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Introduction to
CHARLES K IT TEL
14
PARAMAGNETISM 420
PARAMAGNETIC SUSCEPTffiILITY OF
SUMMARY 436
PROBLEMS 436
=
8. Paramagnetism of S 1 system 440
REFERENCES 440
NOTATION : In the problems treated in this chapter the magnetic field B is always
closely equal to the applied field Ba, so that we write B for Ba in most instances.
t
+ --------
Or---------~T_--------------------------------
Pauli paramagnetism (metals) Temperature
Diamagnetism
416
CHAPT ER 14: DIAMAGNE T ISM AND PARAMAGNE TISM
M
(Ce S) x = 13 ' (SI) X = /-LoM
B
(1)
where B is the macroscopic magne tic field intensity. In both systems of units X
is dimensionless. We shall sometimes for convenience refer to MIB as the sus
ceptibility without specifying the syste m of units .
Quite frequ e ntly a susceptibility is defi ned refe rred to unit mass Or to a
mole of the substance . The molar susceptibility is written as XM ; the magnetic
moment per gram is sometimes writte n as CT. Subs tances with a negative mag
netic susceptibility are called diamagnetic. Substances with a positive suscepti
bility are called paramagnetic, as in Fig. 1.
O rdered arrays of magn etic moments are discussed in Chapter 15; the
arrays may be fe rromagne tic, ferrimagnetic, antiferromagne tic, helical, or
more complex in fo rm. N uclear magnetic moments give rise to nuclea r
paramagne tism . Magnetic moments of nuclei are of th e order of 10- 3 times
smalle r than the magnetic momen t of th e electron.
417
418
If the field is applied slowly, the motion in the rotating reference system will be
the same as the original motion in the rest system before the application of the
field .
If the average electron current around the nucleus is zero initially, the
application of the magnetic field will cause a finite current around the nu
cleus. The current is equivalent to a magnetic moment opposite to the applied
field. It is assumed that the Larmor frequency (2) is mu ch lower than the fre
q uency of the original motion in the central field . This condition is not satisfied
in free carrier cyclotron resonance, and the cyclotron frequency is twice the
freq uency (2).
The Larmor precession of Z electrons is equivalent to an electric current
ZtfB
(S I) JI. =- 4m (p'l) ; (4)
Here (p'2) = (x'2) + (y'2) is the mean square of the perpendicular distance of the
electron from the field axis thro tigh the nucleus. The mean square distance of
the electrons from the nucleus is (r'2) = (x 2) + (y2) + (Z2). For a spherically
symmetrical distribution of charge we have (x 2) = (y2) = (Z2), so that (r 2) =
i(p2).
From (4) the diamagnetic susceptibility per unit volume is, if N is the
number of atoms per unit volume,
2
(ces) X
= NI.L = _ NZe (r'2) (5)
B 6mc'2 '
14 Diamagnetism and Paramagnetism 419
2
(SI) x = ILQNIl- = ILQNZe (r 2 )
B 6m
He Ne Ar Kr Xe
From (G . 18) the effect of a magnetic field is to add to the hamiltonian the
terms
ieh e2
J-C = -(V' . A + A V') + - - A2 , (6)
2mc 2mc2
for an atomic electron these tenns may usually be treated as a small perturba
tion . If the magnetic field is uniform and in the z direction , we may write
A x = -~yB , Ay = hB, Az = 0 , (7)
and (6) becomes
iehB(d
J-C = - - x- d)
e - (x 2 + y2)
- y- + - 2
2
B
2
(8)
2mc dy dx 8mc
The first term on the right is proportional to the orbital angular mUlnen
tum component Lz if r is measured from th e nucleus. In mononuclear syste ms
this term gives rise only to paramagnetism . The second term gives fo r a spheri
cally symmetric system a contribution
2 2
E' = e B2 (r 2 )
-1 (9)
n1C 2 '
The moment is
netic:
in with
ta is in:
g =l + ~---'----~--'---'-
14 Diamagnetism and Paramagnetism 421
s:: 1.00 1 4
.02
--',
".
'If
( /// 2ILB
ms
-2
1
IJ.z
- IL
!J.
1 0.75
0.
8. 0 .50
"s::
B025
e
c.... o1 I i i 1
o 0.5 1.0 1.5 2.0
ILBlkBT
Figure 2 Energy level splitting for one electron
in a magnetic field B directed along the positive z Figure 3 Fractional populations of a two-level
axis. For an electron the magnetic moment JL is system in thermal equilibrium at temperature T
opposite in sign to the spin S, so that JL = in a magnetic field B. Th e magnetic moment is
-gJLBS. In th e low energy state the magnetic proportional ta the difference between the two
moment is paraIJel ta the magnetic field. curves.
