1098 T. HOLS TE I N AND H.

P RI MAKOF F

than any d& thus far found among the rare gases, gases, all of which have values about 1.4. Not
and reacts with 3s5 (from which it is separated too much importance can be placed on this
by only 1 cm ') to produce Paschen-Back point, however, for this configuration is badly
effects. * distorted. Indeed, 4d~ seems to be far below its
The very large discrepancy in 2s2 is not so usual position, being lower than 4d6 which is
easy to account for. It looks, almost, as if the usually the lowest level of the P5d configuration.
level were improperly classified, although it The levels 3ps and 3p9 are only 5.5 cm ' apart
appears to be in about the correct position. and perturb each other sufficiently to distort the
Perhaps 2s2 and BsI' should be interchanged. patterns of lines involving them. Their g values
The level 4d& seems to have an abnormally were determined by methods already described. '
low value when compared with the other rare (See Fig. 2.)
* The calculations of the Paschen-Back interaction of 9
J. B. Green and J. F. Eichelberger, Phys. Rev. 56, 51
3s5 and 4d2 will be discussed in a separate communication. (1939); J. B. Green and J. A. Peoples, ibid. 56, 54 (1939).

DECEMBER 15, 1940 PH YSICAL REVIEW VOLUM E 58

Field Dependence of the Intrinsic Domain Magnetization of a Ferromagnet

T. HQLsTEIN
¹m York University,¹m York, ¹m York
AND

H. PRIMAKOFF*
Polytechnic Institute of Brooklyn, Brooklyn, New York
(Received July 31, 1940)

In this paper, the variation of the intrinsic domain magnetization of a ferromagnetic with the
external magnetic field, is obtained. The basis of the treatment is the exchange interaction
model amplified by explicit consideration of the dipole-dipole interaction between the atomic
magnets. Approximations appropriate to low temperatures and equivalent to those used by
Bloch in his derivation of the T law, are introduced. The resultant expression for the intrinsic
volume susceptibility decreases slowly with increasing field; at high fields the functional de-
pendence is as the inverse square root of the field. The variation with temperature is linear; at
room temperature and for fields of about 4000 gauss, the order of magnitude of the (volume)
susceptibility is 10 '. The results are compared with experiment and satisfactory agreement is
found.

I. INTRQDUcTIQN When technical saturation has been reached,

CLOSELY allied to the problem of the tem- there are still, as a result of temperature agita-
~ perature variation of the intrinsic mag- tion, some atomic magnetic moments which are
not oriented in the direction of H. Further
netization, M, of a ferromagnetic body, is the
problem of its variation with an external mag- increase of magnetization is then to be ascribed
netic field, H. This intrinsic magnetization is to the progressive alignment of the temperature
characteristic of a single ferromagnetic domain disoriented atomic magnets by an increasing
and is identical with the experimentally observed field. The phenomenon is physically similar to
magnetization when "technical saturation" has that which obtains in the magnetization of a
been achieved, i.e. , when all of the domains in all paramagnetic substance; however, the existence
of the individual crystal grains of the specimen of the strong ferromagnetic coupling forces
have parallel magnetization vectors. ' between the atomic magnets changes completely'
* Present address: Queens College, Flushing, New York. both the magnitude of the effect, and its de-
' "Technical saturation" is achieved at fields of 2000—
4000 gauss, depending on the metallurgical treatment of
the (polycrystalline) specimen. ' Cf. Eq. (30), (31) below.
 FIELD DEPENDENCE OF MAGNETIZATION 1099

pendence upon the external magnetic field and of the magnetization M(T, H) from its maximum
upon the temperature. possible value, Mo, is small. This condition always
The problem of the variation of M with H has prevails at temperatures sufficiently below the
been treated by Akulov' on the basis of the Curie temperature. '
phenomenological Weiss-Heisenberg internal field It has also been found possible to take account
theory;4 his result is in strong disagreement with of the magnetic interactions between the atomic
subsequent experiments. 5 magnets. These interactions are important,
The basis of the treatment of the variation of since, in most of the experiments thus far per-
M with H given in the present paper is the formed, the magnetic energy of an atom due to
exchange interaction model of a ferromagnetic, the magnetic moments of all of the other atoms,
wherein the electrons responsible for the ferro- — 4~PMO/3 is usually larger than the magnetic
magnetism are anchored to the atomic cores and energy due to an external magnetic field, =pH
do not wander about the metallic interior. The It will be seen that the effect of the magnetic inter-
essential approximation used in the treatment of actions cannot be expressed correctly by replace-
this model is that the condition of "quasi- ment of H by II+yM ' in the final expression for
saturation" obtains; vis. , the percent deviation the magnetization (cf. (30), (31), (32), below).

I I. THE HAMILTONIAN

The exchange interaction model of a ferromagnetic, amplified by the inclusion of magnetic inter-
actions, is described, in the space of the atomic spin variables by the following Hamiltonian, "
H= —, Q 2Jg~(R(„)S( S„+—
—'
3S).R(~S R)~) —Q
', Q (4p'/R'( )(R'(~S( S„— 2pSI, '*~H. (1)
m=1 l, m=1 l,

Here, N is the total number of atoms, while the sums over I, and m each run from 1 to N, summands
with l =m being omitted. R&„— — R& —R„~ is the distance between the centers of gravity of the Lth
~

and nth atoms; Jl the exchange integral between these atoms; Sl the spin angular momentum
operator of the atom at Rl in units of fi; the magnetic field FI is directed along the s axis.
The first term in H is the Heisenberg exchange energy expressed in terms of the atomic spin
operators (Dirac vector model). ' The second term arises from the magnetic dipole-dipole interaction
between electrons on different atoms. The effects of exchange and of higher magnetic poles on the
magnetic interaction are both neglected;" hence, the centers of gravity of the atoms constitute the
N. S. Akulov, Zeits. f. Physik 69, 822 (1931). See, also, R. Becker and W. Doring, Ferromcgrietismus (Julius
Springer, Berlin, 1939), p. 35.
See, for example, J. H. Van Vleck, Theory of Electric and Magnetic Susceptibilities (Oxford University Press, 1932),
Ch. 12.
~ A full discussion of the various experimental results and comparison with theory is given below in Section VI.
6 W. Heisenberg, Zeits. f. Physik 49, 619 (1928).
~ The exchange interaction model, with the specimen in the condition of quasi-saturation, has been approximately
treated by Bloch in his derivation of the temperature variation of the intrinsic magnetization. Cf. Zeits. f. Physik 61,
206 (1930); 7'4, 295 (1932). Using mathematical methods different from those in the present paper, Bloch derives the
well-known T& law for atoms with spin S=-', . Bloch's methods have been extended by Moiler to the case S&-, Cf. '.
Zeits. f. Physik 82, 559 (1933).
8 Bohr magneton.
' py is the
is
a numerical factor whose value lies between 0 and 4m.
'~ It is to be noted that (S&)' commutes with the Hamiltonian of Eq. (1); therefore, the magnitude of the spin of each
atom has a definite integral or half-integral value, S, and thus, each atomic magnetic moment should be an integral multi-
ple of the Bohr magneton. However, experimental values of the intrinsic magnetization extrapolated to absolute zero,
i.e. experimental values of M0, give for the atomic magnetic moments, Fe:2.2p; Ni: 0.6p; Co:1.7p. The deviations of these
magnetic moments from integral rnultiples of P is due, presumably, to the interchange of electrons between the atomic 3d
shells, where the electrons contribute to the ferromagnetism, and the conduction states, where they do not. The problem
of the extension of the exchange interaction model to include these interchanges has not yet been solved.
"See reference 4, Ch. 12.
" Magnetic quadrupole interactions have been invoked to explain ferromagnetic anisotropy, cf. R. Becker, Theoric der
Electrizitat, Vol. II (Teubner, Leipzig, 1933) pp. 177—183; in order that these, alone, account for the observed ansiotropy
their ratio to the dipole interactions need only be =1/10. In this connection it. should further be mentioned that the
use of magnetic quadrupole interactions to explain ferromagnetic anisotropy has been &r&t;it;&zpQ by Van Vleck, Phys. Rev.
52, 1178 (1937), p. 1188.
1&00 T. HOLSTEIN AND H. PRI MAKOFF

