field. An introductory discussion of various effective field theories of
magnetism is given by Smart (1966).
The nature of the exchange interaction in magnetic materials is a direct
consequence of the electronic distribution within the material in question.
A study of the internal field Be, might therefore present a method of obtaining
information about that electronic structure, which itself is the key to the type
of magnetism found in the material. The evaluation of Be, carries with it the
implication that the ionic magnetic moments are being used as the probe or
sensing magnets. This is not entirely satisfactory because they themselves are
not independent of the electronic struoture which we are trying to investigate.
There is, however, a more elementary probe of electronic structure which
makes use of a truly magnetic interaction. That probe is the nucleus.
 Internal Hyperfine Fields in Magnetic Solids 391

Nuclei with spin I greater than zero possess, by virtue of that spin angular
momentum, a magnetic dipole moment pI. Such nuclei may interact with
their electronic environment by means of a magnetic interaction, which for
historical reasons is called the magnetic hyperfine interaction. If we write
the magnetic hyperfme interaction energy as Wb.f, we may then define an
internal hypefine field Bh.f.,as experienced by the nucleus, by

We now have a second internal field which is sensitive to electronic structure.

Moreover this one has the advantages that first the probe magnetic moments
may be obtained independently of any electronic structure in a magnetic
material and secondly that it can be conveniently measured by accurate
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nuclear spectroscopic methods such as Mossbauer spectroscopy or nuclear

magnetic resonance, n.m.r., spectroscopy. Space does not permit an account
to be given here of any of the methods by which &.i, may be measured.
There are many. The Proceedings of the NATO Advanced Study Institute
edited by Freeman and Frankel (1967) contains a collection of articles covering
a whole range of techniques, including n.m.r. and Mossbauer spectroscopy.
The application of Mtlssbauer spectroscopy and n.m.r. to the metallic magnetic
state is covered in the review by Weisman et al. (1973), and the Mtissbauer
effect itself was dealt with in an earlier Contemporary Physics article (Dale 1976).

2. The magnetic hyperSne field

The hyperfine field Bhmi.,as defined by eqn. (1) in terms of the hyperfine
interaction energy, is composed of a number of contributions, not all of which
are significant in all magnetic materials. I n this section we shall identify the
individual contributions and leave their particular signiscance to be illustrated
in the following section. We shall find, as the section proceeds, that there are
three basic contributions. One is from the electronic orbital angular momen-
tum, the second is from the distribution of non-s-electron spin outside the
nucleus and the third arises from the presence of s-electron spin at the nuclear
site. For pedagogical reasons the approach of this section will be semi-
classical with the quantum mechanical concepts being introduced in a super-
ficial fashion.

2.1. The orbital hyperfine $eZd

A naive view of the origin of this field component is that an orbiting electron
constitutes a circulating current, which in turn produces a magnetic field at
its centre; the site occupied by the nucleus. To obtain an expression for the
interaction energy Worb,between the nucleus and an electronic current density
Jorb due to the orbital angular momentum of a charge element dq, we may
write (Bleaney and Bleaney 1965 a)

Jf'ora = - j A d r ) * Jorb(r) d7 (2)

where A,(r) is the magnetic vector potential of the nuclear current distribution
and d7 is an element of volume. Outside the nuclear volume the magnetic
 392 P.S. Allen
effects of the nuclear current distribution can be represented as a series of
terms of rapidly decreasing magnitude. The first term in the series represents
the effect of a magnetic dipole, the second that of a magnetic octapole, and
so on. If, outside the nucleus we neglect all terms but the first, we may Write
for the nuclear magnetic vector potential at a point r from the origin (Bleaney
and Blemey 1965 a).

