ChapIII-Principles of Quantum Mechanics

1. Introduction to Quantum Mechanics

Topic1: WAVES AND PARTICLES, DE BROGLIE HYPOTHESIS, MATTER WAVES

De BROGLIE HYPOTHESIS

The wave-particle duality of light (or electromagnetic waves in general) led de-Broglie to suggest
that matter might also exhibit such duality and can have wave properties. He thought that if waves
can have properties of particles (matter), particles (matter) should have properties of waves and
there should be a link between the two models.

Hypothesis

In simple terms de Broglie hypothesis states that all moving particles have a ‘matter wave’
associated with them.

He obtained a relation for the wavelength of matter waves based on the energy and momentum
equations of electromagnetic waves/photons.

Expression for de Broglie wavelength

He obtained the expression for wave length of matter waves as follows:

As per the wave model light

hc
E  hf  [ c f]

But by Einstein’s mass-energy relation from theory of relativity, energy, E is expressed as:

E  mc 2

Since both energies are of the same entity we can equate them. That is,

1
 hc
 mc 2

h
Or 
mc
This is relation gives wave length of a photon of momentum, mc.

In accordance with this relation de-Broglie expressed wavelength,  of mater wave associated
with a particle of momentum, p as:

h

p

h
Or 
mv

This relation allows us to calculate the wavelength of the so called matter wave associated with a
moving particle.

Thus de Broglie hypothesis, assigns wave-like properties to something that is normally thought to
be a particle. Acceptance of both particle and wave behaviors of matter is usually referred to as
duality of matter.

Properties of Matter Waves

1. A matter wave is not physical Phenomenon. They are just pilot waves in the sense that
their only function is to pilot or guide the material particles. Hence they are also treated
as probability waves.
2. These waves are not electromagnetic waves (either).
3. The concept of matter waves is given for particles that are in motion. If a particle is at
rest then there is no meaning of matter waves associated with it.
4. Smaller is the velocity of the particle, greater is the wavelength associated with it.
5. Lighter is the particle, greater is the wavelength of the matter wave.
6. The (phase) velocity of matter wave is greater than velocity of light.
7. The concept of matter wave introduces an uncertainty in the location of the particle.
This is because a wave can’t be said to be present at this point or that. However the
chances of finding the particle are large where the wave amplitude is large.

Other forms of the relation:

 In case of a moving particle of KE, E K and mass, m, de Broglie wavelength is given by:
h

2 EK m

2
  In a charged particle of mass, m is moving in a field of potential, V then de Broglie
wavelength is given by:

h

2qVm

Experimental Verification of Matter Waves

If particles possess wave-like properties then they must exhibit the basic phenomena of waves like
interference and diffraction.

Without observing such phenomenon experimentally de Broglie’s matter waves hypothesis can’t
be accepted as a reality though his equation allows us to calculate wavelength associated with
moving particles.

Luckily the required experimental evidence came from many experiments. The first every
evidence was provided by experiments of C. J. Davisson and L. H. Germer of the Bell Telephone
Laboratories, USA and immediately after that by, George P. Thomson of the University of Aberdeen in
Scotland. These two experiments, performed with electrons, showed an excellent interference
phenomenon, which is an ample proof of the wave nature of electrons. After these, similar interference
phenomenon has been demonstrated with protons, neutrons and various atoms.

In the following we will study the Davisson and Germer and the G. P. Thomson experiments in
detail.

Davisson and Germer Experiment

A. Experimental Setup
The schematic diagram of the experimental setup used by Davisson and Germer is shown
in Fig.5.1. EG is the electron gun-that produces a beam of electrons. This beam of electrons is
focused and accelerated by the anode ‘AN’. A narrow beam of electrons thus generated is directed
on to the target: a large Ni crystal. The crystal can be rotated about the axis of the incident beam
of electrons. The electrons which fall on the target are reflected in various directions.

These scattered electrons are collected by the detector D, which is connected to a

Galvanometer. The detector can be moved along a circular scale so that it is able to receive
electrons at all angles between 20o to 90o. The accelerating potential was in the range of 30 to 600
Volts. The entire apparatus was enclosed in a highly evacuated chamber.

