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INTRODUCTION 1
BIBLIOGRAPHY 63
ACKNOWLEDGEMENT 66
1
INTRODUCTION
in the periodic table. For the most part they have three electrons in
the valence shell or conduction band, and as the atomic number increases
the inner l|f shell is gradually filled up. The existence of an unfilled
magnetic coupling in Gd etc. In these metals the Ijf shell of each ion
because their magnetic shells have very little chance to overlap each
interacts with the l^f shell electrons of an ion through the electrostatic
Coulomb exchange effect. This tends to line up the spin of the conduction
electron travels in the crystal it also interacts with other ions and
thus gives rise to a force which tends to line up all the ions in the
The interaction between the conduction electrons and the l*f shell
Most of the rare earth metals have the hexagonal closed packed
revealed their very complicated magnetic structures when they are anti-
each basal plane are parallel and are perpendicular to the c axis. The
The angle between adjacent planes is about 38° at lt5° K and increases
being 132° K. Dysprosium, erbium and thulium may have similar structures
The present work consists of two parts. The first part contains a
regions is obtained.
h
The model for rare earth metals one usually employs consists of a
describes all members of the group except the following: cerium has
has been established that the electrons in this shell couple their
momenta of the electrons couple into L and the spin angular momenta
members of the group this effect is quite small compared with the
interaction between the l|f shell of an ion and the field is given by,
in the units of C = ^ = 1,
where e is the charge of an electron, r^, pj_ and Sj_ are the position,
momentum, and spin vectors of the i-th electron, and the summation is
H» = (|e|H/2m)(Lz + 2SZ)
= Lsii fx + J(J+i)-L(L+i)-ts(s+i)]
2m *- 2J( J+l) >
The quantity in the square bracket is called the Lande g-factor and is
spaced,
El
z * H • (i«)
>
Therefore, with H in z-directicm
6
F"* = - j s ( 1 » + 2 s , )
~ - H B SJz • (7)
M = )exp(-p(Jz)
1 Jz exp(-Of J2)
(8)
and B (a ) = J * V2 (9)
V
In many rare earth metals the spins of the ions are coupled
model for a ferromagnetic crystal is one -where the coupling between spins
Aij represents the exchange energy between the i-th and the j-th ions.
on the ions. For the i-th ion, the effective molecular field is
^ = iki
Is 413 Ti " tài
Alj <7> (n)
approximates
"*/ H B& •
X. = irrV" ™ = A ™ • (12)
rB GN
with
• (13)
crystal, the total effective field is the sum of the external field and
8
H = H 0 + H m = H 0 + ^ M . (Ill)
and temperature.
is given by
M = N gJB (15)
D kT *
*. = ^I Aid , (17)
between ions.
B (ex) = d/3 (J + 1) .
*= H = rrs (is)
•where
= •" W w ) (19)
X (x ) = cot x|
- . (20)
B X (41")
•where
antiferr csnagnetic interaction between them, one may write the effective
Ha = Ho + ^ ,
HB = Ho - a 'ÏA + a Mg . (22)
The applied field is assumed to be in line with M^, Mg. Therefore M^,
With no external field applied, one can find non-zero solutions for %,
Mg provided that the temperature is lower than T^, the Neel temperature,
given by
% = *^ ( 2 1 4 )
•where
forces are so strong that they are the only significant terms in the
one writes the total energy E as a sum of the interaction with the
applied field
Eh = -H * (% + Mg ) ,
6B.
