11.

Diamagnetism and Paramagnetism

• Langevin Diamagnetism Equation
• Quantum Theory of Diamagnetism of Mononuclear Systems
• Paramagnetism
• Quantum Theory of Paramagnetism
• Rare Earth Ions
• Hund Rules
• Iron Group Ions
• Crystal Field Splitting
• Quenching of The Orbital Angular Momentum
• Spectroscopic Splitting Factor
• Van Vieck Temperature-Independent Paramagnetism
• Cooling by Isentropic Demagnetization
• Nuclear Demagnetization
• Paramagnetic Susceptibility of Conduction Electrons

Ref: D.Wagner, “Introduction to the Theory of Magnetism”, Pergamon Press (72)

 Bohr-van Leeuwen Theorem
M = γ L = 0 according to classical
statistics.
→ magnetism obeys quantum statistics.
Main contribution for free atoms:
• spins of electrons paramagnetism
• orbital angular momenta of electrons
• Induced orbital moments
diamagnetism

Electronic structure Moment

H: 1s MS
He: 1s2 M=0
unfilled shell M0
All filled shells M=0

Magnetization M  magnetic moment per unit volume

M
Magnetic subsceptibility per unit volume   In vacuum, H = B.
H
χ M = molar subsceptibility
σ = specific subsceptibility nuclear moments ~ 10−3 electronic moments
 Larmor Precession
1 3 J  x 
A   d x
c x  x
1 mx
Magnetic (dipole) moment: m  d 3 x x  J  x  A
2c r3
1 I
2c 
For a current J d 3x  I d l m x  I d l  Area
loop: c

For a charge moving in a loop: J  x   q v   x  xq  ( charge at xq )

1 q q
m
2c  d 3
x  x  q v  x  x q  
2c
x q  v 
2mc
L  L Caution: we’ll set L to  L
in the quantum version
q e
Classical gyromagnetic ratio    B 
2mc 2mc
dL
Torque on m in magnetic field: Γ  mB   LB
dt
qB
→ L precesses about B with the Larmor frequency L   B 
2mc
dv q qB
Lorentz force: m  vB → cyclotron frequency c   2L
dt c mc
 Langevin Diamagnetism Equation
Diamagnetism ~ Lenz’s law: induced current opposes flux changes. χ<0
eB 1
Larmor theorem: weak B on e in atom → precession with freq L   C
2mc 2

Larmor precession L Z e2 B 1 Z e2 B
I    Ze    I  2
 2
of Z e’s: 2 4 m c c 4 m c2
3
 2  x2  y 2 r 2  x2  y2  z2 → r2  2
2

N N Z e2 2 Langevin diamagnetism
For N atoms per unit volume:   r
B 6 m c2 same as QM result

Good for inert gases

and dielectric solids

experiment

Failure: conduction electrons (Landau diamagnetism & dHvA effect)

 Quantum Theory of Diamagnetism of Mononuclear Systems
Quantum version of Langevin diamagnetism
ie e2
Perturbation Hamiltonian [see App (G18) ]: H     A  A    2
A2
2mc 2mc
1 1    
Uniform B  B zˆ → A B   y , x, 0  → A  0 A   By x 
2 2  x y 
ieB     e2 B 2 2
2   eB e2 B 2 2
H      
2
 x y  x y  Lz  x  y 2
4 m c  y x  8 m c 2mc 8 m c2

The Lz term gives rise to paramagnetism.

e2 B 2 e2 B 2
1st order contribution from 2nd term: E   2
 r 2

8 m c2 12 m c 2

 E e2 r 2
  B same as classical result
B 6 m c2
 Paramagnetism
Paramagnetism: χ > 0

Occurrence of electronic paramagnetism:

• Atoms, molecules, & lattice defects with odd number of electrons ( S  0 ).
E.g., Free sodium atoms, gaseous NO, F centers in alkali halides,
organic free radicals such as C(C6H5)3.
• Free atoms & ions with partly filled inner shell (free or in solid),
E.g., Transition elements, ions isoelectronic with transition elements,
rare earth & actinide elements such as Mn2+, Gd3+, U4+.
• A few compounds with even number of electrons.
E.g., O2, organic biradicals.
• Metals
 Quantum Theory of Paramagnetism
Magnetic moment of free atom or ion: μ    J   g B J J  LS
Caution: J here is
γ = gyromagnetic ratio. μB = Bohr magneton. dimensionless.
g  B   
g = g factor. e
B  ~ spin magnetic moment of free electron
2mc
For electrons g = 2.0023
J  J  1  S  S  1  L  L  1
For free g  1
2 J  J  1
atoms,
U  μ  B  m J g  B B mJ   J ,  J  1,  , J  1, J