locations of magnetic dipoles, each with moment 2PS. The last term is the interaction of the magnetic
moment of each atom with the external magnetic field.
It is to be noted that spin orbit eff'ects have been neglected in Eq. (1). How these effects are to
be treated and what influence they have on the final result will be discussed in a later section.

III. EIGENvALUEs oF THE HAMILToNIAN

The first step in finding the magnetization of the eigenvalues, E of H. In
is the determination
conformance with the essential approximation of "quasi-saturation, LMs M(T, J— l) $/Ms«1 "
mentioned in the introduction, only those eigenvalues, E, are sought whose corresponding eigen-
functions, +E, specify states where the expectation value of the s component of the total spin of the
specimen
N
S( z)
L=l

is close to its maximum possible value NS. "

To proceed, it is convenient to introduce the operators:
S+i=S" +iS'"'i, S i=S( 'i —iS("'i, gi=S —S')i.
i, (2)
n~ the eigenvalue of n~, will be called the "spin deviation" of the 1th atom; for the state
C tt1, ', St),

which is an eigenstate of H& and S('&, n& obviously represents the difference between the s component
of the spin of the lth atom and its maximum value. Also, by way of notation (tt&)z is the expectation
value of the spin-deviation operator, n~, averaged over the eigenstate

bz(nt, , nt, ng)%e, , ",s), "ss,

i.e. ,
(tt[)z = Q ~bz(nt ''' n( ''' npT)~ n[,
whereas,
—
((ti, ))» = Pz(tt, )ze
—«"r/PzS —«»

is the expectation value of the spin-deviation operator when the temperature of the specimen is T,
and involves, first an average over +E, and then an average over the Boltzmann distribution of the
eigenstates of the specimen.
The operators of (2) have the following properties,
S+t%si (2S) &'(1—
—(n~ 1)/2S)—
&(n&)14« —t,

S t+«= (2S)I(nt+1)*'(1 '4's~+»

n~/2S)— tl~@'s~=nt4s~.

Introducing the well-known creation and destruction operators defined by"

a*~4s& —(nt+1) &Os(+1 at@I~ —(nt) &@a~—t, (4)
one obtains, upon comparing (3) and (4)
S+& —(2S) &(1 a*ta&/2S—) "ar&r, S —(2S)'*a*&(1—ac&a&/2S) ',
& n& = a*&a&.
N
n It is to be noted that QS" ~ does not commute with the magnetic interaction portion of the Hamiltonian (I).
" 1

In Eq. (4), nI is allowed to run from 0 to ~ rather than from 0 to 2S as in Eq. (3).. The discrepancy is only apparent,
since the transition from states with n~ 2S to states with nI)2S will never occur. e.g.
S )+2g = (2S)&(2S+1)&(1—2S/2S)+2g+1=0.
 FIELD DEPENDENCE OF MAGNETIZATION 1ioi
When substituted into the Hamiltonian of Eq. (1), (2) and (5) give:
H = —P J~ (2$a*~(1 —a*&a~/2$)'*(1 —a* a /2$)&a„+5' —2$a*~a~+a~~a~a* a„)
l, na

+ s l,Q (4P'/R'~~) (2$a*~(1 —a*ga~/2$) —a* a„/2S) &a +S' —2$a*~a~+a*~a~a~„a„)

&(1
m

+s 2 (4P'/W-)( a*«i+a*««* a )]
([s'i-(5' 2$—
3)—

+[sg (S —a~ga~)(2$)la* (1 —a" a /2$)'*+s~ R~ (S—a*la~)(2$)&(1 —a* a /2$)&a„]

R&

+(2S/4) [(R~ )'a*t(1 —a*~a~/2$) &a*„(1—a*„a /2S) &+(R~~)'(1 —a*&a~/2$)'

Xa~(1 a* a —
/2$)la„+2R&„R~„a*~(1 a*~—
a~/2$)&(1 —a* a /25)&a ])
N
—P 2PH(S a*(a)),— (6)
+
with Rim lxm+Q'!m y Rlm x!~n &elm

The condition of quasi-saturation

1» 2 [Mo M(T, H) ]/Mo= ((ni))av/2$= ((a*tat))A, /2$
is now invoked to effect the following approximations in H.
I. Replacement of (1 —a&*a&/2$)'* by 1. Such a replacement appears reasonable since the expecta-
tion value of (1 — a*«&/2$)'* is =(1 —((n&))A~/2$)'=1.
II. Neglect of terms proportional to a*~a~a* a =H~H . Assuming that there is no correlation in
the location of the different spin deviations, one obtains for the expectation value of these terms,
—
((tt~n„))» ((n~))Ay((n~))A„which is smaller than the expectation value of 2$a*~a&=25((n&))A„by a
factor ((n ))„„/2S«1.
III. Neglect of terms proportional to (2S) &a*««* = (2S) &n~a* . These are terms which cause the
system to make transitions between states of different total spin. Unlike terms of the type 2$a*&a*
which also cause such transitions, they are different from zero only for transitions taking place near
atoms on which spin deviations are already present; the ratio of the number of transitions arising
from the two types of terms is thus =((n&))A„(2$) &«1.
A further discussion of the nature of the approximations I, II, III, is given in Appendix I. In
anticipation of results to be obtained below (cf. Eq. (15 ) and following text), it may be pointed out
that, if the magnetic dipole-dipole interactions are omitted, these approximations lead to the same
energy levels as obtained by Bloch in his derivation of the T& law, ' and are thus equivalent to the
approximations of his method.
An additional simplification of the Hamiltonian results from the fact that summations of the form 4
Qg„f(R( )x, t, s( a*„=P a*„graf(Rg)xjsg
are zero. This fact is obvious if the direction of H, i.e. , the s axis, coincides with one of the crystal-
lographic cubical axes. In the more general case, a transformation of the sum over h to Cartesian
coordinates which are referred to the cubical axes readily leads to the same result.
Applying approximations I, I I, III, and the theorem just stated, one obtains for the Hamiltonian (6)
H =C P~, „2SJ~„(a*~a —a*~a~) +-', P ~, „(4—
P'/R'~„) (2S) (a~~a„—a*~a~)
+-', Q&, (4P'/R', „)( 3)(2$)(-', [x'&„+y'—]a*&a &
s'& a*«&+ 4[(R&„—
)'a*la*„+(R&„)'a&a ])
+ g)2PHa*(a(, (7)
with C= —Qt, „J(„$' 2PSNH ', Q(2PS—I Q„( S—)/R'—
2P— i„(1 3s'(~/R'—
l„) I.
"f(RI ) is any function of RI and Rz —
=R& —R . The two sums areidentical provided that contributions coming from
atoms on the surface of the specimen are neglected; the justification of this neglect is given in the text before Eq. (11).
ii02 T. HOLSTEIN AND H. PRIM AKOFF