Adr) =z(PI
PO
* x r)/r3 (3)

Substituting for A,(r) in eqn. ( 2 ) gives

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If v is the velocity of the charge element dq

Jorbdr=v . dp
Moreover, cyclic permutation of the vectors in the scalar triple product of the
energy equation then enables us to relate v to the quantized orbital angular
momentum ffi by
me(rx v ) = lh

where me is the electronic mass and ? isi Planck's constant divided by 277.
The orbital interaction energy therefore becomes

The integral over the whole charge distribution can then be replaced by a
summation over all electrons, together with the substitition of a n average
value of dq/r3 for each electronic shell and written as - e ( ~ - ~ )where
, e is the
magnitude of the electronic charge.

en
:. Worb=- . -
4.rr m,
. E pI . ii(r,-3) (4)

Electrons in shells with the same quantum numbers n, 1 are expected to have
the same values of ( r ~ - ~ so
) , that the summation will vanish for all closed
shells. Furthermore, this interaction w i l l be zero for s-electrons which have
zero orbital angular momentum. Thus the only contributions to Forb can
come from non-s-electrons in unfilled shells.
By analogy with eqn. (1) we may now write for the orbital component
Barb, of the hyperfine field

where
pB = &/2m,
is the Bohr magneton.
 Internal Hyperfine Fields in MGgnetic Solids 393

2.2. The spin-dipolar hyperfine field

Because of its spin angular momentum, one might consider an electron as a
point magnetic dipole. By virtue of such a magnetic dipole moment, the
electron would produce at the nuclear site a field which would constitute a
spin-dipolar contribution Be-,, to the hyperfine field. Though this description
gives a simple-minded picture of the origin of it does not take account of
the fact t h t the electron spin is spread over the whole of the electronic distri-
bution. Nevertheless, it is possible to start from a classical viewpoint and
develop an expression for BB-d. The interaction energy between two
magnetic point dipoles pI at the origin and MSp(r)separated from it by the
displacement vector r , is (Bleaney and Bleaney 1965 b)
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where ? denotes a unit vector in the direction of r . If one now acknowledges

that the electron is not a disorete point dipole, it is necessary to interpret
) the electronic spin magnetization density at the point r . Moreover
M S p ( r as
the total electronic spin magnetization at r will be the sum over all the electrons
at that point, whence M,,(r) becomes
Msp(r) = - 2PB 2i s @ s i ( r ) (6)

where si is the spin of the ith electron, p s i ( r ) is its spin density at r and where
we have approximated the anomalous g-factor of the electron spin to 2. Thus

By integrating this expression over the whole radial distribution of the ith
electron, one may, by analogy with eqn. (l),extract the following expression
for Bs-d
PO
Bed=-
4rr
* ~ P B
* 2i { [ ~ i - 3 ( s i * 7')31(r,.d-3>i} (8)

where we have used the abbreviation

(LC~A = I rpsi(w31 dr
If the electron spin density is spherically symmetric, as it is for example in the
ca,se of a single s-electron or for a completely filled and unpolarized shell, then
the interaction represented by eqn. (7) vanishes when integrated over the
electronic distribution and is zero. In general therefore contributions
to Bh.t.from this interaction come from unfilled non-s-shells.

2.3. The Pemi contact hyperfine field

As we have seen in the previous section, their spherically symmetric spin
distribution excludes s-electrons from contributing to the spin-dipolar part of
the h y p e f i e field. There is however another mechanism by means of which
they can produce an effective hypefie field contribution. This mechanism
arises because s-electrons have a finite probability of appearing at the nuclear
site, or in other words ' in contact ' with the nucleus, and as a consequence
 394 P.S. Allen
interact with it magnetically. The method of evaluation of the rJpin-dipolar
interaction energy outlined in Section 2.2 is no longer valid as r e 0 and it
therefore becomes necessary to develop another means of deriving the magnetic
interaction energy. However, because it is somewhat unrealistic to try to
obtain a classical model of the nucleus in its own vicinity and so develop a
classical but meaningful evaluation of the interaction energy, we shall instead
concentrate directly on evaluating the effective magnetic field produced at the
origin by a spherically symmetric distribution of electron spin magnetization
and we shall label this field B,,, to denote that i t is the ' contact ' field.
From Maxwell's equations, a spatial distribution of spin magnetization may
be considered to arise horn a current density distribution JBpwhere
J,p = curl Wsp ( r ) 1
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If for simplicity we suppose that the spin magnetization is parallel to the

z axis, then using eqn. (6) for Msp(r),together with a spherical density dis-
tribution pai(r), gives

This current density distribution will then produce a z component of magnetic

field, which may be obtained &om the following volume integral (Bleaney
and Bleaney 1965 a).