The properties of the system depend on the relative sizes of the
Hs = l/2nM [ 1 - to- ] .
nl(2'
"When H becomes greater than Eg the system goes into the ferromagnetic
13
to 179° K.
neighboring JUf shells. Kasuya (1956a) was the first to point out that
(Zener, 1951; Zener and Heikes, 1953)» namely the indirect exchange
where a^creates an electron with momentum k and spin up, ak»| destroys
—»• -*> >
—
an electron with momentum kT and spin down etc; k',k are the initial and
the ion, one may consider only the interaction within the manifold of
Hamiltonian (29) will be given in the text of the present work. It will
one can show that the interaction in Equation (29) leads to an inter
assumed that the interaction between the spins Jj. and Jj located at Ri
Hjj - -(s»J^)(s»Jj)
The first term represents the coupling which arises when the electron
is first scattered by the i-th ion and then by the j-th ion, the second
the limits and infinity because all levels below are filled, so
by the Paull principle k1 must take on seme value greater than 1%. The
|A (]%,k^)|2 and take it outside the integral signs. Summing over the
Hj_j - - M | 2 (g-lj
Here Rjj = Rj_ - Rj. If one assumes an isotropic energy band structure for
16
E(k) = "fi2k2/2m* ,
then the integral in Equation (31) can be readily evaluated. The final
where
(~7)^(2kBPijcos(2iyiij) - sin(2k^ij )J
XJ
Therefore, one obtains Equation (10) if one sums Hj_j in Equation (32)
is the same for all members of the group. If the metals have similar
conduction band structures, then the free electrons should have the
rare earth metals. The same result was also obtained by Brout and Suhl
relationship J = L + S, so
which is the Neel formula. This result is in agreement with the observed
The long range nature of the indirect exchange coupling may give
rise to the peculiar magnetic structure of some of the rare earths. For
the study of this effect Villain (1959) proposed a very interesting way
structure.
h = jAijJ^kT) (38)
Near the critical (or Neel) temperature one has I j «J. The
T(k) = Z iJiexp(ik.Ri) ,
~T(k) = J 1 } 5(k)T(k).
where ICQ is the k -which gives a maximum value to Ç (k)% In this way
Assuming for simplicity that there exist only two vectors k0 which
19
are symmetric with respect to the center of the lattice, one can show
(ia)
spiral axis along the c direction. This has been verified experimentally
this kind is stable below the Neel temperature by showing that any small
deviation from this arrangement tends to raise the free energy of the
it becomes 38°.
earth metals where the spin orbit coupling must be taken into account.
Since the filled shells of the ion do not contribute to any angular
N
«X =2 «1 (b2)
i^l?i -FN+1|
where
of the form
which is the Pauli wave function for a Bloch wave normalized in a large
volume. 1( is the Pauli spinor. The wave function for the magnetic
electrons couple into L, spin angular momenta couple into 5, and then
9
— —»
J = L +S
L = 2
S =2?; .
XVs,M-m(1'2'**#K)- ^
The wave function ^Tjn anà 3jre ®iëen functions of the operators
*p
L , Lz and S , Sz respectively, and are constructed according to the
Hund's rule
S = N/2,
L = Ni - N(N - l)/2,
= L + S = JL + 1/2 for N = 2 Â + 1.
product
J = 2 ?,
P is a permutation operator of the N particles and the sum is taken over
all possible permutations. oc, {3 are the spin up and spin down eigen-
functions; A is the normalization factor which is equal to J N I p 1 (N - p)1 j
and p = S + M - m. The space function contains a linear combination of
• (U7)
H- ' ^ J " r
Putting (It6) and (It?) into (li5), one obtains the wave function for the
magnetic shell.
TShen the magnetic shell is more than half filled (N > 2 X + l),
the space and spin wave functions have more complicated symmetries. It
with respect to all particles in the same row and then antisymmetrizes
•with respect to all particles in the same column of the diagrams. Let
there be 2q electrons that are paired off and n electrons that are
S = n/2,
L = nJl -n(n-l)/2,
J — L + S = n ^ - n(n—2)/2 .
