Quantum Free Electron Theory
Course Instructor
Dr. Nitish Kumar Singh
Associate Professor, Faculty of Physical Sciences
Email: [Link]@[Link]
Dean
Dr. R. G. Singh
Associate Professor, Faculty of Physical Sciences
Institute of Natural Sciences & Humanities
Email: [Link]@[Link]
SHRI RAMSWAROOP MEMORIAL UNIVERSITY, BARABANKI-225003
Introduction
Drude and Lorentz had tried to explain the electrical properties of
metals using free electron theory.
The free electron theory can be classified into two categories
according to used statistics:
Classical Free Electron Theory
Quantum Free Electron Theory
Quantum Free Electron Theory
Classical free electron theory was failed to explain some properties
of metals.
To explain these properties Sommerfeld developed a new theory
using the quantum statistics.
This new theory is called quantum free electron theory.
This theory is based on the following assumptions:
Assumptions of Quantum Free
Electron Theory
Metals are made up of positive ion cores and valence electrons.
The valence electrons moves freely among these ion cores.
The valence electrons are bound to move within the metal under the
influence of electrostatic attraction acting between the positive ion
cores and the valence electrons.
The potential field (responsible for electrostatic attraction) of these
ion cores is considered to be constant throughout the metal.
Assumptions of Quantum Free
Electron Theory
The mutual repulsion among the electrons is neglected.
The valence electrons obey the Pauli’s exclusion principle and
responsible for electrical conduction.
The potential energy of valence electrons is constant because they
move under uniform electrostatic field of ion cores and it is
normally taken as zero. Thus the valence electron have only kinetic
energy as total energy.
Assumptions of Quantum Free
Electron Theory
The potential energy of a stationary electron inside the metal is less
than the potential energy of an identical stationary electron just
outside it. This difference of potential energy act as potential barrier
for electron inside the metal and restrict the valence electron to leave
the metal surface.
The valence electron obey the Fermi-Dirac statistics which is the
quantum statistics.
Assumptions of Quantum Free
Electron Theory
The possible electronic energy states in the potential energy box is
governed by quantum statistics.
The distribution of electrons in these electronic states is also
governed by the quantum statistics.
Quantum Free Electron Theory
To find out the possible electronic energy states, let us consider an
electron having mass m and bound to move within a one dimensional
crystal of length L. The presence of large potential energy barrier at the
surfaces restrict the electron to leave the crystal. Thus the above
situation is similar to the motion of electron in a one dimensional
potential box as shown in Fig.1.
Quantum Free Electron Theory
𝑉𝑉 𝑥𝑥 = ∞ 𝑉𝑉 𝑥𝑥 = ∞
The potential energy of the electron
is given by
𝑉𝑉 𝑥𝑥 = 0 𝑓𝑓𝑓𝑓𝑓𝑓 0 < 𝑥𝑥 < 𝐿𝐿
𝑉𝑉 𝑥𝑥 = ∞ 𝑓𝑓𝑓𝑓𝑓𝑓 0 ≤ 𝑥𝑥 ≥ 𝐿𝐿 (1)
𝑉𝑉 𝑥𝑥 = 0
𝑥𝑥 = 0 𝑥𝑥 = 𝐿𝐿
Fig.1: Electron in one dimension
infinite potential well
Quantum Free Electron Theory
The wave function 𝜓𝜓𝑛𝑛 of the electron occupying the nth energy states is
given by the solution of time independent Schrodinger wave equation
𝑑𝑑 2 𝜓𝜓𝑛𝑛 2𝑚𝑚
+ [𝐸𝐸𝑛𝑛 − 𝑉𝑉 𝑥𝑥 ]𝜓𝜓𝑛𝑛 = 0 (2)
𝑑𝑑𝑥𝑥 2 ћ2
Where 𝐸𝐸𝑛𝑛 represents the kinetic energy of the electron in the nth energy
states & V is its potential energy. The potential energy inside the box is
zero (𝑉𝑉 = 0), thus eq.(2) becomes
Quantum Free Electron Theory
𝑑𝑑 2 𝜓𝜓𝑛𝑛 2𝑚𝑚
+ 𝐸𝐸 𝜓𝜓 =0 (3)
𝑑𝑑𝑥𝑥 2 ћ2 𝑛𝑛 𝑛𝑛
The general solution of above equation is given by
𝜓𝜓𝑛𝑛 𝑥𝑥 = 𝐴𝐴 sin 𝑘𝑘𝑘𝑘 + 𝐵𝐵 cos 𝑘𝑘𝑘𝑘 (4)
where 𝜓𝜓𝑛𝑛 (𝑥𝑥) is the wave function associated with the electron. k is the
waver vector and given as
2𝑚𝑚𝐸𝐸𝑛𝑛
𝑘𝑘 = (5)
ℏ2
Quantum Free Electron Theory
A & B are arbitrary constant that can be determined from the boundary
condition of the problem. The boundary condition for the wave function
is given by
𝜓𝜓𝑛𝑛 0 = 0 & 𝜓𝜓𝑛𝑛 (𝐿𝐿) = 0 (6)
These conditions can be derived from the fact that at boundaries
𝑥𝑥 = 0 & 𝐿𝐿, the potential energy approaches infinite, hence the product
𝑉𝑉(𝑥𝑥)𝜓𝜓𝑛𝑛 𝑥𝑥 in eq.(2) also approaches infinite.
