Origin of magnetism

Stephen Blundell
University of Oxford

European School of Magnetism 2020

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Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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 Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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Lagrangian for a charged particle in a magnetic field

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 Lagrangian for a charged particle in a magnetic field

Bohr-van Leeuwen theorem

Niels Bohr Hendrika Johanna van Leeuwen

(1885-1962) (1887-1974)

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 Bohr-van Leeuwen theorem
p = mv + qA
= Z= ··· exp( E({ri , pi }) dr1 · · · drN dp1 · · · dpN

In a magnetic field, we replace pi by pi qA

Bohr-van Leeuwen theorem

p = mv + qA
= Z= ··· exp( E({ri , pi }) dr1 · · · drN dp1 · · · dpN

In a magnetic field, we replace pi by pi qA

F =kB T log Z
⇥
F
M=
B T

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 Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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Orbtial magnetism – connection to angular momentum

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 Orbtial magnetism – connection to angular momentum

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Orbtial magnetism – connection to angular momentum

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 Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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Spin

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 Spin

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Spin

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 Spin

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Spin

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 Spin

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Spin arrangements

⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥
⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥
⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ antiferromagnet
⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥
⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥ ⇥

ferromagnet

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 Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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Spin precession

spin precession

E-fields don’t do
this to electric
dipole moments

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 Spin precession

Classical treatment of spin precession

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Spin precession

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 Spin matrices and states

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Spin matrices and states

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 Spin precession

Quantum mechanical treatment of spin precession (1)

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Spin precession

Quantum mechanical treatment of spin precession (2)

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 Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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31

S. J. Blundell, Magnetism in Condensed Matter (OUP, 2001)

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 Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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 Hamiltonian for electrons in an atom in a B field

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 S. J. Blundell, Magnetism in Condensed Matter (OUP, 2001)

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43

Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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 Orbitals

s-orbitals

p-orbitals

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S. J. Blundell, Magnetism in Condensed Matter (OUP, 2001)

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Orbitals
d-orbitals

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S. J. Blundell, Magnetism in Condensed Matter (OUP, 2001)

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 Magnetic atoms and ions

3d

4f

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S. J. Blundell, Magnetism in Condensed Matter (OUP, 2001)

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Transition metal
(3d) ions

Partially filled 3d shell gives

rise to a magnetic moment

S.J. Blundell, Contemp. Phys. 48, 275 (2007) 48

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 Transition metal
(3d) ions

CuII = 3d9
Partially filled 3d shell gives
rise to a magnetic moment

S.J. Blundell, Contemp. Phys. 48, 275 (2007) 49

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Spin-orbit and Lz eigenstates

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 Crystal field

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 A parable: p-orbitals

real eigenfunctions, for V(r) which is real

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A parable: p-orbitals

Ylm ( , ⇥) l=1 m = 0 cos

m = 1 sin ei
m = 1 sin e i

⇥
L̂z = i imaginary, |m eigenfunctions
⇥
|pz = |0
|1⇥ + | 1⇥ note that these contain
|px ⇥ = ⇤ the eigenfunctions |m and
2 | m⇥ in equal mixtures
|1⇥ | 1⇥
|py ⇥ = ⇤
2i 54

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 d-orbitals
|2, ±2i
sin2 ✓e±2i
|2, 0i
3 cos2 ✓ 1

|2, ±1i sin ✓ cos ✓e±i 55

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d-orbitals

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Jahn-Teller distortion in a 3d4 ion

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 Example (1)

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Example (2)

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 Outline
1. Bohr-van Leeuwen theorem

2. Orbital magnetism

3. Spin magnetism

4. Spin precession

5. Hund’s rules

6. Diamagnetism and paramagnetism

7. Orbitals and the crystal field

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