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Chapter Eleven Diamagnetism and
Chapter Eleven Diamagnetism and
M (emu/cm3)
diamagnetism
H (Oe) H (Oe)
Magnetic susceptibility per unit volume
χ≡
M M : magnetization, magnetic moment per unit volume
H B : macroscopic magnetic field intensity
CGS
B = H + 4π M = µ H
M=m
N
m : magnetic dipole moment
m=− ∑ ri × p i = − L = −µB L
[emu/cm3] V e e
Angular
2m i 2m momentum
m = µ Bg o ∑ si = µ Bg o S
Spin
i
electron I v
4
L and S are quantum operators with no basis in classical physics.
Theory of diamagnetism
was first worked out by Paul Langevin in 1905.
Negative magnetism present in an applied field
even though the material is composed of atoms
that have no net magnetic moment.
Emf = −
Faraday’s law dΦ B
Paul Langevin
[volt] dt 1872~1946
N A ρ e2 Z
I χ =− R 2
µ
r
A 6mc 2
[emu/Oe-cm3]
5
H
The change in moment of a single orbit :
π r 2 dH
E= =− =− =−
2π r dt
Emf A dH r dH
dt
∫ ∫ − 2mc dH
2 dt
er
a= = =− =
dv eE er dH
dv
dt mc 2mc dt
∆v = −
er
H
2mc
∆µ = ∆v = −
er e2r 2 the plane of the orbit is perpendicular
2
H
2c 4mc to the applied field
2 ∫
( )( )
π /2
= θ π θ θ =
R2
2πR 0
2 2 2
sin 2 R sin Rd R
3 6
A single electron with consideration of all possible oriented orbits,
∆µ = ∆v = −
eR e2 R 2
2
H
2c 6mc
∆µ = ∑ − 2 ∑ i
For an atom that contains Z electrons,
H=−
z
e 2 Ri2 e2H z 2
R Ri is the radius of the ith orbit
i =1 6mc i =1
2
6mc
N A ρ e2 Z
Susceptibility, χ = −
2 ∑ i
N A ρ e2 z 2
On the volume basis,
∆µ = − R H
2
R
A 6mc i =1 A 6mc 2
Classical Langevin result
( ) ( ) (0.7 ×10 )
Carbon (radius =0.7Å)
6.02 ×10 23 2.22g/cm 3 4.80 ×10 −10 esu 6
( )( )
χ =−
2
−8
Negative susceptibility
magnitude : 10-5 ~10-6 cm3/mole
χ is independent of temperature
The other consistency is that
χ= χ=
T −θ
C C'
in general
T
Curie law Curie-Weiss law (1907)
9
1 Q
Quantum theory of diamagnetism
H= p − A + QV
2
2m c
Hamiltonian
H '=
ie
2mc
(
∇ • A+ A•∇ +
) e2
2mc 2
A 2
∂
∇ × A = î +
∂ ∂
(
ĵ + k̂ × Ax î + Ay ĵ + Az k̂ )
∂x ∂y ∂z
∂Az ∂Ax ∂Ax ∂Az ∂Ay ∂Ax
= − î + − ĵ + − k̂
∂y ∂z ∂z ∂x ∂x ∂y
( )
2 2
ieB ∂ ∂ e 2 B2 2
H '= x − y + +
4mc ∂y ∂x 8mc 2
2
x y
~ 10
Lz
z-component of angular momentum
∂ ∂
L z = −i x − y
~
∂y ∂x
paramagnetism
x +y = r
2 2 2 2
For a spherically symmetric system
3
11
Vibrating Sample Magnetometer (VSM)
14
A unit volume material contains n atoms with a magnetic moment µ each.
E = − µ • H = − µH cosθ
H
θ
Let the direction of each moment be presented by a vector,
µ
and let all vectors be drawn thru. the center of the sphere.