the Young diagrams such that the first (2 Jl +1) electrons are in the
long column of the space diagram and in the long row of the spin
2h
SPACE DIAGRAM
SPIN DIAGRAM
ing the particles in different ways in the same frames. The completely
Z V-i^tOL.S,—N) «) (to)
•«here the summation is taken over all possible tableaux with the same
frame. One should note that since the terms in the above sum are not
and Jz is
Now one can calculate the exchange part of the matrix elements of
from (U3) and (U5)« The wave function of the system of one conduction
^ Y(%+1) (51)
the magnetic shell electrons. It can be proved that one obtains the
i = hfy JM(l,2,—i,-'N
v/ 'i *•
)Y'(N+l)
5i = V-JMU»2,...N)V(N+1) ,
5f = VjM'(l,2,'"N) f'(N+D ,
where
V'(N+l) = ug(i^+1)exp(ik*r^+;L)XN+1 ,
27
2
one finds the contribution of the term —— to the matrix
I ri_rN+ll
element to be
>2
% = V-'*(N+iw®
' |ri -^r+xl
* "Vtitt1'2,•••!» •• -N)"V(
- B+l••a^
+1
2
-Jf^,(1,2,"-i,—N)V'*(N+!)[=-?
ri "*rN+l'
x ''-N+:L'*'eN)Y'(i)di^dr^••'df^+i (53)
after seme simple manipulations. The second term is the exchange part
one is interested in. For the entire shell the exchange part of the
matrix element is
= - M/f I
M = - N % C(LSJ;m,M-m)C(lSJ;m%M'-m')
ex
In each term of (55) the spin functions are multiplied together to form
* X j U ) X 2 ( 2 ) - ^ N + 1 ( i ) » AT h CN) AT i(H+l) ,
X j = Xj jàîior N+l
If these are satisfied the product equals unity. The following four
(^ex)l = - C(LSJ$m,M--ni)C(LSJjm',M,-m')(S-fiI-m)
x Im,^,2j""i, * "N)u^,(r^^)exp(-ik'"%^)
e2
X IF. -r T - 1I ^ 2'''*N+1> 'e *N )
i N+l
after putting p = S + M - m.
(N-p)/k = (S-M-hn), so
(MeX)2 = - Z C(L5J;m,M-4n)C(LSJ;m',M'-m')(S-M-#m)
mm'
= |v/(S-*M-ra)(S-M4m+1)
x v M-m,M'-m'+l.
(Mexb = - Z C(LSJ;m,M-m)G(lSJ;m',M'-m')
ram'
xJ(S«-m)(S-M-hn+l) ^-m,M'-m'+l
(^ex)li = - 2 C(LSJ;m,M-m)C(LSJ5m',M'-ml )
mm1
xj(S-4Hm)(S-tM-m+l) 5 M-m,M'-m'-l
only the s electrons penetrate appreciably into the ion core. So one
may neglect the effect of the 5d electrons and take ug(r) of the Bloch
expdkTi)=4JrZiJ,jjl(tel)T*m(k)Vn) .
31
If the radius of the Uf shell is small compared with the wave length of
If one is concerned with the effect of the leading term only, the
integral reduces to
(1,2,--M,—Dag.tifra^tk'rma.) . .
J I i N+l I
x ^Iffi(l#2,.-.N+l,."N)uk(ri)j0(kri)dri..' di^+1 .
^ Lm = 2 (^+l)
y- r
(^)ug,(rH+1)j0(k,rN4.1)^_L !^N+1i'
4f+l"
Kk.k') = j R*(r1)R(^+l)"k.(->|+l)%(ri)
(Mex)2 = -2 C2(LSJ;m,M-m)(S-M-ta)l(R,k') ,
m
(^6X^3 ~ ~2 C(LSJjm,M-ni)C(LSJ$m,M-m-l)
m
xJ (S4M-m)(S-M-hn+l)l(k,k')^MjM,+1 ,
(Mex)^ = -2 C(LSJjm,M-m)C(LSJjm,M-m+l
m
Therefore
<JM' I Sz I JM ) = 2 c2(LSJ.m,M-m)(MHn)^* H, .
m
Similarly
33
x J(S-tM-m)(S-ÏHm+1)f ,
( il' | S+ | JM y = 2.C(l£Jjm,M-m)C(LSJ;m,M-m+l)
m
J
x (S-M+m)(S*ttî-ffl+l) &u ui_i
In terms of the spin operator "s of the conduction electron the above
H = -2I(k,k')s.S*
Mex = ^ + V&
Hamilton!an (28).