The Bohr magneton J-tB is defined as eh/2mc in ces and eh/2m in SI. It is
closely equal to the spin magnetic moment of a free electron .
The energy levels of the system in a magnetic field are
U = - P' B = mjgJ-tBB , (14)
where mj is the azimuthal quantum number and has the values J, J - l, ... ,
- J. For a single spin with no orbi tal moment we have mj = i and g = 2,
whence U = J-tBB. This splitting is shown in F ig. 2.
If a system has only two levels the equilibrium populations are, with
T == kBT,
NI exp(J-tBIT)
(15)
N exp(j.LBiT) + exp(- j.LBIT) ,
Nz exp(- J-tB IT)
(16)
N exp(J-tBIT) + exp( - j.LBiT) ,
here N j , N z are the populations of the lower and upper levels, and
N = N j + N 2 is the total number of atoms. The fractional populations are plot
ted in Fig. 3.
The projection of the magnetic moment of the upper state along the field
direction is - J-t and of the lower state is J-t. The resultant magnetization for N
atoms per unit volume is , with x == J-tB/kBT,
eX - e- X
M = (N I - N 2 )J-t = NJ-t x + _, = NJ-t tanh x . (17)
e e
For x ~ l , tanh x = x, and we have
M =NJ-t(J-tB/kBT) (18)
In a magnetic field an atom with angular momentum quantum number J
has 2J + 1 equally spaced energy levels. The magnetization (Fig. 4) is given by
M = NgJJ-tB Bj(x) , (x == gJ J-tBB/k BT ) , (19)
422
7.00 1TIIInITT':D:o:F:::P:I5F~FiTi'
BIT in kG deg- L
Figure 4 Plot of magnetic moment versus BIT for sphe rical samples of (1) potassium ch romium
alum, (II) ferric ammonium alum , and (III) gadolinium sulfate octahydrate. Over 99.5% magnetic
saturation is achieved at 1.3 K and about 50,000 gauss. (ST). After W. E . Henry.
B,(x) =
2J + 1 ctnh ((2J + l)x) - - 1 ctnh ( - x ) (20)
. 2J 2J 2J 2J
Equation (17) is a special case of (20) for J = t.
For x <s:; l, we have
1 x x3
ctnh x = - + - - - + (21)
x 3 45
and the susceptibility is
M NJ(J + 1)g2JL~ C
-=
B 3k B T
(22)
T
H ere p is the effective number of Bohr magnetons, defined as
p == gU(J + 1)F /2 . (23)
14 Dianwgnetism and Paranwgnetism
40~--------~----'~~-~------~~
Temperature, Je
Figure 5 Plot of l/X vs T for a gadolinium salt, Gd(C zH 5 S0 4h . straight line the
Curie law, (Aftel' L. C. Jackson and Onnes,)
atom
state is charac
different
14 Diamagnetism and Paramagnetism 425
c + 4P5s2 p6 2F
s I2 2. 54 2.4
Pr 3 + 4j25s 2 p6 3H
4 3. 58 3. 5
Nd 3 + 4P5s 2 p6 41 912 3.62 3.5
Pm 3 + 4f 4 5s2 p6 514 2. 68
Sm 3 + 4f s5s 2p 6 6H
sf2 0.84 1.5
Eu3+ 4f6 5s 2 p6 7F
o 0 3.4
Gd 3 + 4F5s 2 p6 8S 712 7.94 8.0
Tb 3 + 4j'B5s 2 p6 7F
6 9.72 9.5
D y 3+ 4f 9 5s 2 p6 6H
1SI2 10.63 10.6
Ho3 + 4po5s2 p6 s Is 10.60 10.4
E r3+ 4f1l5 s2 p6 41 1S12 9.59 9.5
Tm 3 + 4P 25s 2 p6 3H
6 7. 57 7.3
Yb 3 + 4P 3 5s 2 p6 2F7i2 4.54 4.5
Ti3+, y4+ 3d l 2D
3I2 1.55 1. 73 1.8
y 3+ 3d 2 3F
2 1.63 2.83 2.8
Cr3+, y2+ 3d 3 4F 3/2 0. 77 3.87 3.8
M n 3+, Cr+ 3d 4 5DO 0 4.90 4.9
F e 3+, Mn 2 + 3d 5 65 51 2 5.92 5.92 5.9
Fe 2+ 3d6 5D
4 6.70 4.90 5.4
C o 2+ 3d7 4F 9/2 6.63 3.87 4.8
Ni 2+ 3d 8 3F
4 5.59 2.83 3.2
Cu 2 + 3d 9 2D5/ 2 3.55 1.73 1.9
"Representative values.
lated as if the orbital moment were not there at ail. We say that the orbital
moments are quenched.
