QUANTUM

MECHANICS
THE FREE ELECTRON GAS MODEL
• The Fermi energy is equal to the maximum kinetic energy:
ℏ2
𝐸𝐹 = 3𝜌𝜋 2 2/3
2𝑚
• In 1D k-space, one point occupies 𝜋/𝐿 in k-space. The number of points in k-
𝜋
space is 𝑘𝐹 ൗ .
𝐿

2 𝑛𝜋𝑥 2
• 𝜓𝑛 𝑥 = sin = sin 𝑘𝑛 𝑥 . Each value of 𝑘𝑛 defines a 𝜓𝑛 𝑥 .
𝐿 𝐿 𝐿
THE FREE ELECTRON GAS MODEL
• For the infinite cubical well, we set 𝐿𝑥 = 𝐿𝑦 =
𝐿𝑧 = 𝐿.
𝑛𝑥 𝜋 𝑛𝑦 𝜋 𝑛𝑧 𝜋
𝑘𝑥 = , 𝑘𝑦 = , 𝑘𝑧 =
𝐿 𝐿 𝐿
• In 3D k-space, each point represents a wave
function. We plot points to a maximum radius 𝑘𝐹 .
We have 𝑁𝑞 free electrons in the system. They
are fermions and so obey the Pauli exclusion
principle – only 2 electrons (with opposite spin)
can occupy one wave function.

• For example, 𝜓111 − ↑↓, 𝜓121 − ↑↓

THE FREE ELECTRON GAS MODEL
ℏ2 𝑘 2 𝜋 2 ℏ2 𝑛𝑥2 𝑛𝑦2 𝑛𝑧2
𝐸𝑛𝑥𝑛𝑦 𝑛𝑧 = = 2
+ 2+ 2
2𝑚 2𝑚 𝐿 𝐿 𝐿

8 𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦 𝑛𝑧 𝜋𝑧
𝜓𝑛𝑥𝑛𝑦 𝑛𝑧 𝒓 = sin sin sin
𝑉 𝐿 𝐿 𝐿

• 3 wave functions can be linked to a single

energy level for the first excited state-3-fold
degeneracy
• Nq electrons fill up in pairs 1/8 of a sphere in 3D
k-space, whose radius 𝑘𝐹 is determined by the
fact that each pair of electrons (each point)
requires a volume 𝜋 3 /𝑉 in k-space.
THE FREE ELECTRON GAS MODEL
1 4 3 𝑁𝑞 𝜋 3
𝜋𝑘𝐹 =
8 3 2 𝑉
⇒ 𝑘𝐹 = 3𝜌𝜋 2 1/3

where the free electrons density is

𝜌 = 𝑁𝑞/𝑉

• 𝑘𝐹 is the Fermi wave vector magnitude. The boundary separating the occupied
and unoccupied states in k-space is called the Fermi surface.
• The maximum occupied energy is the Fermi energy:
ℏ2
𝐸𝐹 = 3𝜌𝜋 2 2/3
2𝑚
THE FREE ELECTRON GAS MODEL
• The total energy (assuming zero potential energy) of the electron gas can be
calculated as follows: a shell of thickness 𝑑𝑘 contains a volume
1
4𝜋𝑘 2 𝑑𝑘
8
• Therefore, the number of electron states in the shell is
1
2 𝜋𝑘 2 𝑑𝑘 𝑉 2
2
3 = 2 𝑘 𝑑𝑘
𝜋 /𝑉 𝜋

ℏ2 𝑘 2
• Each of these states carries an energy , so the energy of shell is
2𝑚

ℏ2 𝑘 2 𝑉 2
𝑑𝐸 = 2
𝑘 𝑑𝑘
2𝑚 𝜋
THE FREE ELECTRON GAS MODEL
• Hence, the total energy of the electron gas is
5
2
ℏ 𝑉 𝑘𝐹
ℏ2 𝑘𝐹5 𝑉 2
ℏ 3𝜋 𝑁𝑞 2 3
𝐸𝑡𝑜𝑡 = 2 න 𝑘 4 𝑑𝑘 = = 𝑉 −2/3
2𝜋 𝑚 0 10𝜋 2 𝑚 10𝜋 2 𝑚

• This is a quantum mechanical energy. It plays a role analogous to the internal

thermal energy 𝑈 of an ordinary gas. In particular, it exerts a pressure on
the walls, for if the box expands by an amount 𝑑𝑉, the total energy decreases:
5
2 ℏ2 3𝜋 2 𝑁𝑞 3
−
5 2 𝑑𝑉
𝑑𝐸𝑡𝑜𝑡 =− 𝑉 3 𝑑𝑉 = − 𝐸𝑡𝑜𝑡
3 10𝜋 2 𝑚 3 𝑉
THE FREE ELECTRON GAS MODEL
• This decrease in energy shows up as work done on the outside 𝑑𝑊 = 𝑃𝑑𝑉
by the quantum pressure 𝑃. Evidently,
2
2 𝐸𝑡𝑜𝑡 2 ℏ2 𝑘𝐹5 3𝜋 2 3 ℏ2
𝑃= = = 𝜌5/3
3 𝑉 3 10𝜋𝑚 5𝑚
• This is a partly why cold objects don’t collapse. There is a stabilizing internal
pressure that has nothing to do with electron-electron repulsion (which we
have ignored) or thermal motion (which we have excluded) but is strictly
quantum mechanical. It derives from the antisymmetrization requirement for
the wave functions of identical fermions. It is sometimes called degeneracy
pressure.