UNIT – II QUANTUM MECHANICS

MATTER WAVES

8.1 DE BROGLIE’S CONCEPT OF MATTER WAVES:

Light radiations (electromagnetic radiation) exhibit the dual property of waves and particles. In
photoelectric effect, Compton and in the continuous spectrum of x-rays, the radiant energy behaves like particle.
But in the phenomena of interference, diffraction and polarization radiant energy exhibits wave nature.
Thus light radiation has a dual nature, i.e., it possesses both particle and wave properties. But it does not
appear to behave as a wave and a particle simultaneously.
In 1924 De Broglie extended the dualism, as already found in light radiation, to include material particles
like electrons, protons atoms and also molecules. Similar to light radiation, matter also has a dual nature (i.e.
particle like and wave like) nature.
Thus a moving particle is always associated with a wave. The particle is controlled by these waves and
they are called matter waves.
De Broglie justified his concept with the following points:
1. Nature prefers symmetry. If radiation like light can act like wave sometime and like a particle at other
time, then material particles (e.g., electron, neutron etc.,) should also act as wave at some time and particle
in some other times.
2. Our universe is fully composed of light and matter.
3. Every moving particles has always associated with a wave. The particle is
controlled by this wave.
MATTER WAVES AND ITS WAVELENGTH:

The waves associated with matter are called matter waves or De -Broglie waves.
He derived wavelength λ for matter waves as follows
Consider a photon of radiant energy hγ moving with the velocity of light ‘c’. According to the Planck’s
theory of radiation, the energy E of the photon is given by

c
E  h [   ]

hc
E ………………(1)

Where
h = planks constant
γ = frequency of radiation,
c = velocity of light
 λ = wave length.
If the photon is considered as a particle of mass m, then according to Einstein mass energy relation, the
energy E of the photon is also given by
E = mc2 ……………..(2)
Where c = velocity of light.
Since the energy of the photon in the two cases is the same, therefore
eq.(1) = eq.(2)
hc
 mc 2

hc

mc 2
h
 …………….. (3)
mc
De Broglie extended this idea to conclude that eq.(3) is applicable to photons of radiations as well as other
particles. Thus if a particle has a mass m and travels with a velocity v its momentum is mv .This particle will
behave as a wave satisfying the equation
h h
  ………………… (4)
mv p
Where  is wavelength of matter waves or De Broglie wavelength.
Equation (4) is called as De Broglie’s wave equation.
DE-BROGLIE WAVE LENGTH IN TERMS OF ITS ENERGY:

If E is the kinetic energy of the material particle then

1 2 m2v 2
E  mv 
2 2m
m 2 v 2  2mE
p 2  2mE
p  2mE

Therefore De Broglie wave length is

h
 ---------------(5)
2mE
DE BROGLIE WAVE LENGTH ASSOCIATED WITH ELECTRONS:

Consider an electron at rest. It is accelerated through a potential difference of V volts and gains a velocity
of v meter/sec.
Mass of the electron = m
Charge of electron = e
Work done on the electron = eV
This work is converted into the kinetic energy of the electron, thus
1
Kinetic energy of the electron = mv 2
2
Therefore eV  12 mv 2

2eV
v2 
m

2eV
velocity of electron v  --------------(6)
m
h
By De Broglie’s equation wave length of electron  
mv

h

2eV
m
m
h
Therefore   ------(7)
2meV
Substituting the values,
h = 6.625 X 10-34 J-s.
e = 1.6 X 10-19 C
m = 9.1X10-31 Kg,
6.625  10 -34
We get  
2  1.6  10 -19  9.1  V

12.25  10 -10
 meters
V
Equation (7) denotes the wavelength of De Broglie’s wave associated with an electron.

PROPERTIES OF MATTER WAVES:

 Lighter is the particle, greater is the wavelength associated with it.