By substituting for the volume element in spherical polars and writing the
electron spin density at the nucleus as the square modulus of the electron
wavefunction a t the origin, i.e. psi(0) = l+s(0)li2, by convention assumed to be
uniform over the nuclear volume, one obtains,

A more complete quantum mechanical derivation yields the vector operator

equation

The Fermi contact contribution to the hyperfine field, as simply outlined in

this subsection, will result only from a single electron in an unfilled s-shell.
Though this is one source of B,,, it is not usually the most important source.
Because of the phenomenon known as ' exchange polarization ', it is possible
for closed shells of s-electrons to exhibit a non-zero spin density at the nucleus
and so contribute to B,,,. These contributions will be described in the next
subbion.

2.4. Exchange p o k r i m t h
To understand the origin of a more signiscant contribution to B,,,, we must
remember that magnetic solids are magnetic by virtue of the unfilled electronic
shell which their atoms contain and which exhibits a net spin. This unfilled
 I n t e r n 1 Hyperfine Piel& in Magmtic Sol& 395

inner shell, besides having exchange interactions with similar neighbouring

atomic spins to cause magnetic ordering at low enough temperatures, can also
have spin dependent exchange interactions with electrons in other shells on
the same atom. From the point of view of this discussion the most important
of these is with the filled s-electron shells. These intra-atom exchange inter-
actions polarize the iilled s-shells and so produce non-zero spin densities from
closed s-shells at the nucleus.
For example, if the net spin of an unfilled inner shell is ‘ up ’, then due to
the exchange interaction, electrons in a closed shell will have a slightly different
energy if their spin is ‘ up ’ or parallel, from what they would have if their
spin were ‘ down ’ or antiparallel to that of the inner d e d shell. The slight
difference in energies of ‘ up ’ and ‘ down ’ spins in the closed shell is due to a
reduction in the electrostatic repuleion between parallel spins undergoing
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exchange interactions. This reduction in repulsion may be viewed as an

effective attraction of paralle1 spins and it will result in slightly Werent radial
distribution functions for parallel and antiparallel spins of the closed shell
electrons. The parallel spins will be attracted towards the unfilled shell,
whereas the density of antiparallel spins will be the greater away from the
unfilled shell. In a magnetic material from the f i s t transition series, in which
the net spin is provided by the &led 3d shell, the parallel spins from the
1s and 2s shells are effectively attracted outwards towards the 3d shell, leaving
a net antiparallel spin density at the nucleus. The 4s shell, h contrast has
its parallel spin effectively attracted inwards and therefore produces a more
dominant parallel spin density a t the nudeus.
The total 8-electron spin density a t r = 0 and mused by exchange polarization
should therefore be written as

where the summation is now over all the ns shells, both filled and partially
filled. A small imbalance at the nuclear site between parallel and antiparallel
spins from iilled shells, leads to a significant contribution to BhSf.through the
Fermi contact interaction, which can be particularly large for the inner core
electrons.

