Chapter 1

Properties of Matter Waves

and Quantum Tunneling

1.1 Wave Function and its significance

The wave function Ψ
The quantity whose variations make up matter waves is called the wave function. It is
denoted by the Greek letter Ψ (psi). The value of the wave function associated with
a moving body at a particular point (x, y, z) in space and at time t is related to the
likelihood of finding the body there at that time.

Physical significance of the Wave function Ψ

-H yd
B -QM
1. The wave function Ψ(x, y, z, t) = Ψ(r, t) has no direct physical meaning. It is
a complex quantity representing the variation of matter waves. It connects the
particle nature and its associated wave nature statistically.
2
2. According to Max Born |Ψ| gives the probability of finding the particle in the
state Ψ i.e., it is a measure of probability density. The probability of finding a
2
particle in a volume dx dy dz is given by |Ψ| dx dy dz. We know that the total
probability of finding the particle some where is unity i.e., the particle is certainly
to be found some where in space i.e.,
Z Z Z
2
|Ψ| dx dy dz = 1. (1.1)
x y z

Ψ satisfying the above equation is said to be normalized.

3. If the Ψ is the amplitude of the matter waves at any point in space, then the particle
2 2
density at that point may be taken as proportional to |Ψ| . Thus, |Ψ| is a measure
of particle density. When this is multiplied with charge of the particle, the charge
2
density is obtained. In this way |Ψ| measures charge density of particles.

Since, the matter waves can exist at any point on the available space and the probability
density has to be finite; the wave function has to be continuous and finite inside the avail-
able space. In view of these physical interpretations of the wave function Ψ(x, y, z, t),

1
2CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

certain mathematical conditions are imposed on the wave function. These conditions
defined the properties of a well behaved wave function. They are
(i) The wave function Ψ must be finite. This property follows from the normal-
ization of the wave function and implies that even if x → ±∞, y → ±∞, z →
±∞, Ψ(x, y, z) must remain finite for all values of x, y and z.
∂Ψ ∂Ψ ∂Ψ
(ii) Ψ(x, y, z) and its space derivatives , and must be continuous every-
∂x ∂y ∂z
where in the space.
(iii) The wave function Ψ(x, y, z) must be single valued at any point in the space, for the
simple reason that any physical quantity and the function related to the physical
quantity cannot have more than one value at that point.
The wave functions which satisfy all the above properties i.e., they are finite, continuous
and single valued are called well behaved wave functions and are the only ones acceptable
as the matter wave functions.

1.2 Schrödinger’s Wave Equation and its Applica-

tions
1.2.1 Schrödinger’s time-independent wave equation
Let us consider a group of waves associated with a moving particle of mass m with a
velocity v. According to de Broglie, the wavelength of these waves is λ = h/(mv). Let

yd
Ψ(r, t) be the displacement of these waves at the site r(x, y, z) at a given instant of time

-H
t. According to classical mechanics, the wave equation is given by

B -QM ∂2Ψ
∂t2
= v 2 ∇2 Ψ (1.2)

∂2 ∂2 ∂2
where, ∇2 = + + is the Laplacian operator and v is the velocity of the
∂x2 ∂y 2 ∂z 2
particle.
Solution of this second order differential equation is given by

Ψ = Ψ0 e−i w t (1.3)

Differentiating the equation twice, we get

∂2Ψ v2
2
= (−iw)(−iw)Ψ0 e−i w t = −w2 Ψ = −4π 2 ν 2 Ψ = −4π 2 2 Ψ (1.4)
∂t λ
In the above equation we have used w = 2πν and ν = v/λ. Equating equations (1.2)
and (1.4), we get
v2
v 2 ∇2 Ψ = −4π 2 2 Ψ. (1.5)
λ
Now from de Broglie λ = h/(mv) = h/p, the above equation (1.5) becomes

p2
∇2 Ψ = −4π 2 Ψ (1.6)
h2
1.2. SCHRÖDINGER’S WAVE EQUATION AND ITS APPLICATIONS 3

Let E and V be the total and the potential energies of a moving particle. Then the
kinetic energy of the particle is given by