 Smaller is the velocity of the particle, greater is the wavelength associated with it.
 If v =0, then,    , i.e., wave becomes indeterminate and if v =  , then  =0.
  This indicates that the De- Broglie waves are generated by the motion of particles. These waves
are produced in the particles whether the particles are charged particles or uncharged particles (in the
equation λ = h / mv, there is no term representing the charge. It is independent of charge). This shows that
these waves are not electromagnetic waves but are a new kind of waves.
 The velocity of matter wave is not constant since it depends on the velocity of the material particle
whereas the velocity of the electromagnetic waves is constant.
 The velocity of these waves is greater than velocity of light. They can travel faster than light.
8.2 HEISENBERG’S UNCERTAINTY PRINCIPLE:

According to the classical mechanics, a moving particle occupies a definite position is space and has a
definite momentum. It is possible to determine exactly its position and momentum simultaneously.
But in the quantum mechanics a particle is described by a wave packet which represents and symbolies all
about the particle and moves with group velocity (equal to particle velocity). The particle may be found anywhere
within the wave packet. This implies that the position of the particle is uncertain within the limit of the wave
packet. Moreover the wave packet has a velocity spread and hence there is uncertainty about the (velocity)
momentum of the particle. This means it is impossible to know where within the wave packet the particle is and
what is its exact momentum.
STATEMENT:

It is impossible to determine precisely and simu1taneolls the values of both the members of
a pair of physical variables which describe the motion of an atomic system.
Qualitatively this principle states that the order (magnitude of the product of the uncertainties in the
knowledge of two variables must be at least Planck’s constant ‘h’.
Considering the pair of physical variables as position and momentum, we have
px  h ……………………..(1)

Where  p - Uncertainty (error) in determining the momentum

x - Uncertainty (error) in determining the position of the particle.
The principle of uncertainty is also applicable to the energy E of body at a time t. And also the
angular momentum J of a particle and its angular position θ

It given by Et  h
J  h
Where E and t - uncertainities in determining the energy and time

Jand - uncertainities in determining the angular momentum and angle.

Experimental illustrations of uncertainty principle:
Determination of the position of a particle by microscope:
As an illustration of the application of the principle of uncertainty, let us consider an ide alized
experiment to locate the position of an electron. According to the principles of physical optics, the
resolving power of a microscope i.e., the smallest distance between the two points can be just resolved
by the microscope is given by


x  …….. (1)
2 sin 
Δx - minimum distance between two points in the field of view of the microscope which
can be distinguished as separate (uncertainty in determining the position of the particle)
λ - wave length of the light used
θ - semi-vertical angle of the cone of light that enters the microscope objective
If we wish to make Δx very small, the wave length of the incident radiation should be small. So let us
assume that very short wave length ‘γ’ rays are used to illuminate the electron at 'O' (fig). If the
electron is to be seen in the microscope, the incident γ - ray photon should be scattered into the
microscope objective. In such a scattering, the electron recoils according to Compton Effect. To be able
to see the electron, the scattered photon should enter the microscope anywhere between OA and 0B i.e.,
within the angle 2θ

MICROSCOPE
|
|
|
|
|
A
B
h h A
A 

Incident Photon

X
Electron

Fig: 8.1

h
Momentum (p) imparted by the photon to the electron during the impact =

 h
Component of this momentum along X-direction (+ ve) = sin θ


h
Component of this momentum along X-direction (-ve) = - sin θ

Hence the uncertainty in the momentum measurement in the X – direction.
h h 2h
p x  sin   ( sin  )  sin  ……….(2)
  
Multiplying equations (1) and (2), we have
 2h
x  p x   sin 
2 sin  
i.e., xp x  h …….. (3) This shows that the product of uncertainties in
position and momentum is of order of Planck’s consta
APPLICATION OF HEISENBERG’S UNCERTAINTY PRINCIPLE:
NON-EXISTENCE OF ELECTRON INSIDE THE NUCLEUS
Heisenberg’s uncertainty principle can help us to establish that electron cannot be present in the nucleus of
the atom. The size of the nucleus of the order of 10 -15 m.
We know that
x.p  h
x.mv  h
h
v 
m.x
6.6  10 34
v 
9.1  10 31  10 14
v  7.25  1010 ms 1

It is quite evident that the value of v , the uncertainty in velocity is much higher than the velocity of light
(3x108ms-1), which is not possible. Hence, electron cannot be present in atomic nucleus.