The numerical constant C is the value of the energy when all of the atomic magnets point in the
direction of the field H. The first sum in C is the exchange energy, the second the interaction between
the atomic magnets and the external field, and the last the mutual dipole-dipole interaction of the
atomic magnets. (In fact, the expression in the curly brackets is the sum of the Lorentz local-field,
4m Mo/3, and the demagnetizing field, as will be shown in another connection below. Cf. text after
Eqs. (44), (45) in Appendix II.
From the form of the Hamiltonian (7), it is apparent that the "spin deviations, specified by the "
integers n& are not localized on any one atom, but are "propagated" through the crystal. That this
propagation is essentially of a wave-like character is seen by the introduction of new variables defined
by the following relations:
ag=N l Q( exp (iK„R))a), a( N l —exp ( —iKg
P—g R()ag,

a*g=N ~
Q( exp ( —iKg R()a), a*, =N l Pg ex—
p (iK), R()a*a.

The a~ and u*„satisfy the relation:

since from Eq. (4),

~l~ m + 0/C
m+l ~ml (10)
In Eq. (8), R& is the vector from an arbitrary origin to the lth atom, whose magnitude measures
the corresponding distance in units of the lattice constant, in contrast to the formulae of the above
text where {R&~ gives distance in centimeters. Kq is a reduced wave-vector; the usual periodicity
conditions require its components to take the values

K &*&g = 2n. X,/G„K &»g = 2s.X„/G„, K&'), =2vrX, /G„

where ), ),
X„, assume any integral values between —~G and -', G, —1, —-', G„and -', G„—1, —-', G,
and ~G, —1, respectively. '~
The replacement of the a& by the a), constitutes the first step in the evaluation of the eigenvalues
of the Hamiltonian. To carry out this replacement, one has to evaluate sums of the type,

„f(R(„)a,*(a
Upon application of (10), this sum becomes

N 'f(R( )a*pa&exp {i(K), Rp —Kz R„) }.

l, m, X, X'

Introducing the vector RI, =R~ —R =R~ one obtains

N 'f(R~)a*q a&, exp {i(Kq —Kq) R~) } exp {iKq Rq }.
l, h, X, X'

Now, the summations over l and h can be carried out independently if one neglects contributions
arising from the surface of the specimen. Such contributions are obviously negligible for the exchange
forces. In this case, the summation over h comprises only nearest neighbors of l, and hence surface
terms arise only if the atom l is, itself, on the surface. However, the number of such terms is smaller
than the total number of terms by a factor —
1/G. As far as the magnetic forces are concerned,
although their short range character is not immediately obvious, one can show that, in the sum over
h, again only small values of { Rz { are important; hence the argument given just above again applies.
The summation over l then yields the factor Nb&. ), and the quadruple sum reduces to
P~(g~f(R~) exp {iK&, R~})a*~a~.

"G„G„,G, are the lengths of the specimen in the x, y, z, directions, divided by the lattice spacing.
 FIELD DEPENDENCE OF MAGNETIZATION ii03

Treating all of the summations in H by this method, one obtains:

a„a „+2B &a „a

H=C+Q„A&a „a„+P„(2B, ~),
where
Aq —3P Pq( —2PS/a'R'q)(1 —3s'q/R'q)+P Pq(2PS/a R'q)(1—3s'q/R'q)(1 —exp (iKq Rq)) ~

+Pl, 2SJ~(R~)(1 —exp (iKq Ry, ))+2PH. (12)

B~ = —3P P~(2PS/a'R'~) (x'~ y'~ — a) /R'~
2i~~y—

+3P Pq(2PS/a'R'q) ((x'q y'q—2ix—

qyh)/R'~) (1 —exp (iKq R~)), (13)
a being the lattice distance.
The sums over b in Aq and Bq are evaluated in Appendix II; the results for i K&, &&1
~
are:
Ay=A —2SJK),'+2PH+47rPM,
g sin2 8&, (14)
Bg nPMO —
—
Bg 4— sin'. eye '"&& (15)
J—
Here, = J~(R~) when RA, is the distance between nearest neighbors; eq, @q are polar angles of Kq
with polar axis parallel to the field, H. As will be shown later in the text, the values of Aq and Bq
which contribute importantly to the magnetization M are those with K&, «1. i i

It might be instructive to point out that, if the magnetic interactions are omitted, H reduces to
' —2PSXH+P&, (Q~J~2S(1 —exp (iKq Rq))+2PH)a*qaq,
NP&JzS— (15')

since the eigenvalues, nq, of nq —=a*qaq are 0, 1, 2, 3, Lcf. Eq. (9)], it is seen that the eigenvalues
of this Hamiltonian are just the energy values which have been found by Bloch and Moiler. ' In this
connection, it is also apparent that n), can be interpreted as the number of "spin-wave quanta"
associated with the wave vector K&, . Further, Pq((nz))«which is equal to Pl((n&))«, gives directly the
expectation value of the deviation from its maximum value of the z component of the total spin of
the specimen.
However, the existence of the magnetic interactions, in particular the terms of (11) in aqa q and
a*),a* ), which do not commute with Itq, necessitates further transformation before the Hamiltonian
is brought to diagonal form. These transformations are, in order:

ag
—2 le'&&(b), +b g); a g —2 'e'& &(b), bg)— — (16)
and similarly for a*&, a* These transformations are defined only for the half-space of K&, i.e. ,
—~(K(&&«, —«K(», «, 0(K(&
&.
«.
ill+ ~2& X ~—X ~1& —'A i2&
(17)
= lac g+l2c&i',
g 0 y = lac —x 12c
with
(1A), +(A'g —~B&, ~')li l (1 A~ —(A'&, —~B~i')'*i '
(18)
E2 (A'„—[B„[')l ) (2 (A'z —iB) i')l )
In terms of cq, c*q, the Hamiltonian (11), becomes:
H = C+Q~((A'~ —iB~i')'C*~C~+l(A'), —iB~i')' —2'A)). (19)
In (19) the sum over X goes over the whole of K~ space, as in (11).
The eigenvalues, E, of H are now immediately available since, by (9), (16), (17), the eigenvalues,
Nq of C*&,C&, are 0, 1, 2, 3, . Thus
= EN& —C+ Pz(2 (A 'z —Bz ') —gA) ) + Zx(A'x —B), ') 'Nx.
E— i i
'*
~ ~
(20)
 T. HOLSTEIN AND H. PRI MAKOFF

IV. CALCULATION OF THE MAGNETIZATION) M(T, H)

The magnetization is obtained from the partition function, Z, by the relation,

(21)
with
Z=gme s" =e c'" exp [—Qi-'((A'i —IBi, !')» —Ai)/kT7+N„exp [—Pi(A'i, — IB&, I')»Ni/kT7

