Quantum Theory of Free Electrons

To overcome the drawbacks of classical free electron theory, Sommerfeld proposed quantum
free electron theory by applying principles of Quantum mechanics in 1928. He treated
electron as a quantum particle. He retains the vital features of classical free electron theory
and included the Pauli Exclusion Principle & Fermi-Dirac statistics instead of Maxwell
Boltzmann statistics. The following are the assumptions of quantum free electron theory.
1. The electrons obey Pauli’s Exclusion Principle, which states that there cannot be more than two
electrons in any energy level.
2. The distribution of electrons in various energy levels obey the Fermi-Dirac quantum statistics.
3. Free electrons have the same potential energy everywhere within the metal, because the
potential due to ionic cores is uniform throughout the metal.
4. The force of attraction between electrons & lattice ions and the force of repulsion between
electrons can be neglected.
5. Free electrons move freely in a constant potential within the boundaries of metal and is
prevented escaping from the metal (high potential). Hence the electrons are trapped in a
potential well.
6. The free electrons in a metal can have only discrete energy values. Thus the energies are
quantized.
7. To find the possible energy values of electrons the Schrodinger time independent equation is
applied. The problem is similar to particle present in a potential box.
𝑛2 ℎ 2
𝐸𝑛 = , 𝑤ℎ𝑒𝑟𝑒 𝑛 = 1, 2, 3 … . .
8𝑚 𝐿2
8. Electrons are treated as wave-like particles.
 Distribution laws, Fermi Level & Fermi Energy
Maxwell Boltzmann distribution (for classical model):
In Maxwell Boltzmann distribution all the particles in the system are distinguishable and no more
restrictions on filling the particles in the energy levels. This is mainly applicable for atoms and
molecules. According to Maxwell Boltzmann distribution, the probability of occupying an energy
1
level (Ei) is: 𝑓 𝐸𝑖 = 𝐸 −𝐸
𝑖 𝐹
𝑒 𝑘𝑇

Fermi Dirac distribution

In Fermi Dirac distribution all the particles in the system are indistinguishable and it obeys Pauli’s
exclusive principle. According to Pauli’s exclusion principle, each energy level can accommodate a
maximum of two electrons, one with spin up (+½) and the other with spin down (-½). At absolute
zero temperature, two electrons with opposite spins will occupy the lowest available energy level.
The next two electrons with opposite spins will occupy the next energy level and so on. Thus, the
top most energy level occupied by electrons at absolute zero temperature is called Fermi-energy
level. The energy corresponding to that energy level is called Fermi energy.
The energy of the highest occupied level at zero degree absolute temperature is called Fermi
energy, and the energy level is referred to as the Fermi level. The Fermi energy is denoted as EF. All
energy levels below Fermi level are completely filled and above which all energy levels are
completely empty.
At temperatures above absolute zero, the electrons get thermally excited and move up to higher
energy levels. As a result there will be many vacant energy levels below as well as above Fermi
energy level. Under thermal equilibrium, the distribution of electrons among various energy levels
is given by statistical function f(Ei).
 Distribution laws, Fermi Level & Fermi Energy
The function f(Ei) is called Fermi-factor and this gives the probability of occupation of a given
energy level under thermal equilibrium. The expression for f(Ei) is given by,

1
𝑓 𝐸𝑖 = 𝐸𝑖 −𝐸𝐹
𝑒 𝑘𝑇 +1

Where f(Ei) is called Fermi-Dirac distribution function or

Fermi factor, EF is the Fermi energy, k is the Boltzmann
constant and T is the temperature of metal under thermal
equilibrium.

Variation of Fermi factor with Energy and Temperature

(i) When Ei < EF & T = 0 K, from the probability function f(Ei) we have
1 1 1
𝑓 𝐸𝑖 = 𝐸 −𝐸 = −∞ = =1
𝑖 𝐹 𝑒 +1 0+1
𝑒 𝑘𝑇 + 1
i.e., f(Ei) = 1 for E < EF at T = 0 K. This implies that at absolute zero temperature, all the energy levels
below EF are 100% occupied which is true from the definition of Fermi energy.
 Distribution laws, Fermi Level & Fermi Energy Continueed ……….
(ii) When Ei > EF & T = 0 K, then f(Ei) becomes
1 1 1 1
𝑓 𝐸𝑖 = = = = =0
𝐸𝑖 −𝐸𝐹 𝑒∞ + 1 ∞ + 1 ∞
𝑒 𝑘𝑇 +1
i.e., f(Ei) = 0 for Ei > EF at T = 0 K. This implies that at absolute zero temperature, all the energy
levels above EF are unoccupied (completely empty) which is true from the definition of Fermi
energy.

(iii) When Ei = EF & T = 0 K, then f(E) becomes

1 1
𝑓 𝐸𝑖 = 𝐸𝑖 −𝐸𝐹
= = 𝐼𝑛𝑑𝑒𝑟𝑚𝑖𝑛𝑎𝑡𝑒
𝑒0 0 +1
𝑒 𝑘𝑇 +1
Hence, the occupation of Fermi level at T = 0 K has an undetermined value ranging between zero
and unity (0 & 1). The Fermi-Dirac distribution function is discontinuous at Ei = EF for T = 0 K.

(iv) When Ei = EF & T > 0 K, then f(E) becomes

1 1 1 1
𝑓 𝐸𝑖 = 𝐸 −𝐸 = 0 = =
𝑖 𝐹 𝑒 +1 1+1 2
𝑒 𝑘𝑇 + 1
i.e., f(Ei) = ½ for Ei = EF at T > 0 K.
 Distribution laws, Fermi Level & Fermi Energy Continueed ……….
The variation of Fermi factor with energy and temperature is as shown in figure given below.