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 Fig.5.1 Experimental set up used by Division and Germer

B. Procedure of the Experiment

Experiment is done for different values of applied voltage. For each voltage, the detector
is moved along the circular path and current values shown by Galvanometer are noted. Fig (5.2b)
shows the graphs of current, I versus angle, q drawn in polar plot. All the graphs show that
intensity of the current is not decreasing continuously with the angle but is showing a peak at a
definite angle. This is the manifestation (indication) of wave behaviour of electrons.

Note 1: How do we measure  and I in the graphs? Take a point in the curve and draw a line pointing from it to the
origin. The angle between line drawn and the x-axis is the angle of the collector and length of the line gives the current
‘I’.
C. Verification ofValues

Theoretical value of 

According to the de Broglie’s theory, the wave length of electrons accelerated with V volts,
is given by
h

2emeV
For, V = 54 Volts, e  1.6 1019 C , me  9.11031 kg

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 6.63 1034

2 1.6 1019  9.11031  54
o
  12.27  1.67 A
54

xperimental value of 

Note that diffraction maximum has occurred at   50 . The interplanar spacing between
the parallel planes having Miller indices (111) is equal to 2.15 A . Then if we consider the
first order ( n  1 ) diffraction maximum, from Bragg’s law, 2d sin   n we will have,
     2.15sin 50  1.65 A
Thus there is an excellent agrement between the experimentally obtained and theoretically
calculated values of de-Broglie’s wavelength. This gives a clear confirmation of the de Broglie’s
hypothesis.

HEISENBERG UNCERTAINTY PRINCIPLE

The Heisenberg uncertainty principle is about our inability in measuring the position and
momentum of quantum (micro) particles simultaneously and precisely.

This limitation has nothing to do with imperfect measuring devices or experimental errors. It
arises because of the intrinsic wave-particle behavior of quantum particles.

Statement:

Uncertainty principle applied to position and momentum of a particle states that, it is impossible
to measure exactly the position and the momentum of the particle simultaneously.

The uncertainty x in position and the uncertainty p in momentum are related by:
h
x  p 
4
where h is the Planck’s constant.

The more precisely the position is determined, the less precisely the momentum is known in this
instant, and vice versa. They are linked variables and are called conjugate quantities.

Measurements of energy and time are also linked variables. Hence there is an uncertainty
relation between them also.

h
t  E 
4

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 t -is the uncertainty in the measurement of time
E -is the uncertainty in the measurement of energy

The implications of this lack of precision are profound. Before quantum theory was
introduced, the physical world was best described by Newton’s laws which are deterministic.
A deterministic theory allows us (in principle) to make absolute predictions about the
future. Quantum mechanics is not deterministic. In other words its future can never be
determined exactly and precisely. The best we can do is to work out a range of possibilities for
its future.
Problem
Example: The position of a proton is measured with an accuracy of 1.0 1011 m . What is the
minimum uncertainty in the proton’s position 1.0 s later?

h h
x  p  ; x  mv 
4 4

h 6.63 1034
v  
4 mx 4 1.67 1027 1.0 1011
 3200 m s -1
Thus uncertainty in position after 1.0s is 3.2 km

Applications of the uncertainty principle

1. Estimate of the energy of an electron in an atom.

2. Impossibility of an electron existing within a nucleus of an atom.
3. Estimate of lifetime of an electron in an excited energy state.

1. Estimate of the energy of an electron in an atom.

When an electron is known to be confined within an atom, then the uncertainty in its
position Δx must be less than the size of the atom, a. If we equate the two, this means the
uncertainty for its momentum can be estimated as:
h h
p  
4x 4 a
Then, p  p , then kinetic energy of the electron would be:

p2 h2
EK  
2m 32 2 ma 2

The diameter of a hydrogen atom is approximately 1.0  10 10 m , so the estimation of the
kinetic energy is:

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 (6.6 1034 ) 2
EK   1.5 1019 J
32  9.3 10  (10 )
2 31 10 2

 1 eV

This calculation is a very rough estimate but correctly predicts the right order of magnitude
for the electron’s kinetic energy of the ground state of electron in H atom is 13.6 eV .

2. Impossibility of an electron existing within a nucleus of an atom.

The above calculation can be repeated imagining an electron being trapped inside the
nucleus of size 1.0  10 14 m . If confined to a space of this small size, the electron’s kinetic
energy would be estimated to be a factor of 108 times bigger. An electron with an energy
of the order of 100MeV cannot be bound to a nucleus and thus it would have enough
energy to escape.