For a free electron, L = 0, S = ½ , g = 2, Anomalous

→ mJ =  ½ , U =  μB B. Zeeman effect

N e   B

N e   B  e   B

N eB
 B
N e  e   B
 N e x
 x e x  e x
B N e  e x M   N  N    N  x  N  tanh x
x e  e x
k BT N ex
 x N 2 B
N e  e x High T ( x << 1 ): M  N x 
kB T

Curie-Brillouin law:
g J B B
M  N g J  B BJ  x  x
kB T

Brillouin
function:
2J 1   2 J  1 x  1  x 
BJ  x   ctnh    ctnh  
2J  2 J  2 J  2 J 
 g J B B
M  N g J  B BJ  x  x
kB T

2J 1   2 J  1 x  1  x 
BJ  x   ctnh   ctnh  
2J  2 J  2 J  2 J 
1 x x3
High T ( x << 1 ): ctnh x    
x 3 45

M N J  J  1 g  B N p 2  B2 C
2 2
 Curie
  
B 3 k BT 3 k BT T law

= effective number
pg N J  J  1 of Bohr magnetons

Gd (C2H3SO4)  9H2O
 Rare Earth Ions

Lanthanide
contraction

ri = 1.11A

ri = 0.94A

Perturbation from higher states

4f radius ~ 0.3A significant because splitting
between L-S multiplets ~ kB T
 Hund’s Rules
For filled shells, spin orbit couplings do not change order of levels.

Hund’s rule ( L-S coupling scheme ):

Outer shell electrons of an atom in its ground state should assume
1.Maximum value of S allowed by exclusion principle.
2.Maximum value of L compatible with (1).
3.J = | L−S | for less than half-filled shells.
J = L + S for more than half-filled shells.

Causes:
1. Parallel spins have lower Coulomb energy.
2. e’s meet less frequently if orbiting in same direction (parallel Ls).
3. Spin orbit coupling lowers energy for LS < 0.

Mn2+: 3d 5 (1) → S = 5/2 exclusion principle → L = 2+1+0−1−2 = 0

2
Ce3+: 4f1 L = 3, S = ½ (3) → J = | 3− ½ | = 5/2 F5/2
3
Pr3+: 4f2 (1) → S = 1 (2) → L = 3+2 = 5 (3) → J = | 5− 1 | = 4 H4
Iron Group Ions

L=0
 Crystal Field Splitting

Rare earth group: 4f shell lies within 5s & 5p shells

→ behaves like in free atom.
Iron group: 3d shell is outer shell
→ subject to crystal field (E from neighbors).
→ L-S coupling broken-up; J not good quantum number.
Degenerate 2L+1 levels splitted ; their contribution to moment diminished.
 Quenching of the Orbital Angular Momentum
Atom in non-radial potential → Lz not conserved.
If  Lz  = 0, L is quenched.
μ   B L  2S  L is quenched → μ is quenched

L = 1 electron in crystal field of orthorhombic symmetry ( α = β = γ = 90, a  b  c ):

e   A x2  B y 2  C z 2  2  0  A B C  0 → e   Ax 2  By 2   A  B  z 2

Consider wave functions: U j  xj f  r → L 2 U j  L  L  1 U j  2 U j

d rU Uj
3 *
For i  j, the integral i is odd in xi & xj , and hence vanishes.

i.e., Ui e  U j  i j Ui e  Ui

U x e  U x   d 3r f  r   A x 4  B x 2 y 2   A  B  x 2 z 2   A  I1  I 2 
2

I1   d 3r f  r  I 2   d 3r f  r 
2 2
where x 4j xi2 x 2j

Similarly Uy e Uy  B  I1  I 2  U z e  U z    A  B   I1  I 2 
 Uj are eigenstates for the atom in crystal field.

