Module – 4: QUANTUM MECHANICS-II

Transition from the deterministic to probabilistic description:

In classical physics the physical quantities like position, momentum etc can be
determined exactly at any time and the value of these quantities at a later time can be
predicted through equation of motion. In quantum mechanics, uncertainty principle imposes
a restriction on the exact value of a physical quantity. So, in quantum physics, instead of
having exact values, there are a number of allowed values with different probabilities. In
classical physics, intensity of a wave at a point depends on square of amplitude of the wave
at that point, whereas in quantum physics, probability of finding a particle at a point depends
on square of amplitude of the wave at that point.

For a system, instead of a single sharply defined value, a physical quantity can take a
large number of different values with different probability. Each of these values corresponds
to a possible state of the system. The General state of the system is a linear superposition of
all such possible states. The observed value of the physical quantity is the weighted average
of the different values. Example: if a particle can have energy E1, E2, E3 with probability 0.7,
0.2, and 0.1, respectively, then the observed energy will be the weighted average
Eav =0.7E1+0.2E2+0.1E3. The general state of a physical system is described by wave function
Y (x,y,z,t). The state of a system changes with time. The time variation in Y is described by
Schrodinger equation.

Wave function of matter wave and characteristics of wave function:

(i) Wave function of a particle is a mathematical representation which contains all the
information about a system that can be determined.
(ii) is a function of position and time =  (x, y, z, t), it is single valued function.
(iii) is a complex quantity;  = a + ib

(iv)  and it' s derivative are continuous at all places
x
(v) The quantity  * =  represents the probability per unit volum e (probability
2

density) of finding the system in the state

2
 dV =   dV = 1 is called the normalization condition
*
(vi)
V =all space V = all space

(vii)  must be finite and it has no direct physical meaning.

 (Here ψ* is the complex conjugate of ψ, and ψ ψ* = a2 + b2 i.e. real & has physical meaning.
Ψ is called probability amplitude but ψ* ψ is called probability density)

The time dependent Schrodinger equation:

We consider a free particle of mass m is moving along x direction under the action of a force F.
Let motion of the particle is non - relativistic.
we know p x = k and E = 
 px Et  i
i −  (px− Et)
The free particle wave function is ψ = Ae i ( kx − wt ) = Ae    
= Ae  − − − − − −(1)

i
i ( px − Et ) i
= p x Ae  = p x
x  

 2
i
i i ( px − Et ) p x2
= p . p Ae 
= − 
x 2 
x x
 2

 2
or, p  = −
2 2
.......... .......... (2)
x 2
x


i
iE ( px − Et ) iE
= − Ae  = − .
t  

or, E = i . = .......... .......... .........( 3)
t
p x2
We know that for a free particle = E,
2m
In quantum mechanics, we consider both the term in the above equation as operators.
p x2
So the equation is  = E .......... ..( 4)
2m
we put the values of p x and E from eq. (2) and (3) to get
 2  2 
− = i .......... .(5) ; This is free particle Schrodinger equation in one dimension
2m x 2
t

If the particle is moving in a potential V(x), the energy of the particle is

p 2x
E = Kinetic energy + Potential Energy = +V
2m
Thus the Schoredinger equation is
p 2x
 + V = E ........(6 )
2m

or, from eq (2) and (3) -

 2  2 
− + V = i .......... (7)
2m x 2
t
Equation (7) and equation (5) are the required one dimensional Schrodinger’s time dependent
wave equation for a free particle and bound particle respectively.
𝒉 𝒉 𝒉 𝟐𝝅
(E = hν = x 2π ν = ħω and p = = x = ħk, k is called wave number or propagation
𝟐𝝅 𝝀 𝟐𝝅 𝝀
constant)
In three dimension, Schrodinger equation becomes -
2 2   2 2 2 2 
−   + V = i ;  = 2 + 2 + 2 
2m t  x y z 
For a free particle in 3D , V = 0, So the equation becomes
2 2 
−   = i
2m t

The time independent Schrodinger equation:

i i i i
( px − Et ) px x − Et − Et
 = Ae  = Ae  e 
=  0e 
; here 0 is the space part of the wave function.
 2 − Et  
i 2
=e  0
.......... ...(8)
x 2
x 2

  i  −  Et
i
=  0 . − .Ee .......... .........( 9)
t  
  2  2
we substitute (8) and (9) in Schrodinger equation i .=− + V to get
t 2m x 2
 2 −  Et  2 0  i  −  Et
i i i
− Et
− e + V 0 e 
. = i 0 . − .Ee
2m x 2  
 2  2 0
or, − + V 0 = E 0
2m x 2
 2 0 2m
or, + 2 ( E − V ) 0 = 0.......... .(10)
x 2 

For a free particle V = 0 so eq (10) becomes -

 2 0 2m
+ 2 E 0 = 0
x 2 

Equation (10) is the required time independent Schrodinger equation for a bound particle.
Here ψo is only function of position.
Principle of superposition:

The wave function representing a general state of the system is a linear superposition of different
possible states 1 , 2 , .......... ... n in which t he system can exist

It  1 , 2 , .......... ... n are the solutions of Schrodinger equation, then the linear combination of the solutions
 = c1 1 + c2 2 + ......... + cn n =  cn n is also a solution of Schrodinger equation.
n

The square of the coefficients ci is the probability that the system will be in state  i
2

For a given system, the allowed states are obtained by solving the Schrodinger equation.
Probability density:

Probability density : P =  =  * is called the probability density. It is desbcribed as

2

the probability of finding the the system in state per unit volum e.