2.5. The.resultant hyperfine field

We can summarize this section by combining the major contributions to
the hyperfine field from eqns. (5),(8), (9) and (10) and obtain for B,,

In eqn. (11) we have &ained the possibility that ( Q - ~ ) #(rs-d-3). If the

electron spin density were everywhere equally proportional to the electron
charge density then ( r ~ - ~ ) = ( r ~ and
~ - ~the
> , sums over the two terms
involving them are zero for closed shells. However for a,n atom with an
0.P. 2D
 396 P.S . Allen
unfilled inner shell, exchange polarization can take place and therefore the
equality no longer holds. The Fermi contact term in eqn. (11) is basically
that due to exchange polarization.
I n addition to Bh.f.the nucleus will also experience any externally applied
field plus a local field, comprising the demagnetizing field and the Lorentz
field (Bleaney and Bleaney 1965 a), from t,hose magnetic moments which lie
outside the central atomic cell. Since in certain cases these fields can be of the
order of 1 T, their presence must be allowed for in any experimental determina-
tion of Bh.i.

3. Examples of internal hyperfine fields

I n this section we shall illustrate the relative significance of the various
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contributions to the hyperfine field in a number of representative magnetic

systems. I n order to emphasize their different characteristica, systems con-
taining unfilled 3d shells (the iron series transition elements) will be separated
from those containing d e d 4f shells (the rare earth transition elements).
Each of these subsections may therefore contain examples of ferromagnetic,
anti-ferromagnetic or even ferrimagnetic materials of either a metallic or a
non-metallic nature. Moreover an indication will be given, in the examples
quoted, of how knowledge of the hyperfine field has increased our understanding
of the magnetic system investigated.

3.1. Materials containing atoms from the iron group of tramition elements
The iron group of transition elements is charactmized by an unfilled 3d
shell and contains the elements Sc, Ti, V, Cr, Mn, Fe, Co and Ni. The
electronic distribution of any one of these atoms w i l l vary from material to
material, because the interatomic binding within the parent compound will
determine the degree of ionization and the magnitude and symmetry of the
crystal field environment of the resultant ion. As a consequence the hyperfine
field will not be a constant for an atom of any one element, but will depend
on the material in which that atom resides. Conversely, if we understand fully
the origin of hyperfine fields, then their experimental measurement in EL series
of compounds should provide an exoellent indicator of the electronic con-
figurations producing them.
For example, consider the Mn ions in antiferromagnetic MnF2,for which a
hyperfine field of - 64T has been observed at OK by n.m.r. (Jones and Jefferts
1964). The negative sign indicates that the hyperfine field is antiparallel to
the ionic spin. I n this material the ionic state is Mn2+ corresponding to an
electronic configuration of 1 9 2 2s2 2p6 3s2 3p6 3d5. The half-filled d shell
gives, accordmg to Hund’s rule, a ground state for the free ion with zero
resultant orbital angular momentum (Eisberg and Resnick 1974), i.e. the
spherically symmetric 6S5,2 state for which Borband Bs-d are both zero.
However, exchange polarization of the s-shells results in a fLnite Bh.f.through
the Fermi contact interaction. In table 1 the individual s-electron contri-
butions to B,,, ar0 included for Mn2+. Two points to notice from the Mn2+
listing in this table are, (i) the 1s contribution is a small difference between two
very large quantities and as such is very sensitive to uncertainties in these
large quantities and (ii) the 3s contribution as a result of competing tendencies
 Internal Hyperfine fields in Magnetic Solids 397

behaves as if it lies outside the 3d shell. The resultant B,,, of -70 T, calcu-
lated for core electron polarization, is in good enough agreeaent with the
experimental value to assure us that our basic understanding is correct. It

always experiences a hyperfine field of -

would, nevertheless, be a mistake to suppose that the nucleus of an Mn2+ion
- 70 T, characteristic of a pure 6S
ground state in a highly ionio environment. Covalent mixing, involving the
3d orbitals with orbitals of adjacent non-magnetic atoms, tends to delocalize
the ionic spin moment, thereby reducing the effective spin localized at the
Mn ion site and as a consequence, the magnitude of B,,,.