@ @ @
===== P"Py
y - ---pz
y
@
(a) (b) (c) (d)
Figure 6 Consider an atom with orbital angular momentum L = l placed in the uniaxial crystalline
electric field of the two positive ions along the z axis. In the free atom the states mL = l, 0 have
identical energies-they are degenerate. In the crystal the atom has a lower energy when the
electron cloud is close to positive ions as in (a) th an when it is oriented midway between them, as
in (b) and (c). The wavefunctions that give rise to these charge densities are of the form zf(r), xf(r)
and yf(r) and are called the Pz, Px, Py orbitaIs, respectively. In an axially symmetric field, as shown,
the Px and Py orbitaIs are degenerate. The energy levels referred to the free atom (dotted !ine) are
shown in (d). If the electric field does not have axial symmetry, ail three states will have different
energies.
magne tic moment of astate is given by the average value of the magnetic
moment operator I-tB(L + 2S). In a magnetic field along the z direction the
orbital contribution to the magnetic moment is proportion al to the quantum
expectation value of L z; the orbital magnetic moment is quenched if the me
chanical moment Lz is quenched.
When the spin-orbit interaction energy is introduced, the spin may drag
sorne orbital moment along with it. If the sign of the interaction favors paraUel
orientation of the spin and orbital magnetic moments, the total magnetic mo
ment will be larger than for the spin alone, and the g value will be larger than 2.
The experimental results are in agreement with the known variation of sign of
the spin-orbit interaction: g > 2 when the 3d shell is more than half full, g = 2
when the shell is half full , and g < 2 when the shell is less than half full .
We consider a single electron wi th orbital quantum number L = 1 moving
about a nucleus, the whole being placed in an inhomogeneous crystalline elec
tric field. We omit electron spin.
In a crystal of orthorhombic sym metry the charges on neighboring ions
will produce an electrostatic potential cp about the nucleus of thJ form
ecp = AX2 + B y2 - (A + B )Z2 , (24)
where A and B are constants. This expression is the lowest degree polynomial
in x, y, z which is a solution of the Laplace equation V2 cp = 0 and compatible
with the symmetry of the crystal.
428
Uy = yf(r) ; Uz = zf(r)
are normalized.
= 2Ui ,
= 0 .
Consider
dx dy dz ; (28)
the integral
the diagonal matrix
elements:
+ dx dy dz
(29)
where
dx dz ;
o.
This effect is
momentum,
age is zero in
magnetic moment also
Paramilgnetttm
(30)
- / l ,
the hetween
g
g
The susceptibility is
(39)
Diamagnetism Paramagnetism 431
COOLING DY
the
partly lined
is also lowered if
1) .
in
Total
Spin
Spin
is removed is l'emoved
Figure 7 During adiabatic dem agnetization the total entropy of the specimen is constant. For
effective cooli ng the initi al entropy of the lattice should be small in comparison with the entropy of
the spi n sys tem.
The steps carried out in the cooling process are shown in F ig. 8. The field
is applied at temperature T l with the specimen in good thermal contact with
the surroundings, giving the isothermal path ab. The specimen is then insu
lated (!la- = 0) and the fi eld removed; the specimen follows the constant en
tropy path he, ending up at temperature T 2 . The thermal contact at Tl is pro
vided by helium gas, and the thermal contact is broken by removing the gas
with a pump.
Nuclear Demagnetization
The population of a magne tic sublevel is a function only of f.LB l kBT , hence
of BIT. The spin -system entropy is a function only of the population distribu
tion ; hence the spin entropy is a function only of BIT. If Bt>. is the effective field
that corresponds to the local interactions, the final temperature T 2 reached in
an adiabatic demagnetization experiment is
1 T 2 = Tl (Bt>.IB ) , 1 (41)
0.7,r---------------------------------------------------------~
0.6
~
~
~ 0.5
B = 0; BA = 100 gauss
S ~4
~
g 0. 3
~
~
S Qi
~
0.1
o6 L ~ 10 15 do ~5' j'J
T, mK
' igure 8 Entropy for a , pin 1 sys tem as a fun etion of te mpera ture, assumin g an intern aI random
magne tic field Be:. of 100 gauss. The specimen is magnetized iso th e rmall y along ab , and is th en
insulated thermally. The external magnetie field is turned off al ong be. In ord e r to keep the figure
on a reasonable seale the initial tem pe rature Tl is lower th an wo uId be us ed in practice, and so is
the exte rn al magnetic fi eld .
We are going to try to show how on the basis of these stati sti cs the fa ct th at many
me tals are diamagnetic, or only weakl y paramagnetic, can be brought into agree
me nt with tb e existence of a magnetic mom e nt of tbe e lectrons .