8.3 SCHROEDINGER’S WAVE EQUATION:

The Schroedinger’s wave equation, like Newton’s laws of motion is a fundamental relationship showing
logical coherence to a vast amount of experimental observation. Newton’s laws of motion can be applied only to
macroscopic systems and events. But the Schroedinger’s wave equation can be applied both to macroscopic and
microscopic systems and events.
The classical wave equation
 2 y 2  y
2
 v (in one dimension) ------------------------(1)
t 2 x 2

Where ‘y’ is the displacement of the particle, which is moving in x-direction at any instant t. This equation can be
applied to waves in a stretched string, sound waves in air and light waves in vacuum. The general solution of this
equation is equal to

y( x, t )  Ae i ( kx t ) ---------------------------------------------(2)
 2 2
Substituting k    and   2 in eq(2) we get
v  
2
i( x  2t )
y( x, t )  Ae 

x
 2i ( t  )
y( x, t )  Ae 
--------------------------------------------(3)
E
substuting the energy of a photon E  h (or )   and Where  is the frequency of the radiation.
h
h
Using de Broglie' s relation the wavelength of the photon .  in eq(3) we get
p
E px
 2i ( t  )
y( x, t )  Ae h h

2i
 ( E t  px )
y ( x, t )  Ae h

i
 ( E t  px ) h
y ( x, t )  Ae 
where  
2
According to Schroedinger, for atomic particle like electron, one must take the whole solution of y, since one
cannot determine the momentum and position of it simultaneously. He called this complex displacement as wave
function ‘Ψ’. So we specify ‘Ψ’ by
i
 ( E t  px )
 ( x, t )  Ae 
------------------------- (4)

This expression for Ψ is correct only for freely moving particles. Differentiating partially with respect to x twice,
we get

 x, t   ip     Et  px 
i
   e -------------------- (5)
x 

 2 x, t   ip   ip     Et  px 
i
     e ----------------------- (6)
x 2     
  2 x, t  p2
   x, t  --------------------------- (7)
x 2 2
 2 x, t 
 2  p 2 x, t  ------------------------------(8)
x 2
Differentiating partially with respect to t, we get

 x, t 
i
Ei   Et  px 
  e 
t 
  x, t 
    x, t 
Ei
t 
  
  x, t   E  x, t  -------- --------(9)
 i t 
The total energy of a particle is sum of its kinetic energy and potential energy. ie.,
1 2
E mv  V ( x) -------------------(10)
2
mv 2
E  V ( x)  ------------------(11)
2
Multiply and divide the R.H.S by ‘m’ we get
m2v 2
E  V ( x)  -----------------------(12)
2m
p2
E  V ( x)  ----------------------(13)
2m
Multiply by  ( x, t ) on both sides we get

p2
E ( x, t )  V ( x) ( x, t )   ( x, t ) --------------(14)
2m
Substituting of the value of p2 x, t  from equation (8) and E  x, t  from equation (9) in eq.14, we get

  x, t   2  2 x, t 
  V x  x, t    ---------------(15)
i t 2m x 2

This is Schroedinger’s time dependent wave equation.

SCHROEDINGER’S TIME INDEPENDENT WAVE EQUATION:

The Schroedinger’s time dependent wave equation given by eqn. (15) is

  x, t   2  2 x, t 
  V x  x, t   
i t 2m x 2
  
substituting    x, t   E  x, t  from eqn.(9) we get
 i t 
  2  2 x, t 
E x, t   V x  x, t    ------------(16)
2m x 2
substituting t=0,we get
 2  2 x 
E x   V x  x    ----------------(17)
2m x 2
 2  2 x 
E x   V x  x    0 ---------(18)
2m x 2
2m
Multiply eqn. (18) by we get,
2
 2 x 
E x   2 V x  x  
2m 2m
 0 ----------(19)
2  x 2
rearranging the eqn.(19) we get
 2 x  2m
 2 E  V x  x   0 ------------(20)
x 2 
This is the Schroedinger’s time independent wave equation.
This can be written in three dimensions as

 2  2  2 2m
   E  V x  x   0 ----------(21)
x 2 y 2 z 2  2
This eqn. can also be written as

 2 
2m
E  V x  x   0 ------------(22)
2
2 2 2
Where   2  2  2
2

x y z

PHYSICAL SIGNIFICANCE OF THE WAVE FUNCTION AND ITS INTERPRETATION:

1. The wave function  is the solution of the Schroedinger’s wave equation and it gives a complete
description of a moving particle.
2. It represents the amplitude of the matter waves associated with a moving particle of mass m and
momentum p.
3. The wave function, in general, need not be real. This is because for a monochromatic plane wave of
specific wave vector K, the velocity of the wave (= /K) is calculated to be greater than the velocity of
light, which is physically unacceptable.
4. Hence wave functions cannot be real and so they cannot be measured directly by any physical experiments.
Therefore no real physical meaning is attached to the wave function .
PHYSICAL INTERPRETATION OF WAVE FUNCTION:
1. No real physical meaning is attached to the wave function  as it may be complex. However, the absolute
square of the wave function is real.
i.e, 2 = *. is real, where. * is the complex conjugate of   (x)
2. As 2 is real, Max Born interpreted it as the probability of locating the moving particle at a given point
in space. 2 is known as position probability density.
3. In other words, if (x, t) is the wave function then, 2 represents the
probability per unit volume of finding the particle around the given point x.
This interpretation is analogous to the intensity of a wave; If (x) is the instantaneous amplitude of a wave
at a point x, then the intensity ‘ I ’ of the wave at x is I(x) = 2 = (x)*. (x) .
CONDITIONS ON THE WAVE FUNCTION: NORMALIZATION OF WAVE FUNCTION
The probability interpretation of the wave function  imposes several conditions on the wave function. As
the total probability is 1 (unity) always, the probability of locating a moving particle (which is really existing and
non-decaying with time) somewhere within the entire space is given by,

+∞
∫*. dv = 1
-∞
where dv is the volume element = dx.dy.dz and
 = (x,y,z)

This integral is called normalization integral and the wave functions, which satisfy this integral condition, are said
to be ‘normalized’.
Conditions on the wave function to be a satisfactory solution of Schroedinger’s wave eqn.

1) To be a satisfactory solution of the Schroedinger’s wave equation, the wave function  must be
normalized as explained above.


i.e., 

 * dv  1

This condition arises because of the probability interpretation. Other similar conditions which are to be obeyed
by the wave function on account of the probability interpretation on  2 are given below.
2) The wave function  must be single valued, finite and continuous in space and obey the standard boundary
conditions. Also it must be normalized.
3) Similarly, the first derivative of the wave function /x etc are also required to be single valued, finite and
continuous and obey the standard boundary conditions.
4) The wave function representing a particle which is truly existing and is not decaying, cannot be zero
identically everywhere.
The probability  2 of locating such a particle somewhere in space is
nonzero.
Therefore,(x) = 0 for any and every point x in space between -∞ and +∞ is not
allowed; if allowed, it would make  2 = 0 everywhere which refers to the
non-existence of the particle.
If a wave function obeys all such conditions, then it represents one of the characteristic states of
the moving particle and it is known as an ‘eigen function’. The physical variables such as energy E etc will also be
characteristic of that state and hence they are known as ‘eigen values’. The set of all eigen functions represents the
different allowed states of the particle. The solutions of Schroedinger’s eqn., which are not eigen functions are
physically unacceptable to represent the particle. Thus any physical system will have only a finite number of
allowed states.

APPLICATION OF SCHROEDINGER’S EQUATION TO ONE-DIMENSIONAL BOX: PARTICLE IN A

ONE DIMENSIONAL POTENTIAL BOX

V(x)= V(x)=

(x)=0 (x)=0
Particle

V(x)= V(x)=
V(x)=0

x
0 L

Fig: 8.2
Consider a particle moving inside a box along the x-direction. The particle is bouncing back and forth
between the walls of the box i.e., particle to be moving to and fro between the two walls at x=0 and x=L. The
particle is suffering perfect elastic collision at these walls. Therefore there is no change in its potential energy. For
simplicity we say that the value of potential energy V of the particle inside is zero. Further because the walls are
infinitely hard the particle cannot get out of the box. We may express the fact by saying that outside the box the
particle potential energy is infinite. Thus the potential function (V) can be expressed as

Boundary conditions

V0 For 0  x  L
V For x<0 and x>L

The potential function is shown in figure and is known as square well potential. The particle cannot exist outside
the box and its wave function  is 0 for x  0 and x  L .Our task is to find what  is, within the box, viz., between
x= 0 and x=L.
The Schroedinger’s wave equation is