Table 1. Core s-electron contributions to B,,, due to exchange polarization

(after Freeman and Watson 1965)
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Mn2+(
3d 5, Fe3+(3d5) Fe2+(3ds)
Shell Shell sum Shell sum
Individual Shell sum
$250; 284

-250; 287 I- -3 -5 -3

+22; 667
-22; 808
+3; 121
I- - 141 -179 -131

-3; 047
+74 + 121 +79
-70 -63 1 -55

Units of B,,, are tesla.

Arrows denote electrons with spins parallel ( t ) and antiparallel ( 1 ) to the
ionic spin.

This last point is illustrated by Fe3+ ions in ferrimagnetic yttrium iron

garnet, Y,Fe50,, or Y.I.G. Fe3+ions are isoelectronic with Mn2+ ions and
therefore have a 6S5,2free ion ground state. As shown in table 1, all the core
eleotron polarization terms contributing to B,,, are larger than for Mi2+.
This is due to the tighter binding of the 3d shell in Fe caused by the larger
atomic number of the nucleus. Nevertheless the resultant core electron B,,,
is smaller at - 63 T. I n Y.I.G., the Fe3+ions reside on two types of lattice
site, one is octahedral and the other is tetrahedral. The ion on the tetrahedral
site experiences a greater covalent bonding to the oxygen atoms than is the
case for the octahedral ions and we therefore expect a reduction in the net
ionic spin localized at the tetrahedral site. Indeed the experimental results
justify this expectation and give hypedine fields at 7 7 K of - 55 T for the
octahedral site and -46.5 T for the tetrahedral site (Ogawa and Morimoto
1962). The octahedral Bh.f.will increase further towards the free ion value as
 398 P. 8.Allm

the temperature approaches absolute zero, but the tetrahedral Bh.f. will
remain 10 T smaller due to the covalency effects desonbed.
N

The antiferromagnetic difluoride of iron (FeF,) gives rise to a measured

hyperhe field of - 33 T (Wertheim and Buchanan 1967), which is significantly
smaller than the calculated Fe2+ free ion B,,, of - 55 T, shown in table 1.
The basic difference between FeF, and MhF, is that Fe2+ as a free ion is in
a 3d6, 5D ground state and the free ion orbital angular momentum is not
completely quenched in the rutile structure of the difluorides. Thus a positive
Borbexists which turns out to be about + 16 T. Moreover the rutile structure
contains the Fe2+ions on a tetragonal framework, so their environment is not
cubic and positive dipolar contributions to the magnetic field at the nuoleus
from surroundmg magnetic ions cannot be neglected. As a result the core
polarization B,,, is offset in FeF, by positive orbital and dipolar fields, whereas
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in MnF, the hyperhe field is almost solely due to core electron polarization.
The 3d series of ferromagnetic metals and alloys are more complex than the
correspondmg insulators because of the presence of the electronic conduction
band. Nevertheless, at first sight &.f.shows a strong and simple correlation
with the impaired spin per ion for the three metals Fe, Co and Ni. This is
illustrated in table 2, from which it appears that the hyperfine field is simply
that due to the exchange polarization of the core s-electrons by the unpaired
spin per ion. This conclusion is reinforced by the knowledge that the orbital
angular momentum in these metals is almost oompletely quenched (giving
Borb 0) and also that their cubic structures cause Be-d to vanish. However
N

when one thinks carefully about the contributions from the conduction band,
one can devise (Freeman and Watson 1965) because of the complex interaction
between the 4s and 3d bands, a number of competing positive and negative
terms with magnitudes up to and of the order of 10 T. A detailed discussion
of these terms is beyond the soope of this article, saxe to say that they must
be quite finely balanced in order to give the experimentally observed results.

Net spin BCO? Bh.f.

Metal per ion core polamation Experimental
in Bohr magnetom in T in T
Fe 2.2 -27.5 -33.9
co 1-7 -21.6 -21.5 (f.C.C.)

