Quantum Mechanics

21PHYS12 PHYSICS FOR CSE STREAM

Introduction to Quantum Mechanics
In the latter part of the 19th century, study of the emission of radiation from black body was
carried out by Wilhelm Wein and Rayleigh Jeans to account for the energy emitted at different
wavelengths. The equation given by Wein fitted to shorter wavelengths and Rayleigh formula fit
the curve at longer wavelength side. Finally Max Plank worked out empirical equation that fitted
the entire curve completely well.

Need of Quantum Mechanics: With this success, Plank analyzed how his equation could be
interpreted and he realized that the energy of the emitted radiations are quantize d. With this
Plank‟s equation for energy density for blank body radiation was derived and his efforts laid the
foundation for quantum mechanics

Wave – particle dualism:

It is well known that light exhibits the phenomenon of interference, diffraction, and
polarization. This phenomenon can be explained using wave theory of light. This phenomenon
shows light behave as a wave, light has wave nature, but photoelectric effect, Compton Effect
and black body radiation can be explained on the basis of quantum theory. According to which
light propagates in small packets of energy h γ. These packets are called photons or quanta, which
behaves like a particle. Thus light possesses waves as well as particles. It is referred to as wave-
particle dualism or dual nature of light and matter. The wave associated with moving particles is
called as matter wave. According to de-Broglie, a moving particle behaves sometimes as wave
and sometimes as a particle.
De-Broglie hypothesis:
According to de-Broglie, a moving particle behaves sometimes as wave and sometimes as
a particle. The waves associated with moving material particle are called matter waves or de-
Broglie waves.
Since nature loves symmetry, if the radiation behaves like a particle under certain circumstances
and as waves under certain other circumstances. Then one can even expect that entities, which
ordinarily behave as a particle to exhibit properties attributable to, only wave under appropriate
circumstances.
h h
Therefore p= or λ =
 p
De-Broglie suggested that this equation applies as well to particle of mass „m‟, moving with a
velocity „v‟. Thus for a particle
P=m v λ is the wavelength of the waves associated with a particle of mass „m‟ moving with
a velocity „v‟ de-Broglie called these waves as matter waves.
h
Thus wavelength of matter waves, λ = , [p=m v] this result is known as de-Broglie equations
mv

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 Quantum Mechanics
De-Broglie wavelength of an accelerated electron:
Consider an electron of mass „m‟ accelerated through a potential difference of „V‟. The energy
acquired by the electron is eV. The velocity acquired by the electron be eV. Then,
1
eV= mv2.
2
p=mv
Squaring on both sides, we get,
p 2=m2v2
mv2= p 2/m
Substituting in Kinetic energy equation we get, eV = p 2/2m
p= 2meV
h h 6.63 10 34 1.226 10 9
λ=    m
p 2meV 2  9.110 31 1.602 10 19  V V

1.226 10 9
 m
V

Relation between Kinetic energy and de-Broglie wavelength of electron:

1
E= mv2.
2
p=mv
Squaring on both sides, we get,
p 2=m2v2
mv2= p 2/m
Substituting in Kinetic energy equation we get, eV = p 2/2m
p= 2mE
h
λ=
2mE
Phase velocity and group velocity

The phase velocity Vp of a wave is the rate at which the wave propagates
in any medium. This is the velocity at which the phase of any
one frequency component of the wave travels.
Vp = w/k

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 Quantum Mechanics
Wave's angular frequency ω, which specifies angular change per unit of time, and wave
number (or angular wave number) k, which represent the angular change per unit of space,

The group velocity Vg of a wave is the velocity with which the overall envelope shape of the
wave's amplitudes—known as the modulation or envelope of the wave—propagates through
space.
Vg= dw/dk

Relation betweenVp and Vg

Vg= Vp + k dVp/dk

Properties of Matter Waves

 Matter waves are not electromagnetic in nature

 Matter-wave represents the probability of finding a particle in space.
 Matter waves or de-Broglie is independent of the charge on the material particle. It
means matter-wave of the de-Broglie wave is associated with every moving particle
(whether charged or uncharged).
 Electron microscope works on the basis of de-Broglie waves.
 Matter waves can propagate in a vacuum, hence they are not mechanical wave.
 The number of de-Broglie waves associated with the nth orbital electron is n.
 The phase velocity of matter waves can be greater than the speed of light.