µH cos θ
= K 2π sin θdθ e
−
dn = KdA e # at angle θ θ+dθ
E
k BT k BT
µH cos θ
π
n = ∫ dn = K 2π ∫ dθ sin θ e k BT
total #
µH cos θ
π
M = ∫ dnµ cosθ = K 2πµ ∫ dθ cosθ sin θ e
0
n
k BT
π
nµ ∫ dθ cosθ sin θ e a cosθ
0 0
Let a = µH/kBT, M = π
∫ dθ sin θ e
0
a cos θ
nµ ∫ dx xe ax
−1
e a + e −a 1
= nµ coth (a ) −
1
= = nµ a −
e −e a
−1 −a
1
∫ dx e
ax a 15
1
Langevin function L(a)=coth(a)-1/a
L(a) can be expressed in series,
L(a) = − + − ...
a a 3 2a 5
M/Mo
3 45 945
When a is small (<0.5),
L(a) is a straight line w/. a slope 1/3.
a=µH/kBT
Two conclusions :
(1) Saturation will occurs at large a implying that at large H and low T the
alignment tendency of field is going to overcome the randomizing
effect of thermal agitation.
(2) At small a, L(a) depends linearly on a implying that M varies linearly
16
with H.
nµa nµ µH
The Langevin theory also leads to the Curie law.
For small a,
M= =
nµ 2
M nµ 2 C=
3 3 k BT
χ= = =
C 3kB
H 3 k BT T
Oxygen is paramagnetic and obeys the Curie law w/. χ=1.08×10-4emu/gOe.
χ= = =
H T − Cγ T − θ
M C C
θ
Intercept reveals information of θ
θ (FeSO4)<0, θ (MnCl2)>0
θ>0 indicates that the molecular field aids the applied field, makes
elementary moments align with H, and tends to increase χ.
θ<0 indicates that the molecular field opposes the applied field, makes
elementary moments disalign with H, and tends to decrease χ. 19
τ = µ×H
Precession of atomic magnetic moments about H,
like gyroscope, angular momentum in the presence of gravitation.
τ = r × mg =
dL
dt
that the value of θ for each atom decreases slightly, until the
the exchange of energy disturbs the precessional motion enough so
21
The orbital and spin magnetic moments for an electron
µ orbit = = =−
e
4πmc 2mc 2π
eh e h
p orbit
2mc
µspin = = =−
e
4πmc mc 2 2π
eh e 1 h
p spin
mc
In general
µ = −g
e where g is spectroscopic splitting factor, or g-factor
p
2mc g=1 for orbital motion and g=2 for spin
In the direction of H, µ H = g m J = gm J µ B
2mc
e
2mc
There are 2J+1 numbers of allowed azimuthal quantum number mJ : 22
J, J-1, … , -(J-1), -J.
For a free atom, the g factor is given by the Landé equation
J(J + 1) + S(S + 1) − L(L + 1)
g = 1+
2J(J + 1)
ms µs
The energy levels of the system in a magnetic field
1/2 -µ
2µB
-1/2 µ
E = − µ • H = m J gµ B H
For a single spin with no orbital moment, mJ=±1/2 and g=2.
The equilibrium population for the two level system :
exp( µH/k BT )
=
N exp( µH/k BT ) + exp( − µH/k BT )
N1
lower level Total number of atoms
exp( − µH/k BT )
is conserved.
=
N exp( µH/k BT ) + exp( − µH/k BT )
N2
upper level N = N1+N2 = constant
23
The resultant magnetization for N atoms per unit volume
µH
= Nµ tanh (x )
ex − e−x
M = (N1 − N 2 ) µ = Nµ x where x =
e +e −x
µ 2H
k BT
U = −m J gµ B H
For a system with known g and J,
Potential energy of each moment in H
∑ m J gµ Be
m J gµ B H/k BT
M=N
Boltzmann statistics
∑
m gµ
mJ
Therefore,
B H/k B T
e J mJ : J, J-1, … , -(J-1), -J
2J + 1 (2J + 1)x 1 x
mJ
(2J + 1)x 1
per unit volume atom in the direction of H
2J + 1 x
= B J (x) = coth −
M
2J
coth Brillouin function, 1927
Mo 2J 2J 2J
= coth (x ) −
Langevin function.
M 1
Mo x
When J=1/2, the magnetic moment
consists of one spin per atom.
= tanh (x )
M x<<1 x
2 2 µBH µ 2H
Mo
M ≅ Nµ H x = Ng J =N
2
k BT k BT
25
KCr(SO4)12H2O
The Brillouin function, like the Langevin, is zero for x equals to zero
and tends to unity as x becomes large. The course of the curve in
µH gJµ B H µ H H
between depends on the value of J for the atom involved.
classical x =
k BT
≠ quantum x = =
26
the atom
When H is large enough and T low enough, a paramagnetic can be saturated.