Ni 0-6 -7.5 -7.5

3.2. Materials containing rare earth atoms

The atoms of the rare earth group of transition elements are characterized
by an unfilled 4f shell. External to the 4f shell are completely m e d 5s, 5p
and 6s shells. This means that the unfilled 4f shell plays only a minor role in
the chemical bonding, is not strongly affected by the crystalline electric field,
and as a consequence retains much of its free ion character, even in the solid
state. This property is in marked confrast to that of the somewhat exposed
 Internal HyperJine Fields in Magnetic Solids 399

3d shell of the iron group elements, where that shell is markedly affected by
bonding and often has its orbital angular momentum quenched by the effects
of the crystalline electric field. As a result of the screening of the 4f shell,
B,,, and Be.&are often dominant in rare earth materials, being of the order
lo2 to 103T, whereas the core electron polarization contribution to B,,,
( - 10 T) plays a much less significant role than in the iron group materials.
N

It is, nevertheless, instructive to begin by considering the more simple case

of a rare earth S state ion, in which the contact term is still important. The
two rare earth S state ions are Eua+ and Gd3+. Such a discussion also gives
us the opportunity to illustrate the important application of hyperhe field
meaaurements to the study of statistical theories of magnetism. These
applications are not restricted to rare earths, but may be gainfully pursued
whenever %.i. is directly proportional to the statio or time average ionic spin,
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e.g. S-state ions. Throughout Section 3 we have loosely referred to hyperhe

field measurements at OK, when we meant at low temperatures very much
less than the critical temperature and usually at liquid helium temperatures.
By working at such low temperatares one ensures that the ionic spin displays
its maximum shtic or time average value. As the temperature rises in the
ordered magnetic state, the ionic spin fluctuations reduce the time average
value (S) of the ionic spin, until at the critical temperature it vanishes alto-
gether. In the paramagnetic state, a finite (S) can only be obtained by the
application of an external magnetio field. The time average (8)is the origin
of the spontaneous magnetization in the ordered state (sub-lattice magnetization
in antiferromagnets) and their temperature dependences are therefore identical.
Understanding the temperature dependence of (S) has presented difficult
theoretical problems, particularly near the critical temperature where highly
accurate data are required to test various theoretical models (Smart 1966,
Brout 1965, Fisher 1967, and Wood 1975). At the low temperature extreme
spin wave theory works quite well. Bulk measurements to determine (8)
from the spontaneous magnetization suffer from a number of serious short-
comings and the most satisfactory method is to use the nucleus as a probe and
measure (S) by means of its hyperfine interaction with that nucleus, using
n.m.r. or Mossbauer spectroscopy. For a review of the experimental deter-
mination of (8)see Heller (1967) or Jaccarino (1965). One such example of
this sort of application has been the investigation of the 153Euhyperfine field
in the insulating ferromagnet EuS, which has a Curie temperature T c =16.5 K.
The crystal structure of EuS is cubic and the E u ~ + ions have *S,I2 ground
states. The only sizable contribution to Bh.f.to be expected therefore, is the

-
contact term from the polarized core electrons, which is calculated (Watson
and Freeman 1967) to be -35 T. The experimentally measured value of
- 34.2 T at 0 K (Charap and Boyd 1964) agrees very well with this theoretical
estimate. The data of Charap and Boyd were obtained between 2 K and 4 K
and these authors concentrated on the spin wave regime in order to obtain the
exchange interaction strengths. Heller and Benedek (1965) on the other
hand followed the hyperfine field from 4-2 K to 0-99 T,, fitted their data to an
equation of the form
Bh.f.(T)/Bh.f.(o) = D {l - T / T c ) '
and obtained for the critical exponent = 1/3.
 400 P.S. Allen
H y p e r h e interactions in ferromagnetic rare earth metals have been exten-
sively reviewed by Bleaney (1972). Metallic Eu and Gd, in common with a
number of their insulating compounds retain, respectively, their divalent and
trivalent ionic S ground states. The experimental value of Bh.f. anti-
ferromagnetic metallic Eu ( - 26-5 T) can be adequately explained by the
addition of (a) B,,, = + 19 T from the conduction electrons polarized by the