=s ""'exp [—2 l((~' —IB I')' —~ )/kT7 II (1 —exp [(~' —IB I')'/kT7) '. (22)
Thus by (21), (22), and replacing graf(Kq) by G, G„G,(2ir) P
f
f(K)dK, one obtains
2p5N G.G„G.2p I p A(K)
( )= " ! dK
(2~)'V - ». ((~(K))' —IB(K) I')*'& «xp [((~(K))'—IB(K) I')'/kT7 —I)-
G, G„G,P A (K)
p —1 dK= Mp 3f—
r(T, —
H) . (23)
Mp(H)—
(2-)'V ~ -((&(K))'- IB(K) I')'
3IIO is the value of the magnetization when all of the spins are parallel to each other complete —
saturation. M~ is the deviation of M from Mo due to temperature agitation; its magnitude, however,
is also dependent on II
and the magnetic dipole-dipole interaction. Finally, 3fp is the deviation of
3f from Mo due to the dipole-dipole interaction, itself; the magnitude of 2IIIp is, in addition, a function
of H. The presence of the term Mp indicates that, even at T=O, comP/eke saturation can be attained
only by the application of a 6eld H&&4xMO.
The T law of Bloch is obtained from (23) by neglecting the magnetic interactions and by setting
H=O. Then, from (14) and (15), A(K) =A( —K) =25JK'; B(K) =B(—K) =0 and

3II(T)sioo"=imp cVqsioo" —Mp —

—G,G„G,2—
—P(2') 'V ' ~(exp [25JK'/kT7 1) 'dK
J
= ~p(1 —[~ 'pG G„Gg V '2P(2pr) —'(k/255)»(2ir) (2)(1.3) 7T»)
= Mp(1 —(const. ) T»). (24)
It is to be noted that in (24) the integration is extended over all K-space rather than over a cube
of side 2m. , and the exchange energy Q&25J&(Rq)(1 — exp [pK Rq7) is approximated by 257K'.
This procedure is permissible provided that k T/25J«1, since in this case the main contributions to
the integral come from regions of K-space for which K (kT/257)». iP I I

Turning now to the evaluation of the integral for cVr in (23), one proceeds most conveniently by
finding the difference between Mr and the known integral for Mr
"'" in (24). Thus,

~&sloch—
G.G„G, 2P q f
A l( 1

(2pr)' U" ((l4' —IBI')»)».exp [(A' —IBI')»/kT7 —1)

dK (25)
exp [252'K'/kT7 —1
with A and B satisfying relations (14) and (15), vis

A(K) =255K'+4irPMp sin' Hx+2PH, IB(K) I

=4prPMp sin' 8x.

'~ The condition kT/253«j. is, in practice, not as well fulQled as is theoretically desirable, e.g. for iron at room tem-
perature k T/253=0. 3.
 FIELD DEPENDENCE OF MAGNETIZATION
The important contributions to the integrand of (25) come from regions of K-space for which
~K( [(4sPMO+2PH)/25J]'. Further, in all practical cases, (4~PMO+2PH)/kT 2X— 10 '. Thus,
in the regions of K-space making important contributions to (25), both (A' —~8~')'* and 25JK'
are small compared to k'1. It is then permitted to expand the exponential in the integrand. Hence

G G„G. 2P ~
A 1
3f& —M&»«h=k 1 t

(26}
v (2~)3 ~

From this point on, the integration is straightforward and yields:

1 (kT q &2P5
Mr &»och=
M— —G,G„G, — (2~)(2)(1.3)
V 5 25J) (2s)'
~

I
i

'](
3~ (2pHq ~ ~21 (p q'*H+4~MO 4~MD
sin . (27)
8(1.3) ( kT ) 8(1.3) &kT) (4wMo)& EH+4mMO)
/

As regards Ms(H), it has not been found possible to evaluate the integral for it in a closed form for
all values of II. However, in the two limits, II«4x3IIO and II&)4m Mo, the integral has been evaluated.
One obtains:
G.*G„G.
" (4~PM, q ——'(25Jy '*

iu, (H) = *Pi— if Il»4~m„

V & 2SJ ) &2PH)

G.G„G. (4~PM, y
—P( —'( 25J—),
**-

p
ic&(H)= f H«4 M, .
V & 25J )
) (
44' pMO)
An estimate of the relative importance of the terms Ms(H) and Mr(T, H) is obtained by studying
the change of these two quantities when H varies from zero to, say, 4~PM0. Then

G.G„G. ( kT q ' (4~PM, y -'*

SMr = Mr(Z', 4~PM, ) Mr(Z', O) =- — P(

V &25J) 1
kz )

aM p = M~(4~PM, ) Ms(0) =
"
G, G„G,
—P( ( 25J y1(4~pMoq'
v «pM) &2sJ)
DMs/AMr 4m PMo/k T. —

This ratio is negligibly small (5X10 ' for iron, 1.5X10 ' for nickel); hence, Ms shall be omitted
completely in what follows.
Thus, from (23), (24}, and (27):

M(T, H) =M,
G,G„G, ( )
"(2Ps)- i—
1 kT l (2m)(2)(1.3} ( 3s (2PH) &

V 5 &25J) (2w)' & 8(1.3) I kT )

(8~PM, q II+4~M& 4~350

'( (
*'

sm (29)
8(1.3) ( kT ) 4sM0 (H+4sM())
f

) f
ii06 T. HOLSTEIN AND H. P RI MAKOFF

The quantity most often found in the experiments is the "intrinsic susceptibility, " BM/BH. One
obtains from (29),

BM G, G„G. kT ) )(2)(1.3)
(2P')- (
1 & (2m. 1
]
BH U S E2SJ) (2p)'

1 (4pr~Mpl *(( oMol I+»n

'
.
'I (
4oMo
16(1.3)2* E kT ) 0 E II i &H+4nMp) .)

Up to the present time, it has not proved feasible to calculate in terms of atomic constants; in J
practice its numerical value is obtained from an experimental measurement of Mp —M(T, 0). This
latter quantity may be equated to Mr '"" since the other contribution to Mo —M(T, 0), namely
Mr(T, 0) —Mr "'" and Mp, is relatively small. Thus from (30) and (24), one finally obtains:

BM (Mo M(T, 0)) —

( l 1 (47rPMol *
( (4pMol *
( 4sMo
+sin ' . (31)
BH ( Mo ) ((16)(2l)(1.3)] 4 kT ) E ( H ] ~

EH+4mM'p) )
The application of this result to the experiments is considered in Section VI.
It is instructive to compare the above result for BM/BH with what would be obtained if the
magnetic interactions were not treated quantum-mechanically, but classically by means of the
Lorentz local field. The result of such a procedure can be obtained directly from (30) by
(1) Passing to the limit Mp~0.
(2) Replacing H by H+pM where y is a numerical factor =4o./3.
The constant J can then be eliminated as above, and one obtains

(BM) (M, M(T, O)q ( —1 q (4~PMp) '*( 4oMp q

'*

(32)
& BH) L„„ t, . ( Mp 3 E(8)(1.3)(21)) E kT '
) EII+yMp)

The important differences between (BM/BII)L„,„„and BM/BH of (31) occur for H((47rMp. In
t»s case (&M/&H)I, g predicts a field-independent susceptibility, while (31) has an inverse square-
root dependence on H. On the other hand for H»4xMo, the two expressions become identical; both
then vary with H as H '. The inverse square-root dependence of the susceptibility on the magnetic
field for H»4~Ho is thus seen to be a general feature of the exchange interaction model subject to
approximations I, II, III, quite independent of the details of the treatment of the magnetic inter-
action.
It should finally be noted from (30) that the susceptibility is proportional to the absolute
temperature.