Orbital moments are zero since U j Lz U j 0 Quenching

For lattice with cubic symmetry,

e   A  x2  y2  z 2   2  0  A0

 there’s no quadratic terms in e φ .

→ Ground state remains triply degenerate.

Jahn-Teller effect: energy of ion is lowered by spontaneous lattice distortion.
E.g., Mn3+ & Cu2+ or holes in alkali & siver halides.
 Spectroscopic Splitting Factor
λ = 0 or H = 0 → Uj degenerate wrt Sz.
In which case, let A, B be such that ψ0 = x f(r) α is the ground state, where
α (spin up) and β (spin down) are Pauli spinors.
1st order perturbation due to λ LS turns ψ0 into
   
  U x  i U y   Uz  where 1   y   x 2   z   x
 21  2 2

α | β  = 0 → term Uz β ~ O(λ2) in any expectation values.

 It can be dropped in any 1st approx.

Thus  Lz   
1
  
 z   B  Lz  2S z      1  B
 1 
  
Energy difference between Ux α and Ux β in field B : E  g  B H  2  1    B H
 1 
  
→ g  2 1  
 1 
 Van Vleck Temperature-Independent Paramagnetism
Consider atomic or molecular system with no magnetic moment in the ground state , i.e.,
0 z 0  s z s 0

In a weak field μz B << Δ = εs – ε0 ,

B B
0  0  0  s s z 0 s  s  s  0 0 z s
 
B 2
0 z 0  0  z 0  2 s z 0

B 2
s z s  s  z s  2 s z 0

a) Δ << kB T b) Δ >> kB T

N0  N s  N N0  N s  N
2 k BT
2B 2 N 2B 2
M s z 0 M s z 0 N
 2 kB T 
1 2N 2 van Vleck
N s z 0
2
Curie’s
 s z 0 paramagnetism
kB T 
law
 Cooling by Isentropic Demagnetization

Was 1st method used to achieve T < 1K.

Lowest limit ~ 10–3 K .
Mechanism: for a paramagnetic system at fixed T, Δ  < 0 as H increases.
i.e., H aligns μ and makes system more ordered.
→ Removing H isentropically (Δ  = 0) lowers T.

Lattice entropy can seeps in

during demagnetization

Magnetic cooling is not cyclic.

 Isothermal magnetization

Isoentropic demagnetization
T2

S  k B ln  2S  1  N k B ln  2S  1
N
Spin entropy if all states are accessible:

 is lowered in B field since lower energy states are more accessible.

Population of magnetic sublevels is function of μB/kBT, or B/T.

B B B
 Δ=0→  or T2  T1 BΔ = internal random field
T1 T2 B
 Nuclear Demagnetization
B
T2  T1
B
m p ~ 1836 me
5.58
g p ~ 5.58 →  p ~ e ~ 1.52 103  B
2  1836
g n ~ 3.83
T2 = T1 ( 3.1 / B )
→ T2 of nuclear paramagnetic cooling
~ 10–2 that of electronic paramagnetic cooling.

p B
B = 50 kG, T1 = 0.01K, →  0.5
k B T1
B
 6.72 10 5 G / K
kB

Δ on magnetization is over 10% max. →

phonon Δ negligble.
Cu: T1 = 0.012K
102 100G
BΔ =3.1 G T2  0.01K  2 10 7 K
50kG
 Paramagnetic Susceptibility of Conduction Electrons
N  B2 B
Classical free electrons: M ~ Curie paramagnetism
k BT

Experiments on normal non-ferromagnetic metals : M independent of T

Pauli’s resolution:
Electrons in Fermi sea cannot flip over due to exclusion principle.
Only fraction T/TF near Fermi level can flip.

N  B2 B T N  B2 B
 M  
k BT TF k B TF
Pauli paramagnetism at T = 0 K

 
T=0 1 F 1 F 1
N   d  D     B    d D      B D   F  parallel moment
2  B 2  B 2

 
1 F 1 F 1
N   d  D     B    d  D      B D   F  anti-parallel moment
2  B 2  B 2

3N  2
M Pauli    N   N     B D F 
2
 B χ > 0 , Pauli paramagnetism
2k BTF

Landau diamagnetism: M Landau N2 N2

 B M  M Pauli  M Landau  B
2k BTF →
2k BTF
χ is higher in transition metals due to higher
Prob. 5 &6