1 p2
mv 2 = = E − V ⇒ p2 = 2m(E − V ) (1.7)
2 2m

From (1.6) and (1.7), we get

8π 2 m
∇2 Ψ + (E − V )Ψ = 0 (1.8)
h2

The equation (1.8) is known as the Schrödinger time-independent wave equation. Sub-
stituting ~ = h/(2π), the Schrödinger wave equation can be written as

2m
∇2 Ψ + (E − V )Ψ = 0 (1.9)
~2

For a free particle V = 0, hence the Schrödinger wave equation for a free particle can
be expressed as
2mE
∇2 Ψ + 2 Ψ = 0 (1.10)
~

1.2.2 Schrödinger’s time-dependent wave equation

Schrödinger’s time dependent wave equation can be obtained from Schrödinger’s time

yd
independent wave equation by eliminating E. Differentiating (1.3) w.r.t. time, we get

-H
B -QM
∂Ψ E
= −iw Ψ = −i Ψ (1.11)
∂t ~

where, we have used E = hν = ~ 2πν = ~w. Therefore, we have

∂Ψ
i~ = EΨ (1.12)
∂t

Substituting the value of EΨ in Schrödinger’s time independent wave equation (1.9), we

obtain
 
2 2m ∂Ψ
∇ Ψ + 2 i~ −VΨ = 0
~ ∂t
~2 2 ∂Ψ
⇒− ∇ Ψ + V Ψ = i~ (1.13)
2m ∂t

This equation is known as the time dependent Schrödinger’s wave equation. It can be
rewritten in the following form
HΨ
b = EΨb (1.14)
2
where H b = i~ ∂ is the energy
b = − ~ ∇2 + V is the Hamiltonian operator and E
2m ∂t
operator.
4CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

1.3 Applications of Schrödinger’s wave equation

1.3.1 Schrödinger’s equation for non-relativistic equation
We know for any free particle, the wave function can be written as

ψ(x, t) = A expi(kx x−ωt) (1.15)

We know that

E = hν (1.16)
2π
E = hν ×
2π
hω
E = ×
2π
E = }ω (1.17)
pc = }c.k
p = }×k (1.18)
p
k = (1.19)
}
E
ω = (1.20)
}

Hence substituting in above equation of ψ(x, t) for 1-D case, we get

-Hyd
i
ψ(x, t) = A exp } (px x−Et) (1.21)

B -QM
Differentiating Eq.1.21 with respect to time (t), we get
 
−} ∂ψ(x, t)
= Eψ(x, t) (1.22)
i dt

Differentiating Eq.1.21 with respect to position ’x’ twice, we get

}2 ∂ 2 ψ(x, t)
 
− = p2x ψ(x, t) (1.23)
2m dx2

Comparing the above equations, we get,

 
−} ∂ψ(x, t)
= Eψ(x, t) (1.24)
i dt
2
  2
} ∂ ψ(x, t)
− = p2x ψ(x, t) (1.25)
2m dx
}2 ∂ 2 ψ(x, t)
   
−} ∂ψ(x, t)
= − (1.26)
i dt 2m dx2

Eq.1.26 is the Schodinger equation for non-relativistic particles for one dimention. for
three dimention, add x, y, and z co-ordinates to the ψ(x, y, z, t) and solve.....
1.3. APPLICATIONS OF SCHRÖDINGER’S WAVE EQUATION 5

1.3.2 Momentum Operator

In quantum mechanics, the momentum operator is the operator associated with the lin-
ear momentum. The momentum operator is, in the position representation, an example
of a differential operator.The ”hat” indicates an operator. The ”application” of the
operator on a differentiable wave function is as follows. In three dimensions, the plane
wave solution to Schrodinger’s equation is:
i
ψ = A exp } (px x−Et) (1.27)

and the gradient is

∂ψ ∂ψ ∂ψ
Oψ = ex + ey + ez (1.28)
dx dy dz
 
i
Oψ = (ex .px + ey .py + ez .pz ) (1.29)
}
 
i
Oψ = p~ψ (1.30)
}

Here, it should be remembered that (ex , ey , ez ) are are the unit vectors for the three
spatial dimensions, hence
p̂ = −i}O (1.31)

For convience, let us change the equation from momentum vector p~ to the propagation
p
vector k = 2π
yd
λ and k = } . Then we have

-H
B -QM
ψ = A. expik.r (1.32)

The above equation also form the momementum wave function. Using the ψ state,
probability density of the particle in that state can be find out.