"Within the manifold of constant J value, one may apply the pro-
—^ ^
H = -
= - 2I(k,k')(g-l)s.J (63)
Discussion
satisfy the Neel formula (36). That the elements cerium, praseodymium,
them. The results of Hall measurements on rare earths seem to give seme
temperature. The Hall constants for terbium and holmium have not been
measured.
also shows that the interaction does not exist or is very weak in these
pure elements.
the s-f interaction to exist between the free electrons and the solute
by Trombe (19^5, 1951, 1953), and by Elliott et al. (195U); they found
spontaneous moments lie always in the basal plane. Above 110° K the
direction along the line joining two next nearest neighbors in the
basal plane.) In their paper they gave the experimental results for
direction in the basal plane for both the ferromagnetic and anti-
ferromagnetic regions.
magnetic regions. The content of this theory has been reviewed earlier
Above 110° K the isotropy in the basal plane suggests that the inter
action between the sublattices depends only on the angle between their
energy terms, one may assume a two term Fourier expansion for the inter
action energy E% = acos(fA -<^B) + bcos 2(#& -fe). The second term is
though not unique, does give a consistent fit with the experimental
Basic Equations
magnetic field in either the <( 1010 )> or <( 1120 )> direction;^ and
are the angles between the sublattice magnetizations and the magnetic
anisotropy constant; and the plus sign applies when H is in the ^ 1010^
M = M s /f(/v/kT)(H+JM)j , (65)
is the magnetic moment per ion, and }\ is the molecular field constant.
130° K. The Weiss formula is used below to give M(H) at these higher
temperature.
The material is isotropic in the basal plane so one can put k equal to
E = - MH cos(l/2)(<£A+^B)cos(l/2)(<£A-^B)
$k = - » (67)
the dependences shown in Figure 2. For small field H, case <X applies
and <p ^ at the minimum of E is near 7T/2j for large field, case /?
near ^ A = 7T/2 that an expansion for small cos 5^A applies, one finds
and that the discontinuity takes place at the field value given by
(T = M2H/(Ua-l6b) (72)
for weak fields, Equation (65) for strong fields, and with a
hi
0
<ÊA
In Figures 3 and U the values of M, a, and b -which give the best agree
plotted and the actual agreement for three of the magnetization curves
is shown in Figure 6(A). The solid lines are the theoretical curves
and the marked points show the experimental results from Behrendt et al.
(1958).
rewritten as
+ a cos(^A-fB) + b cos2(<£a-^b)
meters. The one that leads to agreement with the experimental data has
CT = M2H/(l;a-l6b+36k) , (7lta)
cr = M , (7Uc)
where the first equation applies for weak fields, the second for inter
mediate fields, the third for strong fields. An analytical formula for
the field at the transition from Equation (7Ua) to Equation (7i*b) would
and Figure 6(B) shows the agreement with the experimental data at 100° K.
with the field in the (1120 ^ direction. Equation (6b) applies with
the minus signs. One can see that the simple relationship
* k = -*B
does not hold because it would imply that at small field the magnetic
conditions are
The first condition gives the minimum exchange energy and the second the
1500
Tc2 200
T .TEMPERATURE IN °K
CO
h-
z
ZD 3
CO
(D
O 120 °K
IO I40°K-
O 2
Z
z
o 1 I70°K -
h~
<
N
h-
LU SE
Z 0,
o (
8 10
<
H, INTERNAL MAGNETIC FIELD IN KILOGAUSS
b"
(A)
(Z)
h-
CO T
O
O
IOO°K
"o 2 H IN <M?0>-
A A A H IN <ldTO>
g
ISI I-
h-
LU
1
2 4 6 8 10
b" H, INTERNAL MAGNETIC FIELD, IN KILOGAUSS
(B)
Figure 6* (Continued)#
it?