The data is well described by the quantum model with J=S=3/2 and g=2 .
L=0 no orbital component
“Spin-only” moment
27
metals
Gd(C2H3SO4)3•9H2O
28
What magnetic moment a metal should have?
incorporate coupling of magnetic moment to determine
Hund’s rule
the magnetic state
29
2S+1 L : 0, 1, 2, 3, 4
Magnetic state LJ S, P, D, F, G
Examples
(1) Full shells : L=0, S=0, and hence, J=0
30
Eg. Cs3+ 4f15S25P6 Eg. Pr3+ 4f25S25P6
(n=4, =3) (n=4, =3)
3 3
2 2
1 2 1 3
0 State F5/2 0 State H4
-1 -1
-2 -2
-3 -3
L=3 and S=1/2 L=5 and S=1
J=L-S=5/2 J=L-S=4
Eg. Dy3+ 4f95S25P6
(n=4, =3)
3
2
1 6
0 State H15/2
-1
-2
-3
L=5 and S=5/2
31
J=L+S=15/2
Rare earth ions
In the iron group ions the 3d shell, the outermost shell, is responsible
for the paramagnetism and experiences the intense inhomogeneous
electric field produced by neighboring ions.
called “the crystal field” breaking L-S coupling (J is meaningless)
splitting 2L+1 sublevels (diminishing the 33
contribution of orbital motion to magnetic moment)
An atom w/. L=1 is placed in the uniaxial crystalline electric field of
two positive ions along the z-axis. Take S=0 to simplify the problem.
x + iy
In a free atom, a single electron in a p-state.
x − iy
R n (r)Y1−1 (θφ ) ∝ f(r)
2 34
ions will produce an electrostatic potential ϕ about the nucleus,
In a crystal of orthorhombic symmetry the charges on neighboring
eϕ = Ax 2 + By 2 − (A + B)z 2
+ perturbed term eϕ
Non-diagonal elements U x eϕ U y = U y eϕ U z = U z eϕ U x = 0
= A(I1 − I 2 )
35
U y eϕ U y = ∫ f(r) y 2 [Ax 2 + By 2 − (A + B)z 2 ]dxdydz
2
= B(I 1 − I 2 )
U z eϕ U z = ∫ f(r) z 2 [Ax 2 + By 2 − (A + B)z 2 ]dxdydz
2
= (A + B)(I 2 − I1 )
nµ B2 H
• Curie-type paramagnetic contribution (electron spins align w/. H)
• Pauli pointed out that only electrons near EF (±kBT) can flip over.
Fermi-Dirac distribution
1.1
1.0
kBT H=0 H≠0
0.9
εεFF
0.8
0.7
f(ε,T)
0.6 T=0
0.5
0.4
T≠0
εF
0.3
ε
0.2
0.1 37
0.0
=
εF
k BT T
Fraction of electron participating TF
T µ B2 H nµ B2 H
M = n =
TF k BT k BTF
independent of temperature
εF ↓ ↓
↑
↑
H
2µH
µH
DOS DOS
38
The concentration of electrons w/. magnetic moment parallel to H
M = (N ↑ − N ↓ )µ = µD(ε F ) µH =
Pauli spin magnetization
µ H= µ 2H
2ε F
3N 2 3N
2k BTF
39
References :
Kittel, Introduction to Solid State Physics, 8th Ed., Ch.11-12, 2005.
S = k B ln Z
where Z is the partition function
Z = ∑ exp
m=I
εM
N
m = -I k BT
41
a
c
b
B/T
Entropy for a spin ½ system depends only for the population distribution.
a→b : the system is magnetized isothermally.
b→c : the magnetic field is turned off adiabatically.
H
Tf = Ti ∆ where H∆ is the effective field
H
µH
If we start at H=5T and Ti=10mK ≈ 0. 5 Tf ~10-7K
k BT
The first nuclear cooling was done on Cu, Ti=20mK Tf ~1.2×10-6K
42
Cu nuclei in the metal
3.1
Tf = Ti
B
where B∆=3.1Oe.
1.2 µ K
Rd
The present record for a
spin temperature is about
280pK. PRL70, 2818 (1993).
43