QUANTUM MECHANICS

DUAL NATURE OF MATTER:

Light exhibits the phenomena of interference, diffraction, polarization and also photo electric
effect and Compton Effect. Interference, diffraction and polarization can be explained by wave nature of
light which is based on transfer of energy. The photoelectric effect and Compton Effect are explained by
quantum theory. This indicates the particle nature of light which is based on transfer of momentum apart
from transfer of energy. So light has dual nature that is wave nature and particle nature.

In 1924 de Broglie proposed that a beam of particles behave as a wave in transferring energy. This is dual
nature of matter. He proposed this without any strong experimental support and hence called Hypothesis.

Matter Waves: Waves associated with the material particle are called Matter Waves.

1. DE BROGLIE HYPOTHESIS:

The dual nature of light possessing both wave and particle properties was explained by combining
Planck’s expression for energy of a photon E = hν with Einstein’s mass energy relation E = mc2

According to Planck’s theory E= hν

Einstein’s mass energy relation E = mc2

c
But we know that ν= , we get
λ

hc
∴ = mc2 or h h
λ λ= =
mc p

The wavelength λ is called de Broglie wavelength. It is defined as the ratio of Planck’s constant to the
momentum of a particle.

h h
λ= =
mv p

Particle does not exhibit the wave nature and particle nature simultaneously.

De Broglie wavelength of electron: When a potential difference ‘V’ is applied to the electron it
accelerates with velocity ‘v’ then the work done on the electron is ‘eV’. This work done is converted into
the kinetic energy of the electron. Thus,

1
eV = mv 2
2
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 QUANTUM MECHANICS

2meV = (mv)2

mv = 2meV

h
Substituting this value in de Broglie wavelength λ = .
mv

h 6.625 ×10 −34

λ= =
2meV ( )(
2 × 9.1 ×10 −31 × 1.6 × 10 −19 × V )
12.27 1.227
= A0 or nm
V V

Properties of matter waves: Waves associated with the material particles such as electron, proton,
etc., are called matter waves.
h
The wavelength of matter waves is given by λ =
mv
1. Greater the mass of the particle, lesser the wavelength associated with it.
2. Greater the velocity of the particle, lesser the wavelength associated with it.
3. The matter waves are generated by the motion of the particles. They are independent of charge of
particle. Whereas the electromagnetic waves are produced by the moving charges only.
4. Particle does not exhibit wave nature and particle nature simultaneously
5. Velocity of the matter waves ‘ω’ is greater than the velocity of light ‘c’.
i.e., E = hν and E= mc2

mc 2
∴ hν = mc2 or ν =
h
h
But from de Broglie Eq. λ =
mv
The matter wave velocity, ω=νλ
Substituting λ and ν we get

mc 2 h c 2
ω= × =
h mv v
As the velocity cannot exceed velocity of light hence the velocity of matter waves is greater than
the velocity of light.

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 QUANTUM MECHANICS

HEISENBERG UNCERTAINTY PRINCIPLE

According to Heisenberg it is impossible to determine the exact position and momentum of a moving
particle.

If △x denotes the error (uncertainty) in the measurement of the position of the particle along x-axis and
△p represents the error in the measurement of momentum, then

△x.△p = h ------------ (1)

Where h is plank’s constant. The above equation represents the uncertainty involved in the measurement
of both the position and momentum of the particle.

In more optimized form the above equation can be written as

h h
(△x. △p) ≥ or ------------ (2)
2 4π
If the time during which a system occupies a certain state is not greater than △t, then the energy of the
state cannot be known to within △E, where:

h
(△E) (△t) ≥ ----------- (3)
2

SCHRÖDINGER’S TIME INDEPENDENT WAVE EQUATION: If particle has wave properties, it

is expected that there should be some kind of wave equation which describes the behavior of the particle.