bouring ions, to the core polarization contact field of -

parent ion and ( b ) a contribution of - 1 1 . 5 T from the net effect of neigh-
- 35 T mentioned
previously for the Eu2+ion. The rare earth metals whose ions exhibit large
orbital angular momenta reflect this fact by having a hyperfine field which is
both positive and usually an order of magnitude larger than those for S state
ions. For example holmium, whose trivalent ion has a ground state (4f10)518.
is a hexagonal ferromagnetic metal below 2 0 K and therefore has a large
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positive contribution from Borband B,, due to the 4f shell. The sum of
BOP,,and B,, is estima.ted to be about + 760 T for H o ~ +which
, by far outweighs
the core polarization contribution to Be,, of - 20 T. Speculation about the
effect of the conduction electrons in holmium has been largely removed by
experiment. By progressively alloying Ho with Gd, Tb and Dy, Mackenzie
et al. (1974) were able to observe the variation in the resulting Bh,f.at the
lS5H0sites as a function of the mean ionic spin of the alloy 8. In this way
they established a linear variation of Bh.f.with 8, which enabled them to extract
a figure of + 12 T for the contribution to B,,, from conduction electrons
polarized by the parent ion and a figure of - 8.3 T per unit of ionic spin, for
the contribution due to the polarization of conduction electrons by neigh-
bouring ions. Thus in pure holmium itself, where 8 = 2 , the various terms in
the conduction electron contribution largely counteract each other, but with
the negative term just gaining the upper hand. The net hyperfine field at the
1 5 5sites
H ~ in ferromagnetic holmium metal, neglecting the Lorentz field, is
therefore + 736 T.

4. Conclusions
I n this article we have discussed the internal magnetic hyperfme field acting
on a nuclear magnetic moment in a magnetically ordered solid. This field
is due to the effects of electronic magnetic moments arising as a result of net
electronic orbital and spin angular momenta. As such, it is governed by the
original electronic configuration plus the inter-eleotronic interactions within
that configuration and between configurations. Its measurement, in suitably
chosen systems can therefore increase our understanding of electronic structures
and interactions in magnetic materials. A rather striking example of this
occurred with the iron group ferromagnetic metals. Before it had been
experimentally established that the h-perfine field in these metals was in the
opposite direction to the ionic spin moment, the magnitude of the field was
plausibly explained in terms of the then current understanding as though it
were a positive field. The discovery that it was in fact a negative field led to
an increase in theoretical activity and a new appreoiation of the role of core
electron polarization.
I n addition to furthering the understanding of electronic structure, hyperfine
field measurements have been able to mrve an important function in the
 Internal Hyper-ne Fields in Magnetic Solids 40 1

experimental testing of statistical models of ordered magnetism. The ability

to fulfil this role stems f b t from the dominance, in the resultant hyperfine
field of many magnetic materials, of terms proportional to the net ionio spin
and secondly from the high intrinsic accuracy of hyperfine field measurements
by nuclear spectroscopic techniques.
Throughout this article we have neglected to mention transferred hyperhe
fields in magnetic materials. These are the hyperfine fields at the nuclear
sites of non-magnetic atoms such as fluorine, in an antiferromagnetic material
such as MnF,. Mewurements of transferred hyperhe fields greatly increase
the scope of hyperfine field investigations but their discussion is prevented by
lack of space. We have also omitted any discussion of hyperfine fields in
non-magnetic solids. This omission also bears no relation to the relative
importance of the field. When non-magnetic materials are placed in a static
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applied field, the applied field induces changes in the electronic distribution
which can result in hyperfine fields through either the orbital or the spin
interaction. Upon the former is based the powerful analytical tool of organic
chemistry known as high resolution n.m.r., while the latter gives rise to the
so-called Knight shift observed by n.m.r. in paramagnetic metals and of
undoubted significance to those who wish to clarify the electronic structure of
metals and alloys.