The probability of finding the particle in a volume dV is given by PdV

The probability of finding the particle in a volume V is  PdV =   dV

2

V V

In one dimension, such as motion along x - axis, the probability of finding the particle
x + dx
between x and x + dx is P = 
2
dx
x

 dV = 1
2
The probability that the particle is somewhere within th e entire space is
V =all space

In this case  is said to be normalized

Dimension of Ψ:

Dimension of 
3
probability −
3D :  ~ L−3 ;  ~ L 2
2
=
Volume
probability
2D :  ~ L− 2 ;  ~ L−1
2
=
Area
1
probability −
1D :  = ~ L−1 ;  ~ L 2
2

length

Normalized wave function:

  dV =   dV = 1 then th e wave function is said to be normalized
* 2
If
V V =all space

 dV = N , then what is the normalized wavefunct ion ?

2
If
V =all space

* 
  dV = N  dV = N or  dV = 1
2 *
or,
V =all space V =all space V =all space N N


In this case, is the normalized wavefunct ion
N
Eigen states, Eigen function and Eigen values:

In quantum mechanics, a general state of a  system is a superposition of a number of states with different
probabilities.
 = c1 1 + c2 2 + ......... + cn n =  cn n
n

These states are called eigenstates and the wavefunct ions i representing these states are called
eigen functions or eigenstates.
Number
In quantum mechanics, each physical quantities like momentum, energy etc are represented
by operators.The value of the quanity in an eigenstate can be determined by operating the corresponding
operator on the eigenfunction. This value is called eigenvalue .
Â i = ai i .......... (1)
The above equation is called eigenvalue equation. Â is an operator and ai is the eigenvalue .
A operates on  i to give back  i multiplied by a quantity ai

 i are in general complex numbers. But eigenvalue s are real quantities. They correspons
to real physical quantities called observables.

(Numbers of definite states which are allowed for the system are called eigen states. The
wave function associated with eigen state is called eigen function. The eigen values of a
physical quantity of a given system is defined as the set of permitted values of the physical
quantity of the given system.)
Momentum, Kinetic energy, and energy operators

We consider a free particle wave function moving along x - direction

i
( p x x − Et )
The free particle wave function is  = Ae 

 i
i
( px − Et ) i
= px Ae  = p x
x  

or, - i = p x
x

- i operates on  to give a value p x
x

Therefore, - i is called momentum operator ; in 3D the momentum operator is - i
x

p x2 1 1 1   2 2
Kinetic energy = , Therefore Kinetic energy operator is px px = px px = - i - i = −
2m 2m 2m 2m x x 2m x 2

 
i
iE ( px − Et ) iE
= − Ae  = −  ; or, i = E
t   t

Therefore, i is called energy operator
t

Expectation Value:
In quantum mechanics we talk of probable values of the physical quantities instead of actual
values (due to inherent uncertainty). If we make several me asurements of a physical
parameter of a system under similar situations then all the measured values do not come out
same. The average of all these measured values of a physical quantity is called its expectation
value.

For any physical quantity defined by an operator O, the expectation value is given by
∞
̂ 𝛹 dx , in one dimension.
< O> = ∫−∞ 𝛹 ∗ O

Here, 𝛹 ∗ is the complex conjugate of Ψ.

∞
For position, < x > = ∫−∞ 𝛹 ∗ x̂ 𝛹 dx
∞
For momentum, < p> = ∫−∞ 𝛹 ∗ p̂ 𝛹 dx
Applications of Quantum Mechanics:

(1) Particle in a one-dimensional box (infinite deep potential well):

We consider one dimensional motion of a particle of mass m confined between two rigid walls
of a box of width a. The potential in the box is zero and the potential at the rigid walls is
infinity. The particle is confined in the box due to infinite potential of the walls. This is one-
dimensional particle in a box problem.
This is the example of a bound system. Classically, the energy of the particle is continuous.
Quantum Mechanics dictates that the energy of the particle will be discrete integral values.

The form of the potential is

V ( x) = 0 for 0  x  a
V ( x) =  for x  0 and x  a

Figure looks like a potential well of infinite height.