Consider a system of stationary waves associated with a particle. Let (x,y,z) be the coordinates of
the particles and Ψ is the wave displacement for the de Broglie waves at any time ‘t’. The classical
differential equation of a wave motion is given by

∂ 2Ψ 2  ∂ 2Ψ ∂ 2Ψ ∂ 2Ψ 
= v  2 + 2 + 2  = v 2 ∇ 2 Ψ ------------ (1)
∂t 2  ∂x ∂y ∂z 

∂2 ∂2 ∂2
Where ∇ =
2
+ + and v is the velocity of the wave.
∂x 2 ∂y 2 ∂z 2

The solution of the equation (1) can be written as,

Ψ(x,y,z,t) = Ψ0(x,y,z)e-iωt ------------(2)

Where Ψ0(x,y,z) is a function of (x,y,z) and gives the amplitude at the point considered. Equation (2) can
also be expressed as

Ψ ( r, t ) = Ψ0 (r) e-iωt ------------- (3)

Differentiating equation (3) twice, we get

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 QUANTUM MECHANICS

∂2Ψ
2
= - ω2 Ψ0(r) e-iωt
∂t

= - ω2 Ψ

Substituting this value in equation (1) , we get

2 2
- ω2 Ψ = v ∇ Ψ

2 ω2
⇒∇ Ψ + = 0 ----------- (4)
v2

v ϖ 2π
But ω = 2πn = 2π ⇒ =
λ v λ

2 4π 2
∴ ∇ Ψ+ Ψ = 0 --------- (5)
λ2
h 1 m2 v2
Now from the de Broglie relation λ = m v or 2 =
λ h2

4π 2 2 2
∇2 Ψ + m v = 0 --------------- (6)
h2

If ‘E’ and’ V’ be the total and potential energies of the particle respectively, then its kinetic energy is
given by

1
mv2 = E – V or
2

m2v2 = 2m (E-V) ------------ (7)

From equations (6) and (7), we have

2 4π 2
∇ Ψ + 2 2m (E-V) Ψ = 0
h

8π 2 m
∇2 Ψ + (E-V) Ψ = 0 ----------- (8)
h2

Equation (8) is known as Schrödinger’s time independent wave equation.

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 QUANTUM MECHANICS

h
Put ℏ =
2 π , the above equation can also be expressed as

2m
∇2 Ψ + (E – V) Ψ = 0 ----------- (9)
h2

2 8π 2 m
For free particle potential energy V = 0, ∴∇ Ψ + EΨ = 0
h2

SCHRÖDINGER’S TIME DEPENDENT WAVE EQUATION:

If particle has wave properties, it is expected that there should be some kind of wave equation
which describes the behavior of the particle. Consider a system of stationary waves associated with a
particle. Let (x,y,z) be the coordinates of the particles and Ψ is the wave displacement for the de Broglie
waves at any time ‘t’. The classical differential equation of a wave motion is given by

∂ 2Ψ 2  ∂ 2Ψ ∂ 2Ψ ∂ 2Ψ 
= v  2 + 2 + 2  = v 2 ∇ 2 Ψ ------------ (1)
∂t 2  ∂x ∂y ∂z 

∂2 ∂2 ∂2
Where ∇ =
2
+ + and v is the velocity of the wave.
∂x 2 ∂y 2 ∂z 2

The solution of the equation (1) can be written as,

Ψ(x,y,z,t) = Ψ0(x,y,z)e-iωt ------------(2)

Where Ψ0(x,y,z) is a function of (x,y,z) and gives the amplitude at the point considered. Equation (2) can
also be expressed as

Ψ ( r, t ) = Ψ0 (r) e-iωt ------------- (3)

Differentiating the above equation, we get

Ψ = Ψ0 e-iωt (-iω)

∂Ψ  E
⇒ = (-iω Ψ) =  − i  Ψ [ ω = 2ᴨυ = 2ᴨ
∂t  h

as we know E= hυ , υ= ]

h ∂Ψ
⇒ -(i/i) =EΨ
i ∂t

∂Ψ
ih = E Ψ ----------- (4)
∂t
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 QUANTUM MECHANICS

From the Schrödinger’s time independent wave equation,

2m
∇2Ψ + (E – V) Ψ = 0
h2

2m
∇2Ψ = − (E – V) Ψ
h2

h2 2
- ∇ Ψ +V Ψ = EΨ -------- (5)
2m

Substituting the value of EΨ from Eq.(4) into Eq.(5), we get

h2 2 ∂Ψ
- ∇ Ψ +V Ψ = i h ---------- (6)
2m ∂t

 h2 2  ∂Ψ
 − ∇ + V Ψ = i h or
 2m  ∂t

HΨ=EΨ

 h2 2 
where H =  − ∇ + V  is called Hamiltonian which gives the total energy of the particle.
 2m 

Equation (6) is called Schrödinger’s time dependent equation which is applicable to non-relativistic
particles.