BIBLIOGRAPHY
Collections of articles relevant to internal hyperhe fields
ELLIOT,R. J., 1972, Magnetic Properties of Rare Earth Metals (London: Plenum
Press).
FREEMAN, A. J., and FRANKEL, R. B., 1967, Hyperjne Interactions (New York:
Academic Press).
MATTBIAS,E., and SHIRLEY, D. A., 1968, HyperJim Structure and Nuclear Radiation
(Amsterdam: North Holland).
RADO,G. T., and SURL,H., 1965, Magnetism, Vol. I1 a (New York: Academic Press).

REFERENCES
BATES,C. A., and WOOD,P. H., 1975, Contemp. Phys., 16, 547-560
BLEANEY, B., 1972, Magnetic Properties of Rare Earth Metals. Ed. R. J . Elliott,
pp. 383-420 (London: Plenum Press).
BLEANEY, B. I., and BLEANEY, B., 1965 a, Electricity and Magnetism, pp .13948
(Oxford: Clarendon Press).
BLEANEY, B. I., and BLEANEY, B., 1965 b, Ibid., pp. 13-16.
BROUT,R., 1965, Magnetism, Vol. I1 A. Eds. G. T. Rado and H. Suhl, pp. 43-103
(New York: Academic Press).
CHARAP, S. H., and BOYD,E. L., 1964, Phys. Rev. A, 133, 811-818.
DALE,B. W., 1975, Contemp. Phys., 16,127-146.
EISBERG,R., and RESNICK, R., 1974, Quantum Physics, Appendix K (New York:
Wiley).
FISHER,M. E., 1967, Reports on Progiws in Phy&m, 30, 615-730.
FREEMAN, A. J., and WATSON, R. E., 1965, Magnetism, Vol. I I A , Eds. G. T. Rado
and H. Suhl, pp. 167-304 (New York: Academic Press).
HEUER, P., 1967, Reports on Progres in Physics, 30, 731-826.
HELLER,P., and BENEDEK, 1965, Phys. Rev. Letters, 14, 71-73.
JACCARINO, V., 1965, Magnetism, Vol. I1 A, Eds. G. T. Rado and H. Suhl, pp. 307355
(New York: Academic Press).
JONES,E. D., and JEFFERTS, K. B., 1964, Phys. Rev. A, 5, 1277-1280.
 402 I & e ~ Hyperfine
l Fie& in Magnetic Solids
M~CKENZIE,I. S., M~AUSLAND, M. A. H., and WAGG,A. R., 1974, J . Phys. F:
Meta2 Phys., 4,315-328.
OGAWA,S., and MOBIMOTO,S., 1962, J . Phys. Soc. Japan, 17, 654-659.
SUT, J. S., 1966, Effective field them& of Magnetism (Philadelphia: Saunders).
WATSON,R. E., and FREEMAN, A. J., 1967, Hyperjne Interactions, Eds. A. J.
Freeman and R. B. Frankel, pp. 53-94 (New York: Academic Press).
WEISMAN,I. D., SWARTZENDRUBER, L. J., and BENNETT, L. H., 1973, Techniques
of Metals Research, Vol. VI, part 2, pp. 165-504, Ed. E. Paseaglia (New
York : Wiley).
WERTHEIM, G. K., and BUCHANAN, D. N. E., 1967, Phys. Rev., 101, 478482.
WOOD,D. W., 1975, Statistical Mechanics, Vol. 11,Ed. K. Singer, pp. 65-187 (London:
Chemical SOC.).
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The Author:
Dr. Peter Allen is currently a lecturer in the Department of Physics at the University of
Nottingham. He obtained his Ph.D. from the University of Leeds,in 1964, and apart from a
sabbatical year a t the University of British Columbia (1970/71), hae been in Nottingham since
thet time. His research activities are concerned with the investigation of molecular solids at low
temperatures by means of nuclear magnetic resonance spectroscopy.