P (r) = ψψ∗ = |ψ|2 (1.33)

State of wave packet with its exact value of momentum can neither be predicted nor
controlled but only the probability can be determined by the wave function, which is an
extension of the wave particle duality to include to momentum space as well as position
space. The equation can be further written as

P (k)dk = |ψ(k)|2 dk (1.34)

1.3.3 BOX-Normalization
Let the box be the momentum functions which obeys perodic boundary conditions with
each side as L centered at the origin. The we must have
Z
P (k)dk = 1
6CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

where integration is taken over the volume of the entire box, so that,
Z
A. expik.r A. exp−ik.r = 1

 
(1.35)
Z
2
A dk = 1 (1.36)
1
A2 = (1.37)
L3
−3
A = L2 (1.38)

The state ψ is said to be normalized if it satisfy the Eq.1.38. In such case, we have the
equation as
−3
ψ=L 2 . exp−ik.r (1.39)

1.3.4 Energy Operator

In quantum mechanics, energy is defined in terms of the energy operator, acting on the
wave function of the system as a consequence of time translation symmetry. It is given
by relation

∂
Ê = i} (1.40)
∂t
This above Equation acts on the wave function ψ(r, t) (the probability amplitude for
different configurations of the system)

-H yd
B -QM
1.3.5 Stationary States
A stationary state is a quantum state with all observables independent of time. It is
an eigenvector of the energy operator (instead of a quantum superposition of different
energies). It is also called energy eigenvector, energy eigenstate, energy eigenfunction,
or energy eigenket.
i
ψ(x, t) = A exp } (px x−Et)
i
ψ(x, t) = A exp } (−Et) (1.41)
∂ψ Ei i
= A exp } (−Et)
∂t }
∂ψ −Ei
= ψ(t)
∂t }
∂2ψ E2
= ψ(x) (1.42)
∂t2 }2
|ψ(x, t)E |2 = |ψ(x)|2 × |A|2 (1.43)

It can be observed that he same functional form and differ only by a multiplying factor
hence they represent the same state and so all measurable quantities of the system
remain constant at time passes such states are called stationary States. The probability
density of this particle does not change with time. For this reason, we call such a
condition for a particle a stationary state
1.3. APPLICATIONS OF SCHRÖDINGER’S WAVE EQUATION 7

If the wave function of a particle at t = 0 is an Eigen function of hamiltonian , the

probability density of the particle remain constant as time passes and the expectation
value of any measurable quantity remains constant as time passes this state is known
as stationary states.

1.3.6 Particle in a one dimensional box (Infinite potential well)

Let us now apply Schrödinger’s equation to a particle of mass m trapped in a one
dimensional box with infinitely hard walls. This particle is restricted to travelling along
the x-axis between the hard walls of the box at x = 0 and x = L.
The particle does not lose energy when it collides with the walls, so its total energy
remains constant. The potential energy of the particle between the two walls is constant
because no force acts on the particle. For convenience, we take this constant potential
energy to be zero i.e., V = 0.
The potential energy of the particle is infinite on both sides of the box. Therefore, the
boundary conditions for the potential can be defined by
(
0 for 0 < x < L,
V (x) = (1.44)
∞ for x ≤ 0 and x ≥ L.

Outside the box/well, since the potential energy is infinite; the wave function is zero.
Within the well, the Schrödinger equation becomes

∂ 2 Ψ 2mE
+ 2 Ψ=0 (V = 0 inside the box) (1.45)
∂x2 ~

-H yd
Let’s take a trial solution for the above equation

B -QM
Ψ = A eα x , (1.46)

where A is a constant. Taking the second derivative and substituting into equation
(1.45), we get
(α2 + k 2 )Ψ = 0 (1.47)
2 2
√ k = 2mE/~ . Now inside the box, Ψ can’t be zero. So we obtain α = ±ik, with
where
i = −1. Thus, the general solution can be written as

Ψ(x) = A eik x + B e−ik x (1.48)

