1

• A propagating disturbance in a medium is wave

 Light waves
 Sound waves Certain quantity varies with position and time
 Water waves

• What varies with de-Broglie wave ?

• Wave function describes the wave as a function of position and time

• is not an observable quantity has no direct physical significance

• In general, is a complex-valued function, gives the probable value of the
measurement
2
A probability interpretation is given by Max Born in 1926

“The square of the magnitude of the wave function 𝟐

evaluated in particular region
represents the probability of finding the particle in that region”
OR
“Probability (P) of finding the particle in an infinitesimal volume is
proportional to at time t”

i.e. 𝟐

Where,
𝟐 is probability density
is probability amplitude

3
Since the particle is certainly in space, the probability P = 1

To make probability a real quantity, is to be multiplied by its complex conjugate ∗

𝟐 gives the probability of finding the atomic particle in a particular region

4
If a particle is somewhere in the space, the sum of the probabilities over all values of 𝑥, 𝑦, 𝑧 must be unity
If 𝜓 is multiplied by a constant C such that

𝜓 𝑥, 𝑦, 𝑧, 𝑡 = 𝐶𝜓(𝑥, 𝑦, 𝑧, 𝑡)

𝜓 (𝑥, 𝑦, 𝑧, 𝑡) 2 𝑑𝑥𝑑𝑦𝑑𝑧 = 𝐶 𝜓(𝑥, 𝑦, 𝑧, 𝑡) 2 𝑑𝑥𝑑𝑦𝑑𝑧 = 1

Where, 𝝍𝑵(𝒙, 𝒚, 𝒛, 𝒕) is a normalized wave function and C is the normalized constant

This is called normalization condition.
1
𝐶 =
∫ 𝜓(𝑥, 𝑦, 𝑧, 𝑡) 2 𝑑𝑥𝑑𝑦𝑑𝑧

Here, 𝜓 (𝑥, 𝑦, 𝑧, 𝑡) 2 𝑑𝑥𝑑𝑦𝑑𝑧 is called the probability density

Whenever wave function is normalized, 𝜓 𝑑𝑉 equals the probability that a particle will found in an element
volume dV

Thus, Probability 𝑷 = 𝝍(𝒙, 𝒚, 𝒛) 𝟐 𝒅𝑽

5
An acceptable wave function must be normalized and fulfil the following
requirements

(i) function must be finite:

(ii) function must be single valued:

(iii) function must be continuous:

6
 Physical significance of Ψ

1. It relates the particle and wave nature of matter statistically.

2. It is a complex quantity and hence we cannot measure it. It shall be expressed of
the form  ( x, y , z , t )  a  ib (1)
where ‘a’ and ‘b’ are real functions of variables (x,y,z,t)
The complex conjugate of Ψ is denoted by Ψ* by changing ‘i” to ‘-i’
  ( x, y, z, t )  a  ib (2)
multiplying (1) and (2)
 ( x, y , z , t )   ( x, y , z , t )  a 2  b 2 (3)

The product (LHS)    is denoted by P

2
Ie. P =  ( x, y, z , t )  ( x, y, z , t )   ( x, y, z , t )
2
 ( x, y , z , t )  a 2  b 2 (4)

3. Its square is a measure of the probability of finding the particle at a particular

position . It cannot predict the exact location of the particle
2
 ( x, y , z , t ) is called probability density
4. For the motion of a particle, the probability of finding the particle in a
volume element ‘dv’ is
Pdv   ( x, y, z, t )   ( x, y, z , t )dv
2
  ( x, y , z , t ) dv

For the motion of the particle in one dimension, Pdx   ( x, t )   ( x, t ) 2 dx

probability per unit

 distance
Therefore , the total probability is 
2
Px   ( x, t ) dx


For 3-dimensional space

2
P   ( x, y, z, t ) dv


5. The normalising condition for the wave function for the motion of
a particle in 3-dimension is 
(7)
  ( x, y, z, t ) dv  1
2



Where Ψ is the function of space coordinates (x,y,z)

6. If the wave function does not satisfy the normalization condition eqn (7), then
it must be multiplied by a constant factor called normalization factor.
For eg.
 dx  N
2
( N 1 )

1
The normalization factor will be and the normalized wave function
will be 1  N
N

7. The wave function Ψ must approach zero as ‘x’ tends to ±α.

8. The wave function satisfying the following condition is said to be an

orthogonal wave function


  ( x)dx  0
i j


The orthogonality condition guarantee the non-interference of the

wave function representing different states.
9. Degeneracy

If Ψi and Ψj corresponds to the same energy “E” then this is called as degenerate
state.
10. Orthonormal set: The normalization and orthoganility conditions may be
combined as follows

i j
 i  j dv  1


0 i j (10)

Wave function of the form eqn (10) is said to be orthogonal wave function.