P
CO
O 3 80°K
10
O
g •o— H IN <1120>
S -A- H IN <I0T0>
N
UJ
z
o
<
b °0 2 4 6 8 10
Figure 6. (Continued),
5o
*A = T + é '
E =-a+b-k+(l/U)/3MH +(l/2)(a-ltb-t9k)é2
<= = -/3MHA(a-Ub49k) ,
S = +yj(MH)2/288k(a-lib-»9k) .
and this gives the initial slope of the magnetization curve. Similarly
for high fields, one finds that the first order solutions for the
A = = 0, 0" = M (77)
H = 2a/M . (78)
Figure 6(B) shows the comparison of the theory with the experimental
data.
where the proper sign of the anisotropy energy should be chosen according
If the field is applied in the easy direction, the material simply remains
field is applied in the <( 1010 )> direction, the plus sign in Equation
<J" = M, (80b)
MH = 36k (81)
Figures 3 and 5 show the choice of M and k which gives best agreement
Figure 6(C).
discuss the large anisotropy relative to the c axis. Assuming the field
where 6 9-q are the angles between the magnetization vectors of the
sublattices and the c axis, and k' is the anisotropy constant for this
the susceptibility
Figure 7.
Discussion
molecular field theory. That the curve goes smoothly through the
A' »
by Zener's theory (Zener, 1954; see also Keffer, 1955; Pincus, 1959) for
>
Q_
O »I
(Z S
h-
o O1
<2 (/)
z E>
< O:
LU
Û•
_)
o o
1
oz
$ 1-
H z
— M < H
CO
CVI z
o
s o
200
T, TEMPERATURE
sin 6^. This term does not appreciably affect the discussion of the
magnetization curve when the external field is out of the basal plane
because k«k'. The agreement of k' with M3 shows that the assumed
the basal plane also introduces some small corrections on k'. However
of the a, b terms to tell definitely whether the use of these tenns out
specific heat can be found by subtracting the lattice and the electronic
The resulting data are shown in Figure 8, together with the curve (in
dashed lines)
h- LU
1 I
50 Tci 100 150 TC2 200
T, TEMPERATURE IN °K
G = U - TS + PV - HI , (86)
Sf = Si
along the equilibrium surface. The subscripts denote initial and final
obtains
58
4 s = "f I?
|p = 1.3xl02 gauss/°K,
dT |P
M = 5*7xlcA cgs/mole,
T^ A s = 15 cal/mole .
This should correspond to the area under the first peak of the specific
~ P ( CX - Of c) .
iîhen "writing the free energy of the system, the elastic energy must be
01 = a T + f . (92)
R
change in Of will be
4 Of = M2 e (93)
+ constant (95)
b
W
should not have the strong temperature dependence as shown in Figure ii.
A7 _ V d#/#
(96)
dP ^s o G/a T)P
3
{JJA F),
P
A F = -2 f> M2( CX T- a c)
Hence
61
(^F)p = -2f
Substituting this result and Equation (93) into Equation (96), one obtains
dTcl = 1 1
~Br o( R Oof T/aT) X . (97)
P- «7 =
K - 1/ a 2R .
Therefore
s r<i
and
dTci _ 1
•f - — • ( 9 8 )
did -5 _
-gp- = 2 cm^ °K/ cal. = 0.05 K/ atoms .
the exchange energy, it does not tell the whole story because seme of
BIBLIOGRAPHY
de Gennes, P.~G. 1958. Sur les propriétés des méteaux des terres rares.
Comptes Rendus 2k7, 1836.
ACKN OELEDGEjvBÏTS
R. H. Good, Jr. for his constant guidance and encouragement during the