3. Estimate of lifetime of an electron in an excited energy state.

An estimate of the lifetime of an electron in the excited state can be made using the
uncertainty principle.

h
E  t 
4
If, E  5  10 7

6.6 1034
t 
4  5 107 1.6 1019
 6.6 1010  1 ns

SCRODINGER WAVE EQUATION

Note about the equation
What is the Schrodinger wave equation?

De Broglie’s hypothesis does not give the complete picture of the wave?Complete description a a wave requires
three parameters: wave length, velocity, amplitude:

de Broglie’s hypothesis tells us that matter is associated with waves. It gives us wavelength   h mv ). But
then what about amplitude?

This is exactly the gap the famous Austrian Physicist, Erwin Scrodinger had filled up. He postulated a differential
equation that gives the amplitude of the matter waves on the lines of classical wave equation,  2 D  v 2  2 D
t 2 x 2

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To be precise, amplitude of matter wave of a particle, of a given physical situation , is the solution of the
Schrodinger of equation. It is like calculating :

2 D 2  D
2
D 
from
  v and E ( x, y, z ) 
from
 Maxwell ' sequations
t 2 x 2
Thus,

 ( x, y, z ) 
from
 Schrodinger's wave Eq

 ( x, y, z ) --Psi-function in a way gives amplitude of matter waves

Schrodinger equation is a second order (complex differential) equation. Its

time independent version is: d   8 m ( E  V )  0

2 2

2 2
dx h

where  ( x, y , z ) of x, y and z.

(Derivation or ) verfication of Scrodinger equation

Schrodinger has just postulated his equation. That is he did not derived it from fundamentals.
Therefore we can only verify it on the lines of classical principles. According to de Broglie’s idea,
a freely moving particle can be compared to a plane wave

 ( x)  aei (t kx ) (1)

where, k  2  and   2 f .
Now differentiating Eq. (1 ) twice w.r.t x. we get.

d
 (ik )ae  i (t  kx ) (2)
dx
Differentiating the above relation again, we get

d 2
 (ik ) 2 aei (t kx )
dx
d 2
 (ik ) 2
dx 2

k  2  and i 2  1

d 2  2 
2

   (3)
  
2
dx

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As per de Broglie’s theory   h p

d 2  2 
2
p2
       (2 )2
  
2 2
dx h

d 2 p2
2
  2 (2 ) 2
dx h

 h  d 1
2 2

p  
2
 (4)
 2  dx 
2

2
In classical mechanics, Ek  p
2m

1  h  d 2 1  h2  1 d 2
2

Ek        2 
2m  2  dx 2   8 m   dx
2

 h 2  1 d 2
Ek    2  (5)
 8 m   dx
2

If the particle is moving in a potential V, it’s total energy E is given by;

E  Ek  V or Ek  E  V (6)

 h 2  1 d 2
E V    2  (7)
 8 m   dx
2

8 2 m d 2
2
( E  V )   2
h dx

d 2 8 2 m
 2 ( E  V )  0 (For 1D) (8)
dx 2 h

In case of 3D
8 2 m
 2  ( E  V )  0 (9)
h2

where, 2 
2 2 2
 2 2 and   i   j   k 
x y z
2
x y z

PHYSICAL SIGNIFICANCE OF WAVE FUNCTION

The wave function denoted by  ( x ) describes the amplitude of the matter wave (i.,e, de
Broglie wave) in a way. But does it mean by amplitude of the matter wave? Schrodinger himself
could not assign any meaning to wave function (or amplitude) of matter wave.

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 Interpretation of what  ( x ) really means came, subsequently, from the German physicist
Max Born. He suggested that  ( x ) itself does not have any meaning, however,  ( x) gives the
2

probability of finding the particle at a location and at a specified time.

In other words if  ( x ) is the wave function of a particle then,  ( x) is the probability

2

finding it with in a unit length around the position x at time t.

P( x, t )  
2

Note unit length becomes unit area in 2D and unit volume in 3D.