√
where, A and B are constants to be evaluated and k = 2mE/~. Since, the particle
cannot penetrate an infinitely high potential barrier, hence Ψ = 0 at x = 0 and at x = L.
Applying these conditions to the equation (1.48) we get for x = 0

A + B = 0 ⇒ A = −B

⇒ Ψ(x) = C sin k x (1.49)

and for x = L

C sin k L = 0. (1.50)
8CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

Here either C = 0 or sin k L = 0. Now C can’t be zero, because if C = 0 then the entire
wave function will vanish. Therefore,

sin k L = 0 = sin n π
√
2mE
⇒ kL = nπ = L where n = 1, 2, 3, . . . (1.51)
~
n2 π 2 ~2 n2 h2
⇒ En = 2
= . (1.52)
2mL 8mL2
From the above equation, it is clear that the total energy of a particle in an infinite deep
potential well is quantized i.e., it can have only discrete set of values for energy. The
discrete values of energy called the eigen values for the first three quantum states are
given by

h2
E1 = (1.53)
8mL2
4h2
E2 = = 4E1 (1.54)
8mL2
9h2
E3 = = 9E1 (1.55)
8mL2

Conclusions from the expression of eigen values

1. A trapped particle cannot have an arbitrary energy, as a free particle can. The
fact of its confinement leads to restrictions on its wave functions that allow the

-H yd
particle to have only certain specific energies and no others. Exactly what the
value of these energies are depends on the mass of the particle and the details of

B -QM
how it is trapped inside the box.
2. A trapped particle cannot have zero energy. For En = 0 we have n = 0. Since, the
de Broglie wavelength of the particle λ = h/p, we have p = ~ k = 0 (using equation
(1.51)), which means an infinite wavelength. Therefore, a trapped particle must
have at least some kinetic energy.
3. Because Planck’s constant h = 6.626 × 10−34 J − s, quantization of energy is
conspicuous (evident) only when m and L are also very small. This is why, we are
not aware of energy quantization in our own everyday experience.

1.3.7 Expression for the wave function

The wave function of a particle in a box, whose energy is En is given by

Ψn (x) = C sin kn x (1.56)

Substituting kn from equation (1.51), we get

 nπ 
Ψn (x) = C sin x (1.57)
L
R∞ 2
The constant C can be obtained by normalization condition of the wave function −∞ |Ψ| dx =
1. Here the limits of integration are from 0 to L, since the wave function is non zero
1.3. APPLICATIONS OF SCHRÖDINGER’S WAVE EQUATION 9

within these limits. Therefore,

Z L Z L  nπ 
2
|Ψ| dx = C 2 sin2 x dx = 1. (1.58)
0 0 L

Now since C is a constant and using sin2 θ = (1 − cos 2θ)/2, we get

L L
C2 C2
Z       
2nπ L 2nπ
1 − cos x dx = x− sin x =1
2 0 L 2 2nπ L 0
r
C2 2
⇒ L=1 or C= . (1.59)
2 L
Therefore, the normalized wave functions called as eigen functions can be written as
r
2 n π 
Ψn (x) = sin x n = 1, 2, 3, . . . (1.60)
L L
Some of the normalized wave functions Ψ1 (x), Ψ2 (x) and Ψ3 (x), together with their
2 2 2
probability densities |Ψ1 (x)| , |Ψ2 (x)| and |Ψ3 (x)| . Although Ψ may be negative as
2
well as positive |Ψ(x)| is never negative.

1.3.8 Rectangular potential Barrier

According to classical mechanics a particle striking a hard wall will not be able to
penetrate it. However the nature of a quantum particle is different due to the wave

yd
nature associated with the particle. We know that, when an electromagnetic wave

-H
strikes the interface between two mediums, a part of it gets reflected while another part

B -QM
gets transmitted and enters the second medium. Similarly a de-Broglie wave also has
the possibility of getting partly reflected and partly transmitted from the boundary of a
potential barrier. This penetration of the quantum particle to get transmitted through
a barrier is called tunneling.
In figure (??), we have shown the shape of a potential barrier of height V0 and thickness
L. The regions around the barrier can be divided into three regions which are shown in
the figure. In regions I and III i.e., for x < 0 and for x > L, the potential is zero, and
the potential has a constant value V0 in the region II i.e., for 0 ≤ x ≤ L. So, the shape
of the potential function V (x) can be written as
(
V0 for 0 ≤ x ≤ L,
V (x) = (1.61)
0 for x ≤ 0 and x ≥ L.