HEISENBERGS UNCERTAINTY PRINCIPLE

According to classical mechanics, a particle can occupy a definite position and momentum at any
instant of time. That is the trajectory of particle can be continuously traced. But, in atomic scale
such notion does not work. According to quantum mechanics [wave mechanics] it is impossible to
determine both position and momentum of particle simultaneously and accurately. If Δx is
uncertainty (error) in the measurement of position and ΔPx is the uncertainty in the measurement
h
of momentum, then Δx. ΔPx  this is called Heisenberg uncertainty principle.
4
It shows that if position is measured with higher accuracy then measurement in momentum P will
have lower accuracy and vice versa.
Statement of Heisenberg„s uncertainty principle (HUP)
“In any simultaneous determination of position and momentum of the particle, the product of
the corresponding uncertainty inherently present in the measurement is equal to or greater
h
than ”
4
h
Δx.ΔPx 
4

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 Quantum Mechanics
The H U P would also be expressed as in terms of uncertainties involved in the measurement of
physical variable pairs such as Energy and time, Angular displacement (θ) and angular
momentum (L)
h
ΔE Δt 
4
h
ΔL Δθ 
4
„Δ‟ is the minimum uncertainty involved in the measurement of the corresponding variable.

Physical significance of H U P:

The physical significance is that one should not think of exact position, or an accurate value for
momentum of a particle. Instead, one should think of probability of finding particle at certain
position or probable value for momentum of particle. The estimates of such probability are made
by means of certain mathematical function named as probability density function in quantum
mechanics.

Application of Heisenberg‟s uncertainty principle:

Non-existence of an electron inside the nucleus:

If the electron exists within the nucleus of an atom it can be anywhere within the diameter of the
nucleus. The maximum uncertainty in the position of electron is equal to or less than the diameter
of the nuclei.
-14
Δx=0.5x10 m.
From H U P, Δx. ΔPx  h
4

Uncertainty in the momentum of the electron is

ΔPx 
h 6.625 x10 34

4x 4 x3.14 x  10 14

ΔPx  = 1.05 x10-20 Ns

which is the uncertainty of the momentum of the electron. Then the momentum of the electron must at
least be equal to the uncertainty in momentum.

 Px= 1.05 x10-20 Ns

We know by theory of relativity

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 Quantum Mechanics
mo c 2
E  mc 2 
v2
1
c2

m0 2 c 6
E  2
c2  v2 ____________________ (1)

mo v
p  mv 
v2
1
c2

m0 2 v 2 c 2
p 
2
c2  v2

Multiplying by c2

m0 2 v 2 c 4
p c 
2 2
c2  v2 ________________ (2)

m 0 2 c 4 (c 2  v 2 )
E p c 
2 2 2
c2  v2

E 2  p 2 c 2  m0 2 c 4

E2= p2c2 +m02c4

E= energy, c= velocity of light, m0= rest mass of electron, p= momentum of electron .

E2  (1. 1x10-20)2x(3x108)2+(9.1x10-31)2x(3x108)4

1.5 x10 12

E  3.3x10-12J  E  eV
1.6 x10 19

E  20.6 MeV

This means that electron to exist inside the nucleus its energy must be greater than or equal to

20.6 MeV .But experimental investigations on β decay reveal that, the kinetic energy of β particles (which
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 Quantum Mechanics
are same as electron) is the order of 3 to 4 MeV .This clearly indicates that; electron cannot exist within

the nucleus.