11. Ψ must be finite for all values of x,y,z.

12. Ψ must be well behaved i.e single valued and continuous every where.
13. Ψ must be continious in all regions except in those region where the
potential energy V(x,y,z) = α
How does one determine the wave function of a particle ??!

“Schrodinger Wave Equation”

11
• The Schrödinger equation is a linear partial differential equation that governs
the wave function of a quantum-mechanical system

• The equation is given by Erwin Schrödinger and therefore called as Schrodinger

wave equation

• Conceptually, the Schrödinger equation is the quantum counterpart of Newton's

second law in classical mechanics

12
• The energy of a relativistic particle can be given as

Multiplying by wave function on both sides

𝟐
−− −❶

Where ( )
−− −❷
is an exponential form of wave equation deduced from the Euler’s formula 13
 𝐸𝜓 = 𝜓 + 𝑉𝜓 −❶ 𝜓= 𝜓 𝑒 ( ) −− −❷

We know,
𝐸
𝐸 = ℏ𝜔 ⇒ 𝜔=
ℏ
𝑃
𝑃 = ℏ𝑘 ⇒ 𝑘 =
ℏ

( ) −− −❸
∴ 𝜓= 𝜓 𝑒 ℏ

Differentiating equation (3) w.r.t. t

𝜕𝜓 𝑖
= 𝜓 𝑒 ℏ × (−𝐸)
𝜕𝑡 ℏ
1
𝜕𝜓 𝐸 1 ∵ 𝑖 = −1 ⇒ −𝑖 =
= 𝜓 𝑖
𝜕𝑡 ℏ 𝑖

𝝏𝝍
∴ 𝒊ℏ = 𝑬𝝍 4
−− −❸
𝝏𝒕
14
Differentiating equation (3) w.r.t x
ℏ 𝜓= 𝜓 𝑒 ( ℏ ) −− −❸

Differentiating again w.r.t x

𝟐
𝟐 𝟐 −− −❺
𝟐
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Putting values 𝐸𝜓 and 𝑃 𝜓 of in equation (1) 𝐸𝜓 = 𝜓 + 𝑉𝜓
𝜕𝜓 ℏ 𝜕 𝜓
𝑖ℏ =− + 𝑉𝜓
𝜕𝑡 2𝑚 𝜕𝑥

𝝏𝝍 ℏ𝟐 𝝏𝟐
𝒊ℏ = − +𝑽 𝝍 −− − 6
𝝏𝒕 𝟐𝒎 𝝏𝒙𝟐

This is a time-dependent Schrodinger wave equation

When extended to three dimensional case,
ℏ 𝜕 𝜓 𝜕 𝜓 𝜕 𝜓 𝜕𝜓
− + + + 𝑉𝜓 = 𝑖ℏ
2𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑡

ℏ 𝜕 𝜕 𝜕 𝜕𝜓
− + + 𝜓 + 𝑉𝜓 = 𝑖ℏ
2𝑚 𝜕𝑥 𝜕𝑦 𝜕𝑧 𝜕𝑡

ℏ𝟐 𝟐 𝝏𝝍
− 𝛁 𝝍 + 𝑽𝝍 = 𝒊ℏ
𝟐𝒎 𝝏𝒕

Where, 𝛻 = + + 16
Therefore, Schrodinger equation for three dimensional motion may be
written as

𝟐
𝟐

17
• The time dependent Schrodinger equation is given as

−ℏ 𝜕 𝜓(𝑥, 𝑡) 𝜕
+ 𝑉 𝑥, 𝑡 𝜓 𝑥, 𝑡 = 𝑖ℏ 𝜓(𝑥, 𝑡) −− −❶
2𝑚 𝜕𝑥 𝜕𝑡

By method of separation of variables, we can write 𝜓 𝑥, 𝑡 as

𝝍 𝒙, 𝒕 = 𝝍 𝒙 𝝓(𝒕)
Also, assume that P.E. is a function of 𝒙 only ⇒ 𝑉 𝑥, 𝑡 = 𝑉(𝑥)