Let us assume that a quantum particle of total energy E approaches the barrier from
the left. In regions I and III, since the potential energy is zero, the total energy of the
particle is equal to it’s kinetic energy. However in region II, the total energy is partly
kinetic and partly potential energy. From classical point of view an electron approaching
the barrier from left will get reflected from the barrier whenever it’s energy is less than
the barrier height V0 . In order to overcome the barrier it must have energy greater than
or equal to V0 . However, in quantum mechanics there is a probability that the electron
can penetrate the barrier and leak to the other side and we say that the electron has
tunneled through the potential barrier. In order to understand the tunnelling, we write
10CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

down the Schrödinger’s wave equation for the electron and solve them in the three
regions.
The the Schrödinger’s wave equation for an electron moving along x-axis is given by
d2 ψ 2m
+ 2 (E − V (x))ψ = 0, (1.62)
dx2 ~
where ψ is the wave function of the electron moving under the potential V (x).
Solution for Region I :-
In region I, V = 0 and the wave equation (1.62) takes the form
d2 ψ1 2mE
+ ψ1 = 0
dx2 ~2
d2 ψ1
⇒ + k02 ψ1 = 0, (1.63)
dx2
2mE
where k02 = ~2 . Whose general solution can be written as

ψ1 (x) = A eik0 x + B e−ik0 x . (1.64)

Solution for Region II :-
In region II, V = V0 and the wave equation (1.62) takes the form
d2 ψ2 2m
+ 2 (E − V0 )ψ2 = 0
dx2 ~
d2 ψ2
⇒ + k 2 ψ2 = 0, (1.65)
dx2
2 m (E−V0 )

yd
where k 2 = ~2 . Whose general solution can be written as

-H
B -QM
ψ2 (x) = C eik x + D e−ik x . (1.66)
Solution for Region III :-
In region III, V = 0 and the wave equation (1.62) takes the form
d2 ψ3 2mE
2
+ ψ3 = 0
dx ~2
d2 ψ3
⇒ + k02 ψ3 = 0, (1.67)
dx2
2mE
where k02 = ~2 . Whose general solution can be written as

ψ3 (x) = M eik0 x + N e−ik0 x . (1.68)

Now in region III, no particle is entering from the right hand side direction so N = 0,
giving the solution for region III to be
ψ3 (x) = M eik0 x . (1.69)
In order to solve further, we apply continuity conditions on the wave function ψ and
its derivative ∂x ψ at the barrier interfaces x = 0 and x = L. Applying the continuity
conditions at x = 0 provides
ψ1 |x=0 = ψ2 |x=0
⇒A+B = C + D, (1.70)
1.3. APPLICATIONS OF SCHRÖDINGER’S WAVE EQUATION 11

and
 
∂ ψ1  ∂ ψ2 
=
∂x x=0 ∂x x=0
⇒ k0 (A − B) = k (C − D). (1.71)

Similarly at x = L

ψ2 |x=L = ψ3 |x=L
−ikL
⇒Ce ikL
+De = M eik0 L + N e−ik0 L , (1.72)

and
 
∂ ψ2  ∂ ψ3 
=
∂x x=L ∂x x=L
⇒ k (C eikL − D e−ikL ) = k0 ( M eik0 L − N e−ik0 L ). (1.73)

Together we obtain a set of four equations (1.70-1.73), for five unknowns namely A, B, C, D
and M . However, we are not interested in solving any one unknown! Rather we seek to
obtain the reflection (r) and transmission (t) coefficients for the system which can be
written as  2  2
B  M 
R=   and T =   . (1.74)
A A
From equations (1.70 and 1.71), we have

A+B = C +D (1.75)

and A − B
-H yd
=
k
(C − D) (1.76)