Complementarity Principle in Quantum Mechanics

The principle of complementarity definition states that, when the particle nature of the matter (for
example light) is measured or displayed, the wave nature of the matter is necessarily suppressed
and at the same time if the wave nature of the matter is displayed then the particle nature will be
suppressed. The inability to observe the wave nature and the particle nature of the matter
simultaneously is known as the complementarity principle.

Wave function:
The variable quantity characterizing the matter wave is called wave function. It is also called the
state function. It is denoted by ψ. The value of the wave function associated with a moving body
at particular point x, y, z in space at the time “t” is related to the wave function in quantum
mechanics which accounts for the wave like properties of a particle. It is given by ψ (x, y, z, t).
Wave function is a complex quantity.
A system is defined by its energy, momentum, position etc. once the wave function ψ
corresponding to a system is known, the state of the system can be determined. A wave function
corresponding to a system will change when system changes its states. In quantum mechanics it is
postulated that the state of the system is completely characterized by a wave function.

Probability density
If we consider a single particle and ψ is the wave function associated with the particle then |ψ|2
is the probability per unit volume that the particle will be found at the
given point. It can also be stated in the following manner V
Let V be a volume inside which a particle is known to be present, but
where exactly the particle is situated inside V is not known. Then the
probability of finding the particle in a certain element of volume dv of V
is equal to |ψ|2 dv. For this reason |ψ|2 is called probability density dv
Probability density | ψ |2=ψ*ψ
ψ*ψ is always positive and real quantity. ψ* is complex conjugate of ψ.
ψ* and ψ may be complex. Probability of occurrence of on event is a real and positive quantity.

Normalization
If Ψ is a wave function associated with a particle, then |ψ|2 dv is the probability of finding the
particle in a volume dv.
According to statistical rule
V 2
 dv  1 . ----------------------(1) That means definite presence of particle in the particular region
0
or space of volume V

If   2 dv  0 . That means that particle does not exist.


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 Quantum Mechanics
 2
 dv  1 . That means the particle is there at somewhere in space.

A wave function that obeys equation (1) is said to be normalized.

Properties of wave function:

Property (1)  “Ψ” is single valued everywhere.

Property 2  ”Ψ” is finite everywhere..

Property 3  Ψ and its first derivative with respect to its variable are continuous
everywhere
Property 4  for bound states Ψ must vanish at infinity. If Ψ is a complex function, then
Ψ**Ψ must vanish at infinity.

One –dimensional time independent Schrodinger‟s wave equation:

According to the de-Broglie theory for a particle of mass m, moving with a velocity of V, the
h
wave length λ= -------------------------- (1)
p
P= m v = momentum of the particle
The wave equation for a de-Broglie wave considered traveling in positive x direction can be
written in complex notation as
ψ=A ei(Kx-w t)------(2)
A=constant, w=angular frequency of the wave, k=propagation constant

By differentiating equation (2) twice with respect to “t” we will get

d
= A ei(kx-wt) (-iω)
dt
d 2
2
= A ei(kx-wt) (-iω) (-iω)
dt
d 2
=-ω2 A ei(kx-wt)= -ω2ψ ------------------------(3)
dt 2

The travelling wave equation is given by,

d 2 y 1 d2y
= 2
dx 2 v dt 2

d 2 1 d 2
= -------------(4)
dx 2 v 2 dt 2

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 Quantum Mechanics
The above equation represents wave traveling with a velocity v, and ψ is the displacement at the
instant t.
2
d 
2
From equation (3) and (4), =( )ψ
dx 2 v2
λ and γ are the wavelength and the frequency of the wave, then
ω =2πγ and v= γλ, substituting for ω and v
d 2  4 2
=
dx 2 2
1 1 d 2
Or, = ----------------------------------------(5)
2 4 2 dx 2
For a particle of mass m moving with a velocity v,
1 m 2v 2 p 2 h
Kinetic energy = m v2= = ------------(6) , But we know p= ,
2 2m 2m 
p 2 (h  )
2
h2 h2 1 h2 1 d 2
 Kinetic energy = =  2  ( 2) ( )
2m 2m  2m 2m  2m 4 2 dx 2