−ℏ 𝜕 𝜓(𝑥)𝜙(𝑡) 𝜕
+ 𝑉 𝑥 𝜓 𝑥 𝜙(𝑡) = 𝑖ℏ 𝜓 𝑥 𝜙(𝑡)
2𝑚 𝜕𝑥 𝜕𝑡

−ℏ 𝜕 𝜓(𝑥) 𝜕𝜙(𝑡)
𝜙(𝑡) + 𝑉 𝑥 𝜓 𝑥 𝜙(𝑡) = 𝑖ℏ𝜓 𝑥
2𝑚 𝜕𝑥 𝜕𝑡
Dividing by 𝜓 𝑥 𝜙(𝑡)
−ℏ 1 𝜕 𝜓(𝑥) 𝑖ℏ 𝜕𝜙(𝑡)
+𝑉 𝑥 = −− −❷
2𝑚 𝜓(𝑥) 𝜕𝑥 𝜙(𝑡) 𝜕𝑡
18
X and t are independent variables, both the functions of x and t must be equal to a constant
 −ℏ 1 𝜕 𝜓(𝑥)
+𝑉 𝑥 =E −− −❸
2𝑚 𝜓(𝑥) 𝜕𝑥

𝑖ℏ 𝜕𝜙(𝑡)
=𝐸
𝜙(𝑡) 𝜕𝑡
Equation (3) can be written as
−ℏ 𝜕 𝜓(𝑥)
+ 𝑉 𝑥 𝜓 𝑥 = E 𝜓(𝑥)
2𝑚 𝜕𝑥

−ℏ 𝜕 𝜓(𝑥)
− 𝐸−𝑉 𝜓 𝑥 =0
2𝑚 𝜕𝑥

𝝏𝟐 𝝍(𝒙) 𝟐𝒎 4
−− −❸
+ 𝑬−𝑽 𝝍 𝒙 =𝟎
𝝏𝒙𝟐 ℏ𝟐

This is a time independent Schrodinger wave equation

In three dimension case, it can be written as,

−ℏ
𝛻 𝜓 + Vψ = 0
2𝑚 19
• The time-independent wave equation is used to study the properties of atomic systems in
stationary conditions.
• The solution of the Schrodinger wave equation gives the possible wave functions

Bound particle: Solution of the wave function is possible for certain desecrate energies only
• These discrete values of energy E1, E2,…..En are called eigen values or allowed values of
the energy of the particle.
• The solutions ψ1, ψ2, ……ψn corresponding to the eigen energy values En are called the
eigen functions.

Free Particle: Solution of the wave function is possible for all the energies
• Therefore, freely moving particle possesses a continuous energy spectrum, No energy
quantization
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• A particle is said to be a free particle when it is moving in space without being subjected to any
external force and its potential energy is constant everywhere
• The time independent Schrodinger wave equation of a free particle moving in +ve -direction is
given as
𝟐

𝟐 𝟐

𝟐 𝟐
−− −❶
𝟐 𝟐

As the free particle is moving with zero P.E., its total energy is K.E.
Equation (1) can be rewrite as
𝟐
𝟐 −− −❷
𝟐
Where
−− −❸
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(a) Wave Function:

The general solution of the equation is

( ) ( )

Since, particle is traveling in the positive x-direction, final wave equation is

given as

𝒊(𝝎𝒕 𝒌𝒙) 4
−− −❸

22
(b) Energy:
8𝜋 𝑚
−− −❸
From equation (3) we have 𝑘 =
ℎ
𝐸
ℏ
Therefore, particle energy is given as
𝟐 𝟐
−− −❺

The particle can have any value of energy as there are no boundary conditions applied on the
motion of particle
Energy is not quantized Freely moving particle possesses a continuous energy
spectrum
From equation (5) , the plot of E as a function of k is a parabola.