W. Pauli, 1927
4N . Kurti , F . N . H . Robinson, F. E. Simon, and D . A. Spohr, Nature 178 , 450 (1 956); for
reviews see N. Kurti, Cryogenies 1, 2 (1960); Adv. in Cryogenie Engineering 8, 1 (1963).
sp. J. Hakonen e t al ., Ph ys . Rev. Lett. 70, 2818 (1993).
434
1 6
~ 5
.,1;0
e
u
4
.S 3
lL-__L-~~~~~~--------~--~
0.3 0.6 2
Figure 9 Nuclear demagnetizations of copper nuclei in the metal, starting from 0.012 K and
various fields . (After M. V. Hobden and N. KurtL)
l 1 ~
Parallel
ta field
1
(a) (b)
Figure 10 Pauli paramagnetism at absolu te zero; the orbitais in the shaded regions in (a) are
occupied . The numbers of electrons in the " up " and "down" band will adjust ta make the energies
equal at the Fermi level. The chemical potential (Fermi level) of the moment up electrons is equal
to that of the moment down electrons. In (b) we show the excess of moment up electrons in the
magnetic field.
N+ = -
l
2
J 'F
- l'-B
dE D (E + fJ-B ) == -l
2
l
0
EF
dE D(E) + -l
2
fJ-B D (EF) ,
21'-B 20 2
B. (43)
the
by
The
UUU1H.l<U.'y high for transition
Ipl"~r"n,,, heat
of atomic Z is X
atomic (Langevin)
the maximum S
consistent with this S. The
and IL - S if the shell is Jess
..
..
is
14 Diamagnetism and Paramagnetism 437
80
r tS iT T T 1 1 1 IIT
7.0
6.0
~ \
~
w
E
"
1
5.0
\ -r--r-2_
\ ~ --~_ I ~
8 Cr
"__ 4.0
\ // ... V
g
~
0. ~~/ .......-~w
'"
:l"
V>
3.0 ~
f--
'\
- r--_ "
2.0
I r- - -
- -~-
~Nb
_J-_+-_r-zr- v -
_ l Rh
~
1'1
1.0
Na
K--
1R'b"'f--- T--t--
'"
-+--1f--+_-J-::H::lr r--- - - Ta
0
0 200 400 600
J
800 1000 1200
J
1400 1600
J
1800 2000 2200
T. in K
Figure 11 Temperature dependence of the magnetic susceptibility of metals. (Courtesy of C. J.
Kriessman .)
2. Huml mles. Apply the H und rules to find the ground state (the basic level in the
notation ofTable 1) of (a) E u + +, in the configuration 4[1 5S 2p6; (b) Yb3+ ; (c) Tb 3 + . The
results fo r (b) and (c) are in Table 1, but you should give the separate steps in applyi ng
the rules.
3. Triplet excited states. Some organic molecules have a triplet (S = 1) excited state at
an energy kBil above a singlet (S = 0) ground state. (a) Find an expression for the
magnetic moment (J-L ) in a fie ld B. (b) Show that the susceptibility for T p il is
approximately independent of il. (c) With the help of a diagram of energy levels
versus field and a rou gh sketch of entropy versus field , explain how this system might
be cooled by adiabatic magne tiza tion (not demagnetization).
438
capacity
interaction between nuclear and electronic
+(),
(1 + () ;
find a similar expression for the total energy and for in the
limit {, ~ 1. Show that the magnetization is
0.5 --,------r---,---,---,--i
r-j
.l
""
.~
S
"
0.3
1
,:;
j
Level2
Level l
,J
'"p,
8 0.2
0.1
00 4 5 6
x = Tlt.
Figure 12 Heat capacity of a two-level system as a function of T/t;,., where t;,. is the level splitting.
The Schottky anomaly is a very useful tool for determining energy level splittings of ions in rare
earth and transition-group metals, compounds, and alloys.
0.008
0006
;.0 eNT" = 4.3 x
1
1
(3
E
E 0.004
.S
h
u " 0.002
u= c=
of are
proportional to the tem
to the heat capacity of dilute
1519 It is al50 used in the
A. J. Freeman, The actinides: electronic structure and related properties, Academie, 1974.
R. D. Hudson. Princip les and Elsevier, 1972.
Knoepfel, Pu/sed North-Holland, 1970.
Lounasmaa, and methods below 1 K, Academie Press, 1974.
Introduction ta transition metal 2nd ed., Wiley, 1966.
Van Vleck, The theory Oxford, 1932. deriva
tions of basic theorems.
G. K. White, 3rd Oxford, 1987.
R. White, Quantum theory
A. J. Freeman and G. H. Lander, actinides. North-
Holland, 1984-1993.
Sturge, "Jahn-Teller effect in solids," Solid state 91 (1967).
O'Brien and C. C. Chancey, "The effect: An introduction and current re
view," Amer. J, Physics 61, (1993),