V. EFFEcTs QF SPIN-ORBIT INTERAcTIoNs

As was stated at the end of Section II, a11 spin-orbit effects have thus far been neglected in the
fo rmulation of the fundamental Hamiltonian (1). If one desires to treat these effects within the
framework of the present development, i.e. , supplementing the Hamiltonian (1) by additional terms,
he first question which arises is whether spin-orbit effects can be described by an equivalent inter-
action energy in the space of the atomic spin variables. This question has been considered by Van
Vleck in connection with the problem of ferromagnetic anisotropy. In Van Vleck's work the spin- "
orbit effects are represented by equivalent "dipole-dipole" and "quadrupole-quadrupole" interactions
 FI EL D DEPE N DENCE OF MAGNETI ZAT I ON 1107

of the type'.
—2
, Q( „C(„(R)„)[S(S„—
—'
3R(„S( Rg„S„R(„], (33)
2+i, yi (Ri )Rt (St Ri )'(S Rt )' (34)

These two terms are discussed in order.

(1) Conveniently, the equivalent "dipole-dipole" interaction (42) is just the same as the magnetic
interaction provided that 4P /R &„ is replaced by C~„(R& ). The effect of this dipole-dipole interaction
then merely consists of additions DA&, AB& to the coefficients A& which appear in the Hamiltonian
(19), and therefore in the integral (23) for M(T, H). One has: (cf. the first two sums in Eq. (12) for
Az and Eq. (13) for B&,)

hA&, = PI, I( —3$/2)C(Rh)(1 —3z'q/R2@)+(S/2)C(Rq)(1 —3z'q/R'q)(1 —exp (fKq Rl)) I, (35)

AB& —P z I ( —3S/2) C(R z) ((x'& —y'z —2ixzy &) /R'z) exp (fK& Rq) I . (36)

It is also reasonable to suppose that C(Ry) is of short range character;" in this case the sums in
(35) and (36) have appreciable contributions only from the nearest neighbors of a given atom.
Taking account of the crystalline cubical symmetry of the specimen, one obtains:

AA~ —g~(S/2) C(1 —3z'I, /R'-~) (1 —exp (iK~ R~)),

ABER = Pz(3S/2) C((xh, ' —yz' —2ix&y&, ) /R'I) (Kz Rl)'+terms in K'q, K'z,

with —C(Rq) for nearest

C= neighbors, l™~10 wave-numbers —J/100.
Equations (35), (36) and the above numerical estimate for C insure that the equivalent "dipole-
dipole" interactions have no effect whatever on the magnetization. As far as the A), +AA~ coefficient
is concerned, the AAz term: Pz(S/2) C(1 — 3Z'&/R'&)(1 — exp (iKz Rz)) will be completely swamped
by the exchange term in Aq. +~2SJ(1 — exp (iKq Rq)). On the other hand, the B&, +AB&, coefficient
—
is altogether important only when it is A&, +DAz, i.e. , only when 4mPMO=Q&2SJ(1 — exp (iK& Rz))
— —
=2SJK'q. Under these circumstances, hB&, SCK'q SC4~PMO/2SJ&&4~PMO, and thus, 6B&,&&Bq,
for the important jB&,.
(2) Concerning the quadrupole-quadrupole interaction, an examination of its diagonal matrix ele-
ment in the representation where the Hamiltonian of Eq. (19) is diagonal indicates that its effect, to the
first order in y, is given by the addition to A& of a constant term —
y. This term may be conveniently
described by a fictitious "magnetic field": H, = —y/2P=anistropy constant/Mo=200 gauss (Fe),
100 gauss (Ni). "b It can then be coupled together with the original 2PH term in Aq in the form
2P(H+H, ) and carried through to the end of the evaluation of M(T, H), without further ado.
Thus, in the expressions for M and BM/BH in Eqs. (30), (31), the term in y has but little effect if H
is, say, greater than 1000 guass.
(3) Finally, it is possible that some portion of the spin-orbit effects is incapable of description by
interactions of the type (33), (34). Until explicit expressions are presented, one cannot, of course,
estimate the resultant corrections. It is to be hoped, however, that these corrections will still be
described by means of a fictitious field, II„whose order of magnitude will be the same as in the above
numerical estimates. ' '

""aVan Vleck, reference 11, p. 1193.

This numerical estimate for C is due to Van Vleck, reference 11, p. 1184.
For experimental values of the anisotropy constant see Becker and Doring reference 3, p. 123, Table 12.
'" It may be remarked in passing that the methods of the present paper offer an approach to the problem of ferro-
magnetic anisotropy at low temperatures. For this purpose the eigenvalues EN& of Eq. (20), with B~ replaced by Bp+bBp
must be determined as functions of the direction of M0 with respect to the crystallographic axes. This calculation and its
relation to other treatments of ferromagnetic anisotropy I Van Vleck, reference 11; Van Peype, Physica 5, 465 (1938) is
now being considered.
j
ii08 T. HOLSTEIN AND H. PRI MAKOFF

