FoP 3B Part I

Dr Budhika Mendis ([email protected])

Room 151

Lecture 5: Diamagnetism
 Summary of Lecture 4
Classical magnetic moments: Magnetic fields in solids:

B = μ0(H + M)

M = H

ferromagnet (MH-curve
M non-linear w.r.t. H)
l paramagnet
∂ H
diamagnet
μ = -γl (for electrons)
𝑒ℏ
𝜇𝐵 = γℏ =
2𝑚
𝑑𝛍
= −γ(𝛍 × 𝐁)
𝑑𝑡

Magnetism in solids is
a quantum mechanical
phenomenon
 Aim of today’s lecture

Introduction to diamagnetism (simplified case of a system of non-

interacting atoms/ions).

Key concepts:
∂
-Classical physics explanation of diamagnetism
-Quantum mechanical origin
-Magnetic susceptibility of diamagnetic ions
Magnetic susceptibility in atoms

Vast majority of atoms are either diamagnetic or paramagnetic. Ferromagnetism is

relatively rare amongst elements.
 Magnetism as a quantum mechanical phenomenon
-The energy E of a magnetic moment μ is E = -μB. Therefore the magnetisation:
𝑑𝐸vol
𝑀=−
𝑑𝐵
where Evol is the energy per unit volume.
- Since the Lorentz force F = -e(v x B) is normal to the velocity v a magnetic field cannot
do any work on a moving electron. Therefore according to classical physics the
magnetisation must be zero!

∂ phenomenon (the Bohr- van Leeuwen

- Magnetism is therefore a quantum mechanical
theorem demonstrates this rigorously using statistical physics).

The torque  is given by:

𝛕= 𝛍×𝐁
dμ
Since  = dl/dt and μ = -γl:
𝑑𝛍
= −γ(𝛍 × 𝐁)
𝑑𝑡
μ
μ precesses around the B-field.
Langevin theory (classical physics)

Let B-field be along z, i.e. B = (0,0,B). The moment μ = (μx,μy,μz).

z 𝑑𝛍
ω From the precession formula 𝑑𝑡
= −γ 𝛍 × 𝐁 :
𝑑𝜇𝑥 𝑑𝜇𝑦
μ = −𝛾𝐵𝜇𝑦 ; = 𝛾𝐵𝜇𝑥
𝑑𝑡 𝑑𝑡
𝑑𝜇𝑧
=0 (μz unchanged)
𝑑𝑡
∂
If at time t = 0 the moment μ is in the xz-plane, we have:
𝜇𝑥 𝑡 = 𝜇 sin 𝜃 cos 𝜔𝑡 ; 𝜇𝑦 𝑡 = 𝜇 sin 𝜃 sin 𝜔𝑡 ;
𝑒𝐵
𝜔 = 𝛾𝐵 =
2𝑚
Larmor frequency

The Larmor precession induces a magnetic field opposing the applied

B-field. This is sometimes described a being due to Lenz’ law and is
the origin of diamagnetism (according to classical physics).
 Langevin theory- Magnetic susceptibility
-The electron precesses in an applied magnetic field B with frequency ω = eB/2m. The precession
period is therefore T = 2/ω = 4m/eB. The precession current is I = e/T = e2B/4m.

-To calculate the induced moment we need to multiply -I by the area of current loop, i.e. <2>,
where <2> is the mean square radius of the precessing electron from the atom nucleus. Note the
minus sign in -I is to indicate the induced moment opposes the applied field.

-For a spherically symmetric atom <x2> = <y2> = <z2>. Since <r2> = <x2> + <y2> + <z2>,
we have <2> = <x2> + <y2> = 2/3 <r2>.

-The moment of a single electron is -I(<2>) or ∂

-e2B<r2>/6m. Assume there are n atoms/ions per
unit volume each with Z electrons. The magnetisation M is therefore:
𝑛𝑒 2 𝑍𝐵 < 𝑟 2 >
𝑀=−
6𝑚

-For weak magnetisation B = μ0(H+M)  μ0H. Therefore  = M/H = μ0M/B. The diamagnetic
susceptibility is then:

𝑛𝑒 2 𝜇0 𝑍 < 𝑟 2 >
𝜒=−
6𝑚
 Quantum Mechanical picture
The electron Hamiltonian in a magnetic field (B =  x A) is given by:
canonical momentum* Energy due to spin moment
𝐩 + 𝑒𝐀 2 (from E = -μB and μ = -gsγs)
෡
𝐻= + 𝑉 + 𝑔𝑠 γ𝐁 ⋅ 𝐬
2𝑚
Lande g-factor (gs  2)

Set the gauge to A(r) = (B x r)/2. Then:

𝐩2 𝑒 𝑒 2 𝐀2
𝑚 ∂
෡=
𝐻 +𝑉 + 𝐩𝐀 + 𝑔𝑠 γ𝐁 ⋅ 𝐬 +
2𝑚 2𝑚
𝑒 𝑒
But 𝐩∙𝐀 = 𝐩 ⋅ 𝐁 × 𝐫 = 𝛾𝐁 ⋅ 𝐫 × 𝐩
𝑚 2𝑚
l
𝐩2 𝑒2
෡=
𝐻 + 𝑉 + γ𝐁 ⋅ 𝐥 + 𝑔𝑠 𝐬 + 𝐁×𝐫 2
2𝑚 8𝑚

paramagnetic term diamagnetic term

*See supplementary reading (non-examinable)

Magnetic susceptibility (Quantum Mechanics)
By first order perturbation theory the energy change (∆E) to the ground state
wavefunction |0> due to the diamagnetic term is:
𝑒2
Δ𝐸 = 0 𝐁×𝐫 2 0
8𝑚
If B is along the z-axis then (B x r)2 = B2(x2+y2). Therefore:
𝑒 2 𝐵2
Δ𝐸 = 0 𝑥2 0 + 0 𝑦2 0
8𝑚
<x2> <y2>
∂
Since <x2> = <y2> = <r2>/3:
𝑒 2 𝐵2 2 (NB: since <r2> is always positive energy
Δ𝐸 = 𝑟 increases due to magnetic field)
12𝑚
The magnetic moment μ = -d(∆E)/dB, so that for n atoms/ions per unit volume each with
Z electrons the magnetisation is:
𝑛𝑒 2 𝑍𝐵 2
𝑀=− 𝑟
6𝑚
For weak magnetisation (i.e.  = μ0M/B):
𝑛𝑒 2 𝜇0 𝑍 < 𝑟 2 >
𝜒=− (identical result to classical physics!)
6𝑚
Experimental confirmation of theory

𝑛𝑒 2 𝜇0 𝑍 < 𝑟 2 >
𝜒=−
6𝑚

Linear relationship between  and Z<r2>

Large diamagnetism in delocalised electron solids

Diamagnetic term:

(B x r)2

<r> If B is in the plane of the delocalised

electrons (B x r)2 = 0 and there is no
magnetic response, i.e.  = 0.
∂
(B x r)2 and  is maximum when B is
perpendicular to the delocalised
Benzene Graphite electrons.

This is known as magnetic anisotropy.

<r> for the ‘molecule’ is much larger than an atom
leading to strong diamagnetism
 Magnetic levitation of diamagnets
Graphite
sheet

Permanent
magnets

Diamagnets will seek minima in the magnetic field causing them to levitate if
the field is strong enough!