B -QM
k0
These two equations can be solved to obtain
     
1 k 1 k
−  " #

A

2 1 + k0 2 1 k0

C α β C

=      = , (1.77)
B 1
1− k 1
1+ k D β α D
2 k0 2 k0

where α = 21 (1 + k
k0 ) and β = 12 (1 − k
k0 ). Similarly from equations (1.72 and 1.73), we
have

C eikL + D e−ikL = M eik0 L + N e−ik0 L (1.78)

k0
and C eikL − D e−ikL M eik0 L − N e−ik0 L


= (1.79)
k
from which we deduce that
k0 k0
 1
i(k −k)L 1
−i(k +k)L 
2 1+ k e 0 2 1− k e
  0  
C M
=  
D 1 k0

i(k +k)L 1 k0

−i(k −k)L N
2 1− k e 0 2 1+ k e 0

 k i(k0 −k)L
− kk0 β e−i(k0 +k)L 

k αe
0 
=   M . (1.80)
N
− kk0 β ei(k0 +k)L k0
k α e −i(k0 −k)L
12CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

Combining equations (1.77 and 1.80) and substituting N = 0, we have

 k
α ei(k0 −k)L − kk0 β e−i(k0 +k)L 

    0 
A α β  k M
= 
B β α 0
− kk0 β ei(k0 +k)L k0
k αe
−i(k0 −k)L

k0
eik0 L α2 e−ikL − β 2 eikL M


k
=   (1.81)
k0 −ikL
ik0 L ikL


k αβe e −e M

which provides the expression for the reflectivity to be

 2  −ikL

2
ikL 
B  α β e − e
R =   =  2 −ikL (1.82)
 
A  (α e − β 2 eikL ) 


and transmissivity
 2  2
M  1 
T =   = 
A  kk0 eik0 L (α2 e−ikL − β 2 eikL ) 


 2
 k 
k0
= (1.83)
 
 2 −ikL
 (α e − β 2 eikL ) 


1.3.9 1-D linear Harmonic oscillator

-H yd
B -QM
A particle undegoing simple harmonic motion (S.H.M) in one-dimention is
called one-dimentional harmonic oscillator.
In S.H.M, the restoring force is proportional to displacement, i.e.,

F = −k.x (1.84)

where k is a positive constant, called the force constant. Additionally, according to

Newton’s second law
d2 x
F =m 2 (1.85)
dt
where ’m’ is the mass of the particle.
Equating both the equation, we have

d2 x k
+ x=0 (1.86)
dt2 m
This equation represents a peiodic motion of angular frequency ω = 2πν

r
k
ω = (1.87)
m
 r
1 k
ν = (1.88)
2π m
1.4. THEORY OF METALS AND BAND THEORY OF SOLIDS 13

The potential energy of oscillator is given as

Z x
kx2
V =− kxdx = (1.89)
0 2

Substituting the above terms of potential (V) in 1.8, i.e.,

2m
∇2 Ψ + (E − V )Ψ = 0 (1.90)
~2
we have
1 ∂2ψ
+ λ − α 2 x2 ψ


= 0 (1.91)
α2 ∂x2
where r
2 mk
α = (1.92)
}2
r
m
λ = 2E. (1.93)
}2 k

Eigen Value in Harmonic oscillator

Value of En which eignen value is given as
 
1
En = n + }ω (n = 0, 1, 2, 3...) (1.94)
2

Equation incidates allowed integral values of n lead to certain discrete value of energy.

H yd
It further indicates the levels of harmonic oscillator are equally spaced.
-
Zero point energy
B -QM
For ground state or lower state (n=0), we have
 
1
E0 = }ω (1.95)
2

Which is known as zero point energy.

1.4 Theory of Metals and Band Theory of Solids

1.4.1 Free Electron Theory of metals
According to free electron theory of metals, the conduction of valence or outermost
electrons of an atom in a metal are assumed to move freely throughout the volume of
the metal, like the molecules of a gas in a container. Free electrons contributed by all
atoms of the metal constitute what we commonly known as electron gas or the Fermi
gas within the metal. Since all atoms loss their valence electrons, they become positive
charged ions. Hence one may look upon a metal as consisting of an array of closely
packed positively charged ions immersed in a sea of free electrons.
One basic assumption of the free electron theory is that the potential field due to the
ion cores is uniform throughout the metal which leads to the important conclusion that
14CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