VI. COMPARISON WITH EXPERIMENT factor of about ten;" this factor is due essen-
tially to the appearance in Eq. (39) of the quan-
(1) Numerical estimates of theoretical values for
tity 4irPM0/k T, which is «1, whereas in Eq. (31),
the susceptibility
there is instead the quantity (4irPMo/kT)*'.
Equation (31) for the susceptibility BM/BH, Further, Akulov's susceptibility is independent
when applied to iron and nickel at T=287'K of H and is proportional to e *~"r/T, while the
and H=4000 gauss, gives: susceptibility of Eq. (31), as has already been
noted at the end of Section IV, is proportional
(BM/BH) i.= 1.7 X 10—', (37)
to 1II ', for a large range of fields.
(BM/BH)N; =1.2X10 4, (38)
taking" (2) Discussion of the various experiments
Information concerning the variation of the
(M 0 M(T, —
0))!3IIO]F —0.018, intrinsic magnetization with II, has been ob-
(41rMO) F = 21,800; tained from experiments" on polycrystalline
samples of nickel and iron. In these experiments
(Mo —M(T, 0))/Mo]N; —0.040,
it has been customary to describe the variation
(4w Mp) N; —6, 400. of the observed magnetization with II by a
formula of the type:
There exists no experimental data for cobalt
for comparison with theory. (BM/BH) b =A/Ii'+B/II3+C, (42)
These numerical results for BM/BH, are to where A, B, C are supposed to be constants.
be compared with those of Akulov, which are The constants A and B depend upon the metal-
based on the phenomenological Weiss-Heisenberg
theory. In this theory, "
for atoms with 5=-'„
lurgical history of the polycrystal1ine specimen;
A is conditioned by the plastic deformation of
M(T, H) = Mo tanh [(pIZ+ prJM) /k T], the material, " whereas B is determined by the
crystalline properties and elastic state. The "
g=-', sJ/PMO' , whence, for low T, Akulov's results physical significance of the constant A is at
may be put in the form: present a matter of speculation; the order of
BM IMo —M(T, 0)) 1 4irPMp magnitude and dependence on temperature and
(39) elastic condition, of the constant B, as well as
- ~II - A k u1 ov 3fp 2' kT the field variation of the term B/H', shows that
8 originates from the ferromagnetic anisotropy
The numerical values for iron and nickel given
by (39) are found from the experimentally ob-
of the component crystal grains of the specimen. "
The latter observation is true whether the
served values of [Mo M(T, 0)]/M'0. One has:
anisotropy is a consequence of the natural
BM/BH]F, = 1.5 X10 ', (40) crystalline properties, or is induced by an ex-
ternal stress. Finally, the constant C has been
&M/BH]N; =1.2X10 ' (41)
" Equation (39) and numerical values (40), (41),
Thus Akulov's susceptibility is numerically represent the maximum estimates which may be obtained
for BM/BII from the Weiss-Heisenberg phenomenological
smaller than the one derived in this paper by a theory. Other estimates obtained by: (1) Use of theoretical
value for (M0 — M(T, O))/M0, i.e., 2e '~~~~. (2) Use of
'8 The values of M0 for Fe and Ni are obtained from Becker Langevin function appropriate to S) e.g. to S= ~
—classical Weiss theory, give consistently&, smaller
and Doring, p. 27, Table 5. At T = 287'K, iron still obeys the results.
T& law while nickel already shows some deviations. Under "P. Weiss and R. Forrer, Ann. de physique 10, 153
these circumstances one must take for L(M0 —M(T, O))/ (1926); 12, 279 (1929). E. Czerlinsky, Ann. d. Physik 13,
M0]» in Eq. (31), not the experimentally observed value, 89 (1932). A. R. Kaufmann, Phys. Rev. 55, 1142, 1939
0.054, but the value obtained by extrapolation of the T& law, and private communication. H. Polley, Ann. d. Physik
the constant 2SJ in it being determined from low temper- 30, 625 (1939),
atures. The resulting value for $(M0 —M(T, O))/M0jN1 is "A. R. Kaufmann, Phys. Rev. 51, 1089 (1939).
0.040. See the experimental work of Weiss and Forrer, and "The theory of the term 8/III and of the constant 8
Fallot as quoted, e.g. in R. H. Fowler Statistical Mechanics has been given by Akulov, reference 3; the experimental
(Cambridge University Press, 1936), p. 500. verification by Kaufmann, Czerlinsky, and Polley, refer-
'9 Cf. Reference 4. is the internal field constant and z
q ence 21. See also, Becker and Doring, reference 3, pp.
the number of nearest neighbors. 167-176.
 FIELD DEPENDENCE OF MAGNETIZATION 1109

observed to be independent of the metallurgical times larger than the valueof Cderived by Akulov
treatment " Lcf. Eq. (41)]. Other values of C have been
The independence of C from metallurgical obtained by Kaufmann;" these are C=1.0X10 '
treatment immediately suggests that it arises and C= 0.7 X 10 4.
from the variation of the intrinsic domain mag- For iron there are available the results of
netization with field. C is thus to be compared Kaufmann" and Czerlinsky" Kaufmann ob-
,

with expression (31) for BM/BH derived in this tained C=3.8X10—' and 4.8X10 ', while Czer-
paper, and with the expression (39) for BM/BII linsky found C=4.4X10 4. The average of these
derived by Akulov. results'4 is about two and a half times the
(a) Field dependence of C=BM/BH]; ~„„. theoretical value found in this paper [cf. Eq.
Unfortunately, all the experiments" except those (37)] and more than twenty-five times Akulov's
of Weiss and Forrer have been carried out in theoretical value $cf. Eq. (40)].
such a range. of fields that, for most of the range, (c) Temperature dependence of C. The ex- —
the A/H' and B/IP terms both predominate pression (30) for BM/BH predicts a linear vari-
over C. A typical example is the work of Polley, " ation of C with temperature. This is experi-
where the range of fields in which C is ~A/H' mentally verified by Polley" in the temperature
+B/H' is from 3000-4000 gauss (cf. p. 641 of range 250'K-320'K '
Polley's paper: Fig. 10). Under these conditions
a weak dependence of C on H such as H ' could (3) Further possible experiments
never be observed. All that can be obtained A great complication in the experiments so far
from these experiments, therefore, is the average performed arises from the presence of the terms
numerical value of C over a field range of about A/H' and I3/H', which are due to the poly-
2000-5000 gauss. crystalline nature of the specimen. It would
The only experiments for which the deter- therefore be desirable to obtain experimental
mination of the field dependence of C is possible data with single crystals and with II in the
"
are those of Weiss and Forrer. In these experi- direction of the various axes of symmetry in the
ments the magnetization as a function of H was crystal. These directions may be either the direc-
determined in a range of fields up to 20, 000 tions of "easy" or of "difficult" magnetization.
gauss. From 5000 to 20, 000 gauss C is the only In the first case, technical saturation is achieved
term of importance; it was found to be inde- for H~50 gauss;" in the second case, technical
pendent of H. However, the slope of Weiss' BID —
saturation isachieved for FI~3H, 600gauss (Fe),
es. H curves, i.e. , C, is so small in absolute mag- , 300 gauss (Ni). "Any furtherobserved variation of
nitude that it is dificult to decide whether this M with H, beyond its technical saturation value,
slope is actually a constant independent of IX. is then to be ascribed to changes in the intrinsic
In this connection, it should also be pointed out magnetization. Thus, using single crystals, one
that Weiss' results have been criticized by other may obtain, directly from the BM/BH vs. FI
authors — particularly Czerlinsky;" vis. , Weiss curves, the various features of theoretical interest.
measured directly 3f as a function of H, with the (a) Functional dePendence of BM/BH on H,
result that small errors in the measurement of mitk H))4m. MO.' Test of the H & dependence. '
M were capable of seriously affecting the deter- " Dr. Kaufmann, in a private communication, has
mination of AM/hH; on the other hand, all the stated that there exists a large experimental error (ca.
100 percent) in his determination of C.
other experimenters measured 2 M/AH directly. "At higher temperatures, deviations from the linear
The relative inaccuracy of Weiss' procedure is variation of BM/BH with T are to be expected, and have
been found by Polley, reference 21. These deviations
indicated by the scattering of his observed values correspond to departures from the T& law in the same
.

of C, i.e. , from 0.72X10 ' to 1.2X10 '. temperature range.