In general P ( x, t ) x , is the probability of finding the particle within a small interval

x around x is given by:
P( x, t )x   x (In 1-D)
2

P( x, t )V   V (In case of 3D)

2

Thus  is just a probability wave. In other words wave function theory only gives probability of
finding a quantum particle somewhere it does not specify the exact position of the particle in space.
This is a radical change from classical physics behavior where objects have well-defined positions
(which is our everyday experience.)

So the resultant pattern observed in Davison-Germer electron diffraction experiment is interfere

pattern of the probability waves of the electrons, rather than interference of any real waves.

Note: Precisely speaking we should write time dependent  ( x, t ) in place of time independent  ( x ) in the above
relations.

PARTICLE IN A POTENTIAL BOX OR WELL

(Potential well is a sample scenario where we apply Schrodinger equation)

Let us assume that a particle is confined to a potential well with very steeped sides as shown
in Figure. Since the potential walls are very steep, the particle can’t escape from the well. The
width of the well is assumed to be ‘L’.

The function of the potential well is given by,

10
 V ( x)   x0
0 0 x L
 xL (1)

The time independent Schrodinger wave equation for this system is,
d 2  x  8 2 m
 2  E  V  x   x   0 (2)
dx 2 h
where E is the total energy of the particle. If E is finite, the wave function must be zero in the
regions out side of the box i.e. for x < 0 and x >0 . Inside the box, potential energy of the particle
is zero. Hence.
d2 8 2 mE
  x     x   0 for 0  x  L (3)
dx 2 h2

8 2 mE
To sole this equation, let us substitute, k 2  (4)
h2
Then the above equation becomes,

d 2
2
 k 2  0 (5)
dx
This is a simple homogeneous second order differential equation. It will have solutions of the
form,

 ( x)  A sin(kx)  B cos(kx) (6)

where A and B are constants whose values can be determined from the boundary conditions of
the potential well.

 ( x)  0 for x0 and x  L;

 ( x)  finite for 0 x L (7)

For x0 , we will have,

 (0)  A sin(0)  B cos(0)  0

A 0  B 1  0

B0 (8)

For x  L , we will have,

11
  ( L)  A sin(kL)  B cos(kL)  0

Since, B  0 ,
A sin(kL)  0  cos(kL)  0

Or  A sin(kL)  0
This implies either A  0 or sin(kL)  0

If A  0  ( x)  0 everywhere within the potential well. That is meaningless. Hence we must

choose the second condition. That is,
sin(kL)  0 (9)

This implies that, kL  n or k  n where n  1, 2,3,....

L

 n 
 n ( x)  A sin  x (10)
 L 
These functions are referred to as Eigen functions

Substituting the value of k from the above equation in k 2  8 mE

2

2
we will have,
h

 n  8 mE
2 2

   (11)
 L  h2

From Eq. (11), we get,

h2  n 
2
h2 2
E    n
8 2 m  L  8mL2

h2 2
En  n
8mL2
h2 2 h2
E1  1 
8mL2 8mL2

En  E1n2 Eigen values, (Characteristic)

E2  4 E1

E3  9 E1

12
 E4  16 E1

En  En1  En  E1 (n  1)2  n2   E1  2n  1

h2 h2
En   2 n  1  n
8mL2 4mL2

h2
En  n (12)
4mL2

or

Large and small boxes

(i) Large box

me 1027 gm ;

L 10cm

h2
En  n
4me L2

En  1028 n erg  1016 n eV

13
Small box

me 1027 gm

L 10 8 cm  1A

En  1010 n erg  102 n eV

Ratio of energy gap between energy levels of small and large boxes is around: 1018
EIGEN FUNCTIONS

 ( x)  A sin(kx)  B cos(kx)
n
We know that , B  0 and k  .Then,
L

 n 
Let us call this as,  n ( x)  A sin  x
 L 

The constant A can be determined by using the condition that the probability of finding the particle,
some where , with in the potential well is unity, i.e.,

P( x, t )x  ( x, t ) x
2

L
P    ( x, t ) dx  1
2


0
n ( x) n ( x)* dx  1

Substituting the value of  n ( x) we will have ,

 n 
L
A  sin 2 
2
x dx  1
0  L 

  2n 
L
1
A2  1  cos  x  dx  1; sin 2   1  cos 2 
0   L  2
L

 dx  1
2
A
0

A2
L 1
2
14
 2
A
L

2  n 
 n ( x)  sin  x
L  L 

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