h2 d 2
 Kinetic energy=  ----------------------------(8)
8 2 m dx 2
The total energy E is the sum of K.E + potential energy
E= K E + PE
Potential energy =V
h2 d 2
Therefore E=  +V ---------------------------(9)
8 2 m dx 2
h2 d 2
Or  =(E-V) -------------------------------------(10)
8 2 m dx 2

d 2 8 2 m
=  2 (E-V)ψ
dx 2 h
d 2 8 2 m
 (E-V)ψ=0 This is the time independent Schrodinger‟s equation in one
dx 2 h2
dimension

Eigen values and Eigen function:

We have Schrodinger wave equation given by, d 2 8 2 m
 (E-V)ψ=0
dx 2 h2

Eigen functions.

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 Quantum Mechanics
Definition: “Eigen functions are those wave functions of quantum mechanics which possess the
properties that are single valued, finite everywhere and also their first derivatives with respect to
their variable are continuous everywhere”.
Eigen values:
When Eigen functions are known, quantum mechanical operators are used to evaluate physical
quantities. There is only a restricted set of Eigen function; there is also restricted set of energy
values. These values are called Eigen values. The wave function must be such that the operator
operating on it must reproduce the wave function multiplied by a constant. This constant value is
the Eigen value.

Application of Schrodinger wave equation:

Particle in one-dimensional potential well of infinite height(Particle in a box):

Consider a particle of mass “m” which is free to move in the x-direction only in the region from
x=0 to x=a. Outside this region, the potential V is taken to be infinite and within this region it is
zero (which mean that the particle is bound within the limits x=0 to x=a) such a type of potential
in space is called infinite potential well. A particle found within such an infinite potential is
referred to as particle in a box.

The Schrodinger equation is,

d 2 8 2 m
 (E-V)ψ=0
x 2 h2
Outside the well the Schrodinger equation is,
d 2 8 2 m
 (E-∞) ψ=0 ---------(1) (since V=∞)
x 2 h2
This equation holds good if ψ=0 for all points outside the well,
|ψ|2=0, which means that the particle cannot be found at all outside the well.

Inside the well the Schrodinger, s equation is given by,

d 2 8 2 m
 (E-0)ψ=0
x 2 h2
d 2 8 2 m
 (E)ψ=0 --------------(2) (since V=0)
x 2 h2

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 Quantum Mechanics
8 2 m 2
In the equation (2) we have to put 2
E =k ,
h
d 
2
We have, 2
+k2ψ=0--------------(3)
dx
Discussion of the solutions;
The solution of the above equation (3) is given by
ψ=C cos(kx)+D sin(kx)----------------------------(4)
But ψ =0 at x=0,  equation (4) becomes, 0= Ccos(k0)+Dsin(k0).
Therefore, C=0----------- -------------(5)
Also ψ =0 at x=a,  equation (4) becomes 0=Ccos(ka)+Dsin(ka).
But C=0 from equation (5), hence D sin(ka)=0, here D≠0
 sin (ka)=0 or ka= n π, where n= 1,2,3… n is called quantum number which is either zero or
positive integer.
n
 k= ------------------------- (6)
a
Substituting for “C” and “k” from equation (5) and (6) in the equation (4) .
n n
ψ =0cos( x)+D sin( x)
a a
n
ψ n=Dsin ( ) x ------------------------(7)
a
Energy Eigen value:
8 2 m n
2
E =k2, since k=
h a
n2 2
8 m2

2
= 2 E
a h
n2 2

2 n 2 2 h 2 n2h2
E= a = 
8 2 m 8 2 ma 2 8ma 2
h2
n2h2 This is Energy Eigen value equation.
En= When n=0, E=0, value zero for n is not acceptable.
8ma2
Because when n=0, ψ n=0

h2
For n=1, E1= = ground state energy = zero point energy
8ma2
4h 2
For n=2, E2 =  4E1
8ma 2
Thus the energy in the first excited state is 4 times the zero point energy.