23
(c) Momentum:
The momentum operator, operating on the wave function gives
ℏ ℏ ( )

( )

ℏ 𝝏𝝍 −− − 6
𝒊 𝝏𝒙 𝒙

is a eigen function and is the eigen value of the momentum operator

(d) Position of the particle:

The probability of finding the particle between and is given by

𝟐
24
• A potential well is a potential energy function
that has a minimum
• If a particle is left in the well with energy less
than the height of the potential well, we say that
the particle is trapped in a potential well
• In quantum mechanics, such a trapped state is
called as a bound state

• Let us consider a particle confined to the region

• It means that in the region and

rises to infinity
• This situation is called a one-dimensional
potential box 25
The Schrodinger equation for a particle trapped in a one-dimensional potential box, V=0 is

−− −❶

Where
As particle can move back and forth freely between and
the solution of the equation (1) can be given as

−− −❷

We can evaluate the constants A and B with the help of boundary conditions

26
Applying 1st boundary condition ψ 𝑥 = 0 𝑎𝑡 𝑥 = 0
∴𝜓 =𝐴+𝐵 =0 𝜓(𝑥) = 𝐴𝑒 + 𝐵𝑒
⇒ 𝐵 = −𝐴 −− −❷
Putting in equation (2)
𝜓 𝑥 = 𝐴(𝑒 −𝑒 )
𝝍 𝒙 = 𝟐𝒊𝑨𝒔𝒊𝒏 𝒌𝒙 ∵ 𝑒 = 𝑐𝑜𝑠𝑥 + 𝑖𝑠𝑖𝑛𝑥
Applying 2nd boundary condition ψ 𝑥 = 0 𝑎𝑡 𝑥 = 𝐿
∴ 𝜓 = 2𝑖𝐴 sin 𝑘𝐿
2𝑖𝐴 sin 𝑘𝐿 = 0
The factor 2iA can not be zero, as it may result in loosing the wave function
∴ sin 𝑘𝐿 = 0
𝑜𝑟 𝑘𝐿 = 𝑛𝜋
𝟐𝑳
As 𝑘 = ⇒ 𝝀= 𝒏
−− −❸

Where n=1,2,3… is an integer

It implies that the wave equation has a solutions only when the particle wavelength is restricted to desecrate
values such that only a whole number of half wavelengths are formed over the length L
𝒏𝝅
It means that particle waves form standing wave pattern within the potential box ⇒ 𝒌 = 𝑳
27
i) The possible values of momentum of the particle are given
by

4
−− −❸

ii) The possible values of energies are

𝟐 𝟐 −− −❺
𝟐

This indicates that particle confined in a certain region can have

certain desecrate values of energy only.
28
The allowed wave function which are the solutions of the Schrodinger equation are given by
𝜓 = 2𝑖𝐴 sin 𝑘𝑥 = 𝐶𝑠𝑖𝑛 𝑘𝑥
𝒏𝝅
𝜓 = 𝐶𝑠𝑖𝑛 −− − 6 ∵𝒌= 𝑳
,
Applying normalization condition, we can determine the value of constant C
𝜓 𝜓 ∗ 𝑑𝑥 = 1

𝑛𝜋𝑥
∴ 𝐶 𝑠𝑖𝑛 𝑑𝑥 = 1
𝐿

𝐶 2𝑛𝜋𝑥
1 − 𝑐𝑜𝑠 𝑑𝑥 = 1
2 𝐿
2𝑛𝜋𝑥
𝐶 𝑠𝑖𝑛
𝑥− 𝐿 = 1
2 2𝑛𝜋
𝐿
𝐿 2 2
∴ 𝐶 =1 ⇒ 𝐶 = ⇒ 𝐶=
2 𝐿 𝐿

𝟐 𝒏𝝅𝒙
Equation (6) can be written as 𝝍𝒏 = 𝒔𝒊𝒏
𝑳 𝑳
29
This is a normalized wave function of a particle in an infinite potential well
The allowed energy states are given by
𝟐
𝟐
𝒏 𝟐

Where n is a quantum number given by n = 1,2,3….

First energy level n=1

Second energy level n=2

Third energy level n=3

Energy levels in the potential well

And so on….
A particle can not have a zero energy. The minimum energy allowed
for a particle is 30
• The probability of finding the particle over a infinitesimal distance at position
in the potential well is
𝑃 𝑥 𝑑𝑥 = 𝜓 𝑑𝑥
2 𝑛𝜋𝑥
= 𝑠𝑖𝑛 𝑑𝑥 𝟐 𝒏𝝅𝒙
𝐿 𝐿 ∵ 𝝍𝒏 = 𝒔𝒊𝒏
𝑳 𝑳
• The probability density is given by
2 𝑛𝜋𝑥
𝑃(𝑥) = 𝑠𝑖𝑛 𝑑𝑥
𝐿 𝐿

The probability density is maximum when

31
32