Quantum Free Electron Theory
The wave function may be continuous across the boundary if the kinetic
energy become infinite which is not possible. Hence 𝜓𝜓𝑛𝑛 𝑥𝑥 must vanish
at 𝑥𝑥 = 0 & 𝐿𝐿.
At 𝑥𝑥 = 0 eq. (4) becomes
𝜓𝜓𝑛𝑛 0 = 𝐴𝐴 sin 𝑘𝑘. 0 + 𝐵𝐵 cos 𝑘𝑘. 0
or, 0 = 𝐵𝐵
Putting the value of B in eq. (4) we get
Quantum Free Electron Theory
𝜓𝜓𝑛𝑛 𝑥𝑥 = 𝐴𝐴 sin 𝑘𝑘𝑘𝑘 (7)
At 𝑥𝑥 = 𝐿𝐿 eq. (7) becomes
𝜓𝜓𝑛𝑛 𝐿𝐿 = 𝐴𝐴 sin 𝑘𝑘𝐿𝐿
or, 0 = 𝐴𝐴 sin 𝑘𝑘𝑘𝑘
But A can not be zero, hence
sin 𝑘𝑘𝑘𝑘 = 0
Quantum Free Electron Theory
or, sin 𝑘𝑘𝑘𝑘 = sin 𝑛𝑛𝑛𝑛
or, kL = 𝑛𝑛𝑛𝑛
𝑛𝑛𝑛𝑛
or, k= , 𝑛𝑛 = 1, 2, 3 … … … … … (8)
𝐿𝐿
Thus the allowed wave function is given by
𝑛𝑛𝑛𝑛
𝜓𝜓𝑛𝑛 𝑥𝑥 = 𝐴𝐴 sin 𝑥𝑥 (9)
𝐿𝐿
Quantum Free Electron Theory
Putting the value of k from eq.(8) to eq.(5), we get
𝑛𝑛𝑛𝑛 2𝑚𝑚𝐸𝐸𝑛𝑛
=
𝐿𝐿 ℏ2
𝑛𝑛𝑛𝑛 2 2𝑚𝑚𝐸𝐸𝑛𝑛
or, =
𝐿𝐿 ℏ2
𝑛𝑛2 ℏ2 𝜋𝜋2
or, 𝐸𝐸𝑛𝑛 = (10)
2𝑚𝑚𝐿𝐿2
Eq.(10) gives the allowed energy states of the electron.
Quantum Free Electron Theory
It can be seen that the allowed energy states and the allowed wave
function can be exist only for the integral value of n. The number n is
called the quantum number. Thus the energy spectrum consists of
discrete energy levels and the spacing between the levels is governed by
quantum number n and length L of the specimen. The spacing between
energy levels decreases with increasing length of the specimen.
Quantum Free Electron Theory
Since electron must exist somewhere in the crystal, the constant A in
eq.(9) can be determined using the condition that the probability of
finding an electron inside the crystal is unity i.e.
𝐿𝐿
� 𝜓𝜓𝑛𝑛∗ 𝑥𝑥 𝜓𝜓𝑛𝑛 𝑥𝑥 𝑑𝑑𝑑𝑑 = 1
0
Putting the value of 𝜓𝜓𝑛𝑛 𝑥𝑥 and 𝜓𝜓𝑛𝑛∗ (𝑥𝑥) from eq.(9) we get
𝐿𝐿
2 2
𝑛𝑛𝑛𝑛
𝐴𝐴 � 𝑠𝑠𝑠𝑠𝑠𝑠 𝑥𝑥 𝑑𝑑𝑑𝑑 = 1
0 𝐿𝐿
Quantum Free Electron Theory
𝐴𝐴2 𝐿𝐿 2𝑛𝑛𝑛𝑛
or, ∫ 1 − cos 𝑥𝑥 𝑑𝑑𝑑𝑑 = 1
2 0 𝐿𝐿
𝐴𝐴2 𝐿𝐿
or, , ∫ 𝑑𝑑𝑑𝑑 =1
2 0
𝐴𝐴2
or, × 𝐿𝐿 = 1
2
2
or, 𝐴𝐴 =
𝐿𝐿
Quantum Free Electron Theory
Substituting the value of A in eq.(9) we have normalized wave function
as
2 𝑛𝑛𝑛𝑛
𝜓𝜓𝑛𝑛 𝑥𝑥 = sin 𝑥𝑥
𝐿𝐿 𝐿𝐿
The energy levels and the wave functions corresponding to 𝑛𝑛 =
1, 2,3 & 4 are shown in Fig.2. Also the probability densities of electron
for 𝑛𝑛 = 1, 2,3 & 4 are shown in Fig.3.
Quantum Free Electron Theory
Fig.2: First four wave functions and Fig.3: Probability densities for first
corresponding energy levels of an four energy levels of an electron in
electron in one dimensional crystal one dimensional crystal
Successes of Quantum Free Electron
Theory
The success of the quantum free electron theory is given below:
It successfully explained the heat capacity and paramagnetic
susceptibility of the conduction electrons.
It explained the linear dependence of resistivity on temperature.
It explained the electrical conductivity dependence on electron
concentration.
Failures of Quantum Free Electron
Theory
With above success, this theory have following discrepancy:
It failed to explain why some crystal have metallic properties &
other do not have.
It failed to explain why atomic array in crystals including metals
should prefer certain structure & not others.
References
Solid State Physics, A. J. Dekker, Macmillan India Limited (1991)
Solid State Physics, R. K. Puri and V. K. Babber, [Link] &
Company Pvt. Ltd.(2014)