all the free electrons have the same potential energy everywhere within the metal. This
constant potential energy is taken to be zero for convenience. In this case, the only
energy that the electrons possess is the kinetic energy. Hence, the total energy of the
free electron is given by
n2 π 2 ~2
En = (1.96)
2mL2
Thus, free electrons occupy quantum states of increasing kinetic energy as the value of n
increases. This equation also shows that the free electrons do not possess any arbitrary
amount of energy but only quantized energy given by the above relation.
Since, the free electrons move randomly in all directions within the metal and collide
with either positive ions or other electrons. All collisions are elastic i.e., there is no
loss of energy. As a result under normal circumstances (when no potential difference
is applied) they do not conduct electricity. But when an electric field is applied to the
metals, these free electrons accelerate in a direction opposite to the direction of applied
electric field and conduct electricity.

1.4.2 Band theory of solids

In case of a single isolated atom, there are discrete energy levels. For example, if we
consider an isolated Cu atom, it has 29 electrons arranged in their respective sub-shells
as 1s2 2s2 2p6 3s2 3p6 3d10 4s1 . We can see that the first six sub-shells in Cu are filled,
but the outermost 4s sub-shell, which can hold 2 electrons, holds only one electron.
If we now consider two Cu atoms placed close together, then it is observed that the
wave function or in simple words the sub-shells of these two atoms start over lapping
each other, beginning with those of the outermost electrons. Thus, we now consider

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them not as two independent atoms but as a single system comprising of two atoms.
This system contains 2 × 29 = 58 electrons. The Pauli’s exclusion principle aplies to

B -QM
this larger system as well. It requires that each of these 58 electrons occupy a different
quantum state. For this two atom system, each energy level splits into two levels.
Now if we bring up more atoms, we gradually assemble a lattice of solid copper. If the
lattice contains N atoms, then each level of an isolated Cu atom must split into N levels
in the solid. Thus, the individual energy levels of the solid form energy bands. An energy
band is basically is a set of very closely packed energy levels. The individual energy levels
within the band are so close together that the energy bands may be considered to be
continuous. Adjacent bands are separated by an energy gap, which represents a range
of energies that no electron can possess.
The bands of lower energy are narrower than those of the higher energy. This occurs
because electrons that occupy the inner sub-shells do not overlap as much as the outer
shells. Hence, splitting of these levels is not as great as it is for the higher energy levels
normally occupied by the outer shells.

Valence band, Conduction band and Forbidden Energy gap

The electrons on the outer most shell are called as valence electrons. The band formed
by a series of energy levels containing the valence electrons is known as valence band.
The valence band may also be defined as the highest occupied band. This band may be
completely filled or partially filled but can never be completely empty.
The valence electrons which are loosely bound to the nucleus leave the valence band even
at ordinary temperatures. These are called free electrons or conduction electrons since
1.4. THEORY OF METALS AND BAND THEORY OF SOLIDS 15

these free electrons are responsible for conduction of curent in a conductor. The energy
occupied by these electrons is called the conduction band. This band lies just above the
valence band. The conduction band may also be defined as the lowest unoccupied band.
This band can be completely empty or partially filled but it can never be completely
filled.
The separation between the conduction band and the valence band is known as forbidden
energy gap. There is no allowed energy states in this gap and hence no electron can
stay in this energy gap. The greater is the energy gap, more tightly are the valence
electrons bound to the nucleus. In order to push an electron from the valence band
to the conduction band external energy is required which is equal to the energy of the
forbidden energy gap.