 2 ( x) 2m
+ 2 (E-V (x)) (x) = 0-----------(1)
x 2 

Here V (x) =0 for x>0 and x<L

 2 2mE
 2  0
x 2 

 2
 k 2  0 --------------------(2)
x 2

2 mE
Where k2 =
2

The general solution of this equation is

 ( x)  A sin kx  B cos kx ----------(3)
The boundary conditions are used to evaluate the constants A and B in eq (2).
When x  0 at x  0, then, eqn.(3),becomes , B  0
Again substitute B=0 in eq(3) we get
 ( x)  A sin kx ----------(4)
when = 0 at x= L, then, eqn (4) becomes
A sin kL = 0 --------(5)
Since A  0,
sin kL = 0-----------(7)

We know that sin n =0--------(6)

Equating (7) and (6),we get
n = kL
n
k -----------(8)
L
Where n is an integer.

Substuting the value of k of eqn.(8) in eqn.(4)

nx
Thus  n ( x)  A sin ---------(9)
L
This means that
2mE 2mE 8 2 mE n 2 2
k  2  2 
2
 2
 h h2 L
4 2

n2h2
 The energy of the particle E n  ------(10)
8mL2
For each value of n, there is an energy level and the corresponding wave function is given by Eq.(10). The particle
in the box cannot possess any arbitrary amount of energy. Rather, it can have discrete energy values specified by
the Eq. (10). In other words .Its energy is quantized. Each value of E n is a called an eigen value and the
corresponding  n is called eigen function.
A few of the energy levels are shown in fig.
 Fig: 8.3 Energy levels and Wave Functions

Normalization of the wave function

The wave functions corresponding to the above allowed discrete energy level could be obtained as follows
From the equation (9) probability density is
 nx 
 2     A 2 sin 2 
 L 
The probability of finding the particle in length dx at x is given by   dx
so we must have,
L

  dx  1(Since the particle is always within the box)



Substituting the value for  

nx
L

A dx  1
2
i.e, sin 2
0
L

2nx
L 1  cos
A2  L dx  1
0
2
2nx 
L

 sin
A2  
x 1 L  1

 2 2 2n 
 L  0

 L 1 sin 2nx 
A2    1
 2 2 2n L 
 L L sin 2nx 
A2   1
 2 2 2n 
The second term of the integrated expression becomes zero at both limits,
A2 L
Thus 1
2
2
 A2  ;
L
2
A
L
The eigen functions  belonging to eigen values En now be expressed as

2 nx
n  sin
L L
This is called the normalized eigen functions .the energy (E n) and the normalized wave functions are given in
figure.
Tunnel diode (Tunneling Effect)

A two thermal device that exhibits a region of incremental negative resistance is the tunnel diode. If p and
n regions of a diode are heavily doped 1025impurities /m3) and it is possible for carriers to tunnel through the
potential barrier if it is narrow enough (10-6cm) and if available energy levels of states exists on the other side.
Tunnel diodes find the greatest application in switching circuits requiring times of les than 10-9 second. This is
possible because tunneling is a quick process and it is nothing but the spreading of the electron wave function
through the potential barrier, which takes place at near the velocity of light value. Referring the current voltage
characteristics of tunnel diode [fig (a)] there are four positions in this. Position (a) represents the condition of the
diode in the absence of biasing. A contact potential exists at the p-n junction and so no current flow. Due to
tunneling, current flows from position (A) to position (b) with forward basing (figure (b), (c), (d)). If we still
increase the forward bias, the conduction band electrons in the n type materials or holes in valence band of p type
and of p type see no vacant energy levels (fig (e)) due to that current decreases even though there is forward
voltage. This region is known as negative resistant region. This region is important for different device operations
like amplifier, oscillator and high-speed switch (c) this position is denoted as in fig (a)). Beyond this region and
for large forward bias, this tunnel diode operates a conventional diode i.e., the current increases exponentially with
the forward bias [position (d) in figure (a)]. The doted line indicates the current voltage characteristics of the
conventional diode .if a reveres bias voltage is applied, the height of the barrier is increased above the open circuit
value Eo. Hence the n-side levels must shift downward with respect to the p-side levels as indicated in fig.(f). So
there are some energy states in the valence band of the p-side, which lie at the same levels allowed empty states in
the conduction band of the n – side. Hence these electrons will tunnel from p to the n side, giving rise to a reverse
diode current. At the magnitude of the reverse bias increases, the shaded area grows in size causing the reverse
current to increase as shown in figure (a).
Fig: 8.5