PHYSICAL SIGNIFICANCE OF THE WAVE FUNCTION ‘Ψ’:

Max Born in 1926 gave a satisfactory explanation for the wave function ‘Ψ’ associated with a moving
particle.

2 *
(
Born postulated that the square of the magnitude of the wave function Ψ or ΨΨ if Ψ is complex )
2
represents the probability of finding the particle in the given region. Ψ is called probability density and
Ψ is probability amplitude. Thus the probability of the particle within an element volume dxdydz (or) dV
2
is Ψ dxdydz.

2
Since the particle is certainly somewhere in the given region, the integral of Ψ dxdydz over all the
space must be unity. i.e,

∞ 2
2
∫∫ ∫ ψ
−∞
dxdydz = 1 or ∫∫∫ ψ
V
dV = 1

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 QUANTUM MECHANICS

A wave function that obeys the above equation is called normalized. Every acceptable wave function
must be normalizable and should fulfill the following conditions:

1. ψ must be finite for all values of x,y z.

2. ψ must be single valued
3. ψ must be continuous in all regions except where the potential energy is infinite.
4. ψ must possesses continuous first order derivative every where
5. ψ vanishes at the boundaries.
6. A wave function satisfying the following condition is called orthogonal wave function.
∞

∫ψ ψ dx = 0
*

−∞
PARTICLE IN ONE DIMENSIONAL POTENTIAL BOX:

When a motion of a particle is confined to a limited region such that the particle moves back and forth in
the region, the particle is said to be in bound state.

Consider a particle of mass ‘m’ bouncing back and forth between the rigid walls of a one dimensional
box.

Suppose that a particle does not lose energy when it collides

with walls, so that its total energy remains constant. This box
can be represented by a potential well or box of width ‘a’.

The potential energy ‘V’of the particle is infinitely high beyond

the walls, while inside the box ‘V’ is uniform.

This potential well can mathematically describe as:

V(x) = 0 for 0 < x < a

= ∞ for x < 0 and x > a

The uniform potential of the particle inside the box is taken as zero for simplicity.

From Schrodinger’s wave time independent wave equation, we have

d 2 Ψ 8π 2m
+ EΨ = 0 or (∵ V = 0 inside the box)
dx 2 h2

d 2Ψ 2
+kΨ=0 ------------ (1)
dx 2
8π 2m
Where k2 = E ---------- (2)
h2
The solution of the above equation is of the form

Ψ(x) = A sin kx + B cos kx ----------- (3)

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 QUANTUM MECHANICS

Where A and B are arbitrary constants can be obtained by applying the boundary conditions of the
problem.

(i) Ψ(x) = 0 at x = 0

(ii) Ψ(x) = 0 at x = a

From the first boundary condition, 0 = 0 + B ⇒ B = 0.

Hence Ψ(x) = A sinkx ---------- (4)

From the second boundary condition, 0 = A sinka (∵ already we got B=0)

If A sinka = 0, either A = 0 or sinka = 0.

nπ
A = 0 is not applicable. So sinka = 0, ka = nπ or k =
a
n 2π 2
K2 = ---------- (5)
a2
nπ x
∴ The solution can be written as Ψ(x) = A sin -------- (6)
a

8π 2m n 2π 2
From equations (2) and (5) E= or
h2 a2

n 2h2
En = ----------- (7) n= 1, 2, 3 …
8 a2m

It is clear that inside the potential box, the particle can have discrete energy levels. That is the energy of
the particle is quantized.

Determination of constant ‘A’ (by using normalization condition):

The wave function of the motion of the particle is

nπ x
Ψn = A sin for 0 < x< a
a

=0 for x < 0, x > a

The probability of finding the particle in the box at some where is unity.

a
2
∴ ∫ Ψ ( x)
0
dx = 1 or

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 QUANTUM MECHANICS

a
nπ x
∫A
2
sin 2 dx = 1 or
0
a

a
nπ x
∫ sin
2 2
A dx = 1 or
0
a

a
1 2n π x 
A 2
∫ 2 1 − cos
0
a 
dx = 1 or

a
A2  2 nπx a 
2  x − sin a 2 n π  = 1 or
 0

A2 a
=1 or [ ∵ sin nπ = 0 for all n]
2

2
A=
a

2 nπ x
Ψ(x) = sin ------------- (8)
a a

Equation (8) gives the wave function of the particle enclosed in infinitely deep potential well.

The wave functions for the first three values of ‘n’ are shown in figure.