(b) Magnitude —
of C. The most consistent
'6 See Becker and Doring, reference 3, p. 102, Fig. 61;
p. 118, Fig. 71.
values of C for Ni have been obtained by Polley. " ~' Becker and Doring, reference 3, p. 102, Fig. 61;
p. 118, Fig. 71; p. 124, Fig. 77.
For T = 287'K and H = 4000 gauss, Polley finds C "To determine experimentally the variation of 8M/BII
to be 1.3 X 10 ', which is in excellent agreement with H, for H»4m. M0, one may also use polycrystalline
specimens, since for such high fields the terms 8/H' and
with Eq. (38) of this paper, but which is ten A/H' are negligible.
iiio T. HOLSTEI N AND H. PRI MAKOFF

(b) Variation of BM/BH with H for 3H (H what it would be in the vapor state, and that
—4x Mo. Test of effect of magnetic interaction the various orbital magnetic moments do not at
in Eq. (31). all influence each other, one obtains, with the
(c) Egect of spin orb-it interactions: With II usual Curie law:
parallel to the direction of "easy" magnetization,
BM/BH= (N/ V) (P'L(L+1)/3k T),
an investigation of the variation of BM/BFI with
H, for 50(H(3H, may be undertaken. There the following paramagnetic volume suscepti-
are then three possibilities: bilities: 3 X i0 ' for iron; 7 X i0 ' for nickel. The
(1) The spin-orbit eRects are entirely de- gyromagnetic experiments, on the other hand,
scribed by the equivalent "dipole-dipole" inter- indicate that:
action (33). In this case, the BM/BH vs. FI curves Either the orbital angular momentum of each
in this field range should be described by Eq. incomplete d shell is destroyed or quenched by
(31). the crystalline electric field, '"
in which case the
(2) An appreciable part of the spin-orbit corresponding susceptibility vanishes in first
effects is due to the equivalent "quadrupole- order;
quadrupole" interaction (34). The BM/BII vs. H Or, the orbital angular momentum vectors of
curves in this field range should now be given by
Eq. (31), with H replaced by H+II, . coupled. ""
the different atoms are "antiferromagnetically
Then an estimate of the suscepti-
(3) An appreciable part of the spin-orbit bility may be obtained by replacing kT in the
effects cannot be described by equivalent inter- Curie law above by kT+kT„where kT„ the
actions of the type (33), (34). The BM/BH ss. Ii interaction energy of the antiferromagnetic
curves in this field range may then show a more coupling, is — "
i4 ev. The resulting paramag-
radical departure from Eq. (31). netic volume susceptibility is thus cut down by
a factor of fifty, and becomes negligibly small.
(4) Inadequacy of other possible mechanisms to In conclusion, it should also be noted that
account for the observed variation of the
the smallness of any paramagnetic suscepti-
intrinsic magnetization with field
bility, described by the Curie-gneiss law, is
These mechanisms are: directly shown by the experimentally observed
(a) Ion-core diamagnetism of the atoms: re- temperature variation of the intrinsic mag-
sulting volume susceptibility, BM/BH is —
10 ', netization; viz , C = .BM/BH]; t,,;„„.= const. T
and is negligible. (see Section VI).
(b) Spin paramagnetism and orbital diamag- The authors wish to thank Dr. A. R. Kauf-
netism of the conduction electrons: resulting mann of the Massachusetts Institute of Tech-
volume susceptibility BM/BH, is —
10 ', and is
negligible " nology for helpful discussions of the experiments,
and for communication of experimental data
(c) Paramagnetism arising from the orbital before publication.
motions of the electrons in the incomplete
d shells. (The exchange coupling of the spins of APPENDI X I
these electrons gives rise to the ferromagnetism. ) The various approximations made at the
Precise estimates of the order of magnitude of this beginning of the treatment are of the following
paramagnetism are dificult since little is known type:
about the orbital states. Assuming that the
orbital moment, L, of the incomplete d shell is I Neglect . of a*~(1 —a*~a~/2S)l —a*~
in com-
"In making this estimate, it is assumed that the
parison with u*g.
II. Neglect of a*~a~a* a /2S= ngn~/2S i—n com-
conduction electrons are perfectly free. This assumption
is reasonable since the conduction electrons are valence parison with @*~a~= —n~.
electrons arising from the 4s atomic shells. The strong
paramagnetism, with volume susceptibility=5 X 10 ', III. Neglect of a* c a*~—=H c~~ in comparison
arising from. electrons in the incomplete inner shells of
some of the nonferromagnetic transition elements, e.g. Pd,
with @*~a* .
30' Van Vleck, reference 4, Ch. 11.
plays no role in ferromagnetic elements, since the incom-
plete inner shells in this case, are responsible for the " Van Vleck, reference 11, p. 1182.
ferromagnetism itself. "Van Vleck, reference 11, p. 1184.
 F IELD DEPENDENCE OF MAGNETIZATION

The neglected terms are important whenever as isolated independent units with no inter-
two or more spin deviations are in close proxi- actions.
mity, since all the neglected terms in I, II, III Now, spin deviations may come into close
are multiplied by short range functions of R& proximity and give rise to (A), (B), and (C), as
i.e. J~„(Rg~) or R 't„. When spin deviations are a result of two mechanisms, The first of these is
to be found on atoms close to each other, the temperature agitation, the second, the action of
following situations may arise: terms in the magnetic interaction of the form
(A) The system makes transitions from states R '~ a*~a in creating two spin deviations close
with n~~i to states with n~+1. Cf. I, i.e. , to each other.
In view of the lack of knowledge of the wave
[a*&(1—a*(a)/2S) i —a*(]No v,
functions of the exact Hamiltonian (6) or (1),
= (nt+1)'((1 S)* 1) vtvn—~+1=0,
n(/2— the approximate Hamiltonian (7) (which is the
exact Hamiltonian (6) or (1), subject to approxi-
unless n~~ i. mation I, II, III) will be used to estimate the
(B) The system occupies states with
n &0. Cf. II, i.e. ,
n& )
0, relative importance of the cases of close proxi-
mity of spin deviations.
Nm + ~tEm (1) Temperature agitation —
The . structure of
0 m~nm = 'kg~em the Hamiltonian (7), (without the part of the
2S 2S magnetic interaction proportional to c*~c* and
ata„) or better the Hamiltonian (11), (without
(C) The system makes transitions from states the terms in Bz and B*z) obtained from (7) by
with n )0, n) to states with n, n)+i. Cf. III, the Fourier transformation (8), indicates that
1.e. )
n a l@vvlvvvvv = n (nt+ 1) '*4'«y& vv
the position of each spin deviation is spatially
uncorrellated with the position of any of the
It is thus seen that I, II, III, imply that any other spin deviations. Thus cases of close
atom having a spin deviation can always be proximity of spin deviations due to temperature
regarded as surrounded by atoms with no spin agitation are relatively infrequent in the condi-
deviations, i.e. , the spin deviations are regarded tion of quasi-saturation.

To verify this lack of spatial correlation, one observes that

«n«-»" —
= (&a*««*-a-))"
=N ' Q exp Ii[(K„— K„) Rv+(K, —Kz) R ]}((a*„a„a*&a,))Av
Pv VvX)P

+N o g„,q exp Ii(K„—K&) Rq}((n„(nq+1)))A„(1—b„q).

=N og„, q((n„n&))„„—
The form of the partition function Z in Eq. (22) (with 8&, =0, and hence Nz = nz), which is involved
in averagingthe rt), gives:

((n„n&)) „=((n„))„((n,)),„(1—8„„)+ (((n„))A„+2((n„)) ') b„g.