Classification of Solids based on band theory

Based on band theory, we can classify the solids into

1. Insulators,

2. Conductors and

3. Semiconductors.

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Insulators :- A solid is said to be an insulator if no current exists within it when we
-
B -QM
apply a potential difference across it. This means that in an insulator there are effectively
no free electrons. The valence electrons are bound very tightly to their parent atoms.
All the bands upto the valence band are completely filled and the conduction band is
completely empty. In this case the forbidden energy gap is so wide that it is impossible
to excite a significant number of free electrons across this region. For example, the
forbidden energy gap in diamond is 5.5eV (which is about 140 times the average thermal
energy of a free particle at room temperature). Diamond is thus a very good insulator.
Conductors :- A solid is said to be a conductor when current flows easily through it.
This means that there will be a large number of conduction electrons available for electric
conduction even at low temperatures. The valence band is either partially filled or (if it is
filled) the conduction band, into which electrons can pass, overlaps with the filled valence
band. In either case, there are unoccupied states for electrons in the uppermost band
and these electrons are available to carry current. Due to the overlapping of the valence
band and conduction band, a slight potential difference across the conductor cause the
free electrons to constitute electric current. Semi-Conductors :- A semiconductor is
a solid whose electrical properties lie in between the insulators and conductors. The
valence band is completely filled and the conduction band is completely empty. The
forbidden energy gap is very small (≈ 1eV ). This means that when a small amount of
energy is supplied, the electrons in valence band can easily jump to the conduction band
and hence become available for conduction of electric current. Germanium and Silicon
are few of the examples of semiconductors. In germanium the forbidden energy gap is of
the order of 0.72eV while in case of silicon, the forbidden band is of the order of 1.1eV .
16CHAPTER 1. PROPERTIES OF MATTER WAVES AND QUANTUM TUNNELING

1.5 Elementary concepts of Statistical Mechanical dis-

tributions
1.5.1 Statistical Physics
Statistical physics or statistical mechanics is a branch of physics that considers how
the overall behaviour of a system of many particles is related to the properties of the
particles themselves. As its name implies, statistical mechanics is not concerned with
the actual motions or interactions of individual particles, but instead it deals with what
is most likely to happen.
Depending on the different kinds of particles, the study of statistical mechanics can be
carried out under the following categories:

(a) Maxwell-Boltzmann (MB) Statistics,

(b) Bose-Einstein (BE) Statistics and

(c) Fermi-Dirac (FD) Statistics.

MB Statistics
• It holds for a system of particles that can be distinguished from one another.

• Classical particles such as gas molecules obey them.

• In quantum terms, the wave functions of the particles overlap to a negligible extent
and hence they can be distinguished from one another.

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• The MB distribution function states that the average number of particles fM B (E)

B -QM
in a state of energy E in a system of particles at absolute temperature T is

fM B (E) = A exp (−E/kB T ) (1.97)

where, A is a constant whose value depends on the number of particles in the sys-
tem and kB is the Boltzmann’s constant. fM B (E) is also called as the probability
of occupancy of the state of energy E.

• There’s no limit to the number of particles that can occupy a single state.

BE Statistics
• It is applicable when quantum effects have to be taken into account.

• It holds for a system of identical particles that cannot be distinguished from one
another because their wave functions overlap.

• The particles obeying BE statistics are called ”Bosons”. Examples are photons,
α−particles, phonons etc.

• Bosons do not obey Pauli’s exclusion principle. It means that any number of
bosons can exist in the same quantum state of the system.

• Bosons are particles having zero or integral spins.

1.5. ELEMENTARY CONCEPTS OF STATISTICAL MECHANICAL DISTRIBUTIONS17

• The BE distribution function states that the average number of particles fBE (E)
in a state of energy E in a system of particles at absolute temperature T is
1
fBE (E) = (1.98)
exp(α) exp (E/KB T ) − 1

where α is a quantity which depends on the particular system and may be a

function of T . When E  kB T , the function fBE (E) approaches that of M B
statistics.

FD Statistics
• Like BE statistics FD statistics is applicable when quantum effects have to be
taken into account.
• It holds for a system of identical particles that cannot be distinguished from one
another because their wave functions overlap.

• The particles obeying FD statistics are called ”Fermions”. Examples are electrons,
protons, neutrons etc.
• Fermions are particles which obey Pauli’s exclusion principle. It means that there
can’t be more than one identical particle in the same quantum state of the system.
• Fermions are particles having half-integer spins i.e., 1/2, 3/2, 5/2, etc.

• The FD distribution function states that the average number of particles fF D (E)
in a state of energy E in a system of particles at absolute temperature T is

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B -QM
fF D (E) = (1.99)
exp [(E − EF )/KB T ] + 1

where EF is the Fermi energy. When E − EF  kB T , the function fF D (E)

approaches that of M B statistics.