If Ei < EF, the probability starts decreasing from 1 and reaches 0.5 (½) at Ei = EF and for Ei > EF, it
further falls off as shown in figure. In conclusion, the Fermi energy is the most probable or average
energy of the electrons in a solid.

In summary: when T > 0 K

f(Ei) < 1 (but > ½) for Ei < EF
f(Ei) > 0 (but < ½) for Ei > EF
Ei = EF , f(Ei) = 1/2
So the Fermi level can be defined as The energy level for which the probability of occupation is ½
or 50% at any temperature.
 Energy Levels for Free Electrons in 1D Box
Consider free electron gas is confined by high (infinite) potential energy barriers
within a one-dimensional crystal of length L. The potential energy everywhere
within the crystal is constant and is equal to zero.
Consider a free electron of mass of mass m in the crystal as shown in the Fig.
Since the potential energy inside the crystal is zero, the time independent
Schrodinger equation has the form,
𝑑2  𝑥 2𝑚𝐸
+ 2  𝑥 = 0 … … … … . (1)
𝑑𝑥 2 ħ
The general solution of this Eq. is of the form,
 𝑥 = 𝐴 𝑠𝑖𝑛 𝑘𝑥 + 𝐵 𝑐𝑜𝑠 𝑘𝑥 … … (2)
Where A, B and k are constants.
We now apply our boundary conditions to find the solution to our particular
system. According to our boundary conditions, the probability of finding the
electron at x=0 or x=L is zero. When x=0, then sin(0)=0 and cos(0)=1;
therefore, B must equal 0 to fulfill this boundary condition giving:
 𝑥 = 𝐴 𝑠𝑖𝑛 𝑘𝑥 … … … … (3)
We can now solve for constants (A and k) to find the wavefunction.
 Energy Levels for Free Electrons in 1D Box continued ….

𝑑
Differentiating with respect to x, 𝑑𝑥
= 𝑘𝐴 𝑐𝑜𝑠 𝑘𝑥 … … … . (4)
𝑑2 
Differentiating again with respect to x, 𝑑𝑥 2
= −𝑘 2 𝐴 𝑠𝑖𝑛 𝑘𝑥 … … … . (5)
𝑑2 
That is, 𝑑𝑥 2
= −𝑘 2  𝑥 … … … . (6)
Substituting (d2/dx2) from Eq. (6) into Eq. (1) and solve for k,
1 2
2𝑚𝐸 8𝜋 2 𝑚𝐸
𝑘2 = →→ 𝑘 = … … … . (7)
ħ2 ℎ2
1 2
8𝜋2 𝑚𝐸
Hence the wavefunction for the electron,  𝑥 = 𝐴 sin ℎ2
𝑥 … … … (8)

Now using the boundary condition that the probability of finding the electron at x = 0 or x = L
is zero, that is for x = L in Eq. (8),
1 2
8𝜋 2 𝑚𝐸
0 = 𝐴 sin 𝐿 … … … (9)
ℎ2

1 2
8𝜋2 𝑚𝐸
Therefore from Eq. (9), ℎ2
𝐿 = 𝑛𝜋 … … … (10)
where, n = 1, 2, 3, ….
 Energy Levels for Free Electrons in 1D Box continued ….
From Eq. (10), it is clear that electronic energy can have only the discrete values,
𝑛2 ℎ 2
𝐸𝑛 = … … … (11)
8𝑚𝐿2
Equation (11) is a very important result and tells us that:
1. The energy of a particle is quantized.
2. The lowest possible energy of a particle is NOT zero. This is called the zero-point energy and means
the particle can never be at rest because it always has some kinetic energy.
This is also consistent with the Heisenberg Uncertainty Principle: if the particle had zero energy, we would know
where it was in both space and time.
𝑛𝜋
Putting Eq. (10) into Eq. (8),  𝑥 = 𝐴 𝑠𝑖𝑛 𝑥 … … … … (12)
𝐿
To determine A, recall that the total probability of finding the particle inside the box is 1, meaning there is
no probability of it being outside the box. When we find the probability and set it equal to 1, we
are normalizing the wavefunction. That is,
𝐿 𝐿
𝑛𝜋
 𝑑𝑥 = 1 →→→ 𝐴
2 2
𝑠𝑖𝑛2 𝑥𝑑𝑥 = 1 … … … … … (13)
0 0 𝐿
2
After integration, one gets, 𝐴 =
𝐿
Hence the normalized wavefunction for an electron in 1D box is,
2 𝑛𝜋
𝑛 𝑥 = 𝑠𝑖𝑛 𝑥 … … … … … … … (14)
𝐿 𝐿
Where, n = 1, 2, 3, ……….
 Free electrons in a box Continued …
Suppose the wavefunctions for an election
in a box at n=1 and n=2 energy levels look
like this:

Then, the probability of finding the electron

a certain spot in the box is determined by
squaring ψ. The probability distribution
for an electron in a box at the n=1 and n =2
energy levels looks like this:

The number of nodes (places where the

particle has zero probability of being
located) increases with increasing n. Also
note that as the energy of the particle
becomes greater, the quantum mechanical
model breaks down as the energy levels
get closer together and overlap, forming a continuum. This continuum means the particle
is free and can have any energy value. At such high energies, the classical mechanical
model is applied as the particle behaves more like a continuous wave. Therefore, the
particle in a box problem is an example of Wave-Particle Duality.