A,

Hence,
((n&n ))A, —N 'g„, ~&(n„))A,((n-&))A, +N ' g„,~ exp Ii(K, —K~) Ra}((n,))Av((%))Av
Also
S[Mo —M(T, 0) ]/Mo = ((nt))av = N Qvvv((nvvv))Av = N Q„((nvv))Av.
Thus «n~n„))A, and ((nt))Av((n~))A„are both of the same order of magnitude, and hence, there are no
spatial correlations among the spin deviations. It follows that the probability for a spin deviation
to be found on atom I when another spin deviation is known to be on atom m, is independent of the
distance between atoms I and m, and is —
((n~n„))Av/((n~))Av=((nt))Av —
S[Mo —M(T, 0)]/Mo&&1 in
the condition of quasi-saturation.
iii2 T. HOLSTEIN AND H. PRI MAKOFF

(2) 3Eogneticinteractions proportional to a*ia*„. and the contributions to the sum for atoms
—The effect of these magnetic interactions is lying outside of this sphere replaced by con-
contained in the terms, gi, -', B*i,u'&, as —i„of the tributions to the corresponding integral, in
Hamiltonian (11). accordance with the prescription:
Now the B~ which make the greatest con-
tributions to M(T, H) have K&, =(4rrpMs/2S&)'
~ ~

[cf. text after Eq. (25)$. Also the main contribu- u ' Qs2PSf(Rs)~Ms ~f(R)dR.
tions to Bi„(cf. (13)), come from summands for
which Rs ~, the relative separations of the spin
~
Thus,
deviations, is 1/Ki. Thus the effective spatial
separation of the spin deviations created by the Zs( —2PS/it'R's) (1 —3s'a/R's)
magnetic interaction is —
(2SJ/4rrP3fs)& lattice
spacings —30 lattice spacings. However the —+( —~s) I [(1—3s'/R')/R'jdR, (44)
average spatial separation of the spin devia-
tions created by the temperature agitation is
=(IVs/[Ms M(T',— 0) j)' lattice spacings 4 — where the integral is extended over all of the
lattice spacings. Thus from the point of view of space outside the small sphere and inside the
causing cases of close proximity of spin devia- outer boundary of the specimen. Now by the
tions, the magnetic interaction is much less divergence theorem,
important than the temperature agitation. "
It should be emphasized that the above
estimates as to the effective separation of the ( —Ms) [(1 —3s'/R') /R']dR
spin deviations created both by temperature
agitation and by the magnetic interaction is
given. on the basis of the approximate Hamil- = ( —Ms) . (ns/R')dr
tonian (7). The final justification of the validity
of these estimates awaits a better knowledge of
the wave functions of the exact Hamiltonian (6)
or (1) than exists at present.

where, on the right-hand side, the first integral

AppENDrx II is extended over the surface of the small sphere,
The sums for Ai, and B&, in (12) and (13) will and the second integral over the outer boundary
now be evaluated. The contribution to the first of the specimen, n being the outer normal to the
sum in Aq, arising from near neighbors of a surfaces, The integral over the surface of the
given atom vanishes because of the cubical small sphere gives 4m Ms/3 and is thus just the
symmetry of the specimen. A small sphere may Lorentz local fieM. The second integral depends
now be drawn enclosing all these near neighbors, on the shape of the outer boundary of the
specimen and is just the demagnetizing field. One
~ The portion of the equivalent dipole-dipole interaction takes the specimen to be an ellipsoid whose
of the form C(R~ )a*~a* (cf. Section V) creates spin major axis is the s axis, and which is so elongated
deviations on atoms which are nearest neighbors, since C
is short range. Nevertheless, the effective spatial separation that the demagnetizing field may be neglected.
of the spin deviations created by the sum of the magnetic Then,
and equivalent dipole-dipole interactions, viz. by terms of the
type, Z)tq(B*y+AB*),)a*pa )„ is not appreciably different
from 30 iattice spacings, since for jK~~(4spMs/2SJl&, 3p Qs( —2pS/asRss)(1 —3s's/R's) =4rrpMs. (46)
the values of ~Ki, where Bi,+aBg as weii as Bg makes
~

its most important contribution to M(T, H), one has

ABy=SCKy'=(4m-PM0) (C/ J)&&4+PM0. Thus, the contri- The second sum in Aq may be replaced by an
bution of DBy to the term Bg+ABg is so small that the integral at once, since this sum has no singu-
effective spatial separation of the spin deviations remains
essentially unaltered. larity at RI, =0. Thus:
 FIELD DEPENDENCE OF MAGNETIZATION iii3
lt Q &(2PS/a'R'&)(1 —3z'&/R'&)(1 —exp (iK& R&))

~PMo~t ((1 —3s'/R')/R')(1 —exp (iK&, R))dR=iPMOK&*&&, (s/R')(exp (iK&, R))dR (47)

by an integration by parts.
The last integral is just equal to 4&riK"&/K'&„(12), (46), (47) then yield:
A&,
—A —4&rPMO
&,
sin' e&, +P&2SJ&,(R&)(1 —exp (iK&, R&))+2'. (48)
To evaluate B& one proceeds similarly. Considering the first sum in B~, one draws a small sphere
about R~ —0, enclosing all the near neighbors. The contributions to the sum from atoms within the
sphere is again zero because of cubical symmetry, while the contributions from atoms outside the
small sphere are calculated by replacing the sum with the corresponding volume integral. Thus,

—3P Q&(2PS/a'R'&)(x'-& y'&, 2ix— R'&~

&y&)/— [(x'
3PMO~~— y' — )/R']dR
2ixy—

=3PM&~t [(a, —ia„) n(x —iy)R ']dZ+3&8Mn~l [(a, —ia„) n(x R ']d'—, (49)
iy)—

where the first surface integral is extended over interactions, both in A), and Bq come from regions
the boundary of the small sphere, the second of K&,-space, where K&, ~
(4&rPMO/2SJ)-:&&1.
~

over the outer boundary of the specimen, and [Cf. text after Eq. (25). ]
a„a„are unit vectors in the x and y directions. The difference between the sums and integrals
Also the integral over the small sphere's surface becomes much more important for problems of
vanishes by symmetry. other types: e.g. , can ferromagnetism arise from
The second sum in B&, just like the second sum pure magnetic dipole dipole -interactions'"
in A& may be replaced at once by an integral, In this case J=O, and the use of (48), (51),
which when integrated by parts gives:
Aq —4&rPMO sin". tt&, +2PH;
—3PMO [(a, —ia„) n(x —iy)R ]dZ 8~=47I.350 sin' 8),e "4'",
J
+4&rPMO(K&*», —iK&»&, )'/¹&, (50) leads to a negative answer to the proposed
where the surface integral is extended over the question. It is to be expected, however, that the
outer boundary of the specimen. Thus from (13), exact expressions for Az and B& determined by
(49) (5o) evaluation of the original sums (12), (13), will
not be given by (48), (51), hence the existence
B&, =B &,
—
K&*»,
4&rpMO(— iK&»&)'—
/K'&, of ferromagnetism arising from magnetic dipole-
=4&rPMo sin' t&&e "~&. (51) dipole interactions cannot be determined from
the knowledge of A), and B~ available at this
I t should finally be stated that the replacement time. The evaluation of the sums for A), and Bq
of sums by integrals in A)„B),is an approximation is being considered at present.
with an error — (K&,)'. This introduces an error
~ This problem has been discussed by
into M(T, H) =4xPMo/2S J«1, since the greatest J. H. Van Vleck,
J. Chem. Phys. 5, 320 (1937), Section 5; J. A. Sauer,
contributions to M(T, H) from the magnetic Phys. Rev. 57, 142 (1940).