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 Quantum Mechanics
2
9h
For n=3, E3 =  9E1
8ma 2
Thus the energy in the second excited state is 9 times the zero point energy.
Thus n=1, E1- Ground state energy or zero point energy.
n=2, E2- First excited state energy
n=3, E3- Second excited state energy.
Normalization
The integral of the wave function over the entire space in the well must be unity because, there is
only one particle is present inside the well somewhere else.
a

 dx  1 ----------------------- (8)
2
n
0

Substituting for ψ n from equation (7), we will get,

a nx
2 2
 D sin ( )dx  1
0 a
1
But we know that sin2 θ= (1-cos 2θ).
2
a 1 nx
D
2
{1  cos( 2 )}dx  1
0 2 a

2nx
a a
1 1
D2 [
20 dx   cos(
20 a
)dx]  1

2nx
sin( )
D2 a D2 a ] a =1.
Or x0  [
2 2 2n 0

a
D2 d2 a 2na 2n 0
Or, (a  0)  [sin( )  sin( )]
2 2 2n a a
D2a
Or,  1 , [since, sin (2nπ)=0, sin (0)=0]
2
2
Or D=
a
Thus the normalized wave function of a particle in one-dimensional potential well is
2 nx
ψ n= sin( ) ---------------------------- (9)
a a

This is the Eigen function.

Wave functions, probability densities and Energy levels for particle in an

infinite potential well:

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 Quantum Mechanics

The most probable location of the particle in the well and its energies are to be evaluated for the
different permitted sates.
We can write the eigen functions ψ 1, ψ 2, ψ 3.. For a particle in the well by considering n=1,2,3
respectively in the equation.
Let us consider the first 3 cases.
Case (i): n=1:
This is the ground state and the particle is normally found in this state.
For n=1, the eigen function is,
2 x
ψ 1= sin( ) , from equation (9)
a a
ψ 1=0, for both x=0 and x =a.
a
But Ψ1 has maximum value for x = ( ).
2
Thus a plot of ψ 1 versus “x” will be shown in figure
And a plot of | ψ 1|2, the probability density verses “x” is also shown below.

It indicates the probability of the finding the particle at different location inside the well.
| ψ 1|2 is 0 both at x=0, and at x=a.
a
ψ is maximum at x = ( ) it says that the particle is cannot be found at all at the walls of the well,
2
and the probability of finding the particle is maximum at the central region.
If n=1
h2
E1= = ------------- (10)
8ma2
This is ground state energy or zero point energy.

Case (ii): n=2:

This is the first excited state i.e. the next immediate higher state permitted for the particle after the
ground state.
The eigen function for this state is
2 2x
ψ 2= sin( )
a a
a a 3a
Now ψ 2=0 for the values x=0, and a, also ψ 2 is maximum for x=( ) and ( ).
2 4 4

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 Quantum Mechanics
a
The plot of | ψ 2|2 verses x in this figure | ψ 2|2=0 at x=0, and a.
2
It means that in the first excited state the particle cannot be observed either at the walls, or at the
center. If n=2, energy equation E2 =4E1, First excited state.

Thus the energy in the first excited state is 4 times the zero point energy.
Case (iii), n=3:
The Eigen function for the second excited state as,
2 3x a 2a
ψ3 = sin( ) , Ψ3 =0, for x=0, , and a.
a a 3 3
a a 5a
ψ 3 will be a maximum value for x= , and .
6 2 6
The plot of ψ 3 verses x and | ψ |2 verses x is as shown bellow.

9h 2
For n=3, E3 =  9E1
8ma 2
Thus the energy in the second excited state is 9 times the zero point energy.

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Quantum Mechanics

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