The probability of finding the particle in the region outside the box is zero due
to infinite potential
P =  ( x) =0 for x  0 and x  a
2

or,  ( x) = 0 for x  0 and x  a.......... ..(1)

The time independent Schrodinger equation inside the box is -

d 2 2m
+ 2 ( E − V ) = 0
dx 2

d 
2
2m
or, + 2 E = 0 [ V = 0]
dx 2

d 
2
or, + k 2 = 0.......... .( 2),
dx 2
2mE
k2 = .......... .........( 3)
2
The general solution of eq(2) is
 = C1e ikx + C 2 e −ikx , which can be written as
 = ASinkx + BCoskx .......... ......(4)
The coefficients A and B are determined from the boundary constant that
dψ
 and should be finite and constant at the boundaries x = 0 and x = a
dx
At x = 0,  = 0 for x  0 and  = ASinkx + BCoskx for x  0
So from the condition of continuity of  we get -
ASinkx + BCoskx x =0 = 0

or, B = 0
So, form eq(4),
 = ASinkx.......... .(5)

Energy eigenvalue s
From the continuity condition of  at x = a, we get  ( x) = 0 at x = a
 = ASinkx x =a = 0
A  0, because this makes  (x) = 0 at all values of x
So, Sinka = 0 or ka = n , where n = 1,2,3,4..... [n = 0 is excluded because
k  0 and a  0]
n
or, k=.......... .....( 6)
a
2mE
From eq(3), k 2 =
2
k 2 2  2 2 2
Therefore, The energy of the particle E = = n .......... .......... (7)
2m 2ma 2

Equation (7) shows that the energy of a particle in an one - dimensional box is discrete or
quantized. Different values of the integer n corresponds to different state of the system.

Features
 2 2
(i) Energy eigen values are discrete.The energy of the particle is lowest for n = 1, E1 = .
2ma 2
This is called the ground state. The energy E is called zero point energy. Ground state energy/zero pont energy
is non - zero. The states n = 2,3,.... are called excited states. n = 2 is 1st excited state, n = 3 is called 2nd excited state etc.
(ii) The energy of the higher states is given by E1  (integer number) 2 i.e. En = n 2 E1 .
(iii) The spacing between two consicutive energy level is (2n + 1) E1 , non - uniform/not - equispaced.
(iv) The spacing between the energy states increases with increasing n.
 Eigenfunctions of particle in a box :


 dx = 1
2
From the normalization condition we know
-

In the present case, = 0 for x  0 and x  a, thereforese

1 − Cos 2kx
a a a

  dx = 1  Sin kxdx = 1, or A  dx = 1,
2 2 2 2
or A
0 0 0
2
A  a Sin2kx
2 a

or x 0 −  =1
2 
 2k 0

2
A
or, a − 0 − Sin2ka − o = 1,
2
From eq (5), ka = n ,  Sin2ka = Sin2n = 0
2
A a 2
Therefore, = 1, or A =
2 a

The eigenfunctions of particle in a box are therefore

2 nx
 n ( x) = ASinkn x = Sin , n = 1,2,3.......
a a
This is the normalized wave function.
First few eigenfunctions are
2 x  2 2
For n = 1,  1 ( x) = Sin , E1 =
a a 2ma 2
2 2x 4 2  2
For n = 2,  2 ( x) = Sin , E2 =
a a 2ma 2
2 3x 9 2  2
For n = 3,  3 ( x) = Sin , E3 =
a a 2ma 2

De-Broglie wavelength for particle in a box:

𝑛𝜋 2𝜋
K= =
𝑎 𝜆
2𝑎
Hence, λ =
𝑛
Ground state, n=1, So, λground = 2a (maximum wavelength)
For first excited state, n=2, λ 1st excited = a
Similarly, for other excited states de-Broglie wavelength can be calculated.

(2) Potential Barrier:

The sharpest increase of potential energy to certain value at a point and a sharpest fall of the
potential energy to zero at another point and remaining constant continuously over the
interval constitute a potential barrier.
 A potential barrier of width a is represented by
V(x) = Vo for 0  x  a
= 0 for x  0 and x  a

We consider a particle of mass m is incident on the potential barrier from the left
The energy of the particle is E  V0
According to classical physics, the particle can not go across the barrier
According to quantum mechanics, there is a finite probability that the particle
will go across the barrier.

Setting up the Schrodinger equation for one dimensional pitential barrier

We divide the one dimensional region into Region I, Region II, and Region III
Schrodinger equation is solved in these three regions with the boundary
d
condition that the wave function and are finite and continuous at the
dx
boundaries

Region I : x  0, V0 = 0 Region II : 0  x  a, V0 = 0 Region III : x  a, V0 = 0

d 2 1 2mE d 2 2 2m( E − V0 ) d 2 3 2mE
+ 2 1 = 0 + 2 = 0 + 2 3 = 0
dx 2  dx 2 2 dx 2 
d 1
2
d 2 2 d 3
2
or, 2
+ k 2 1 = 0.....(1) 2
−  2 2 = 0......( 2) or, 2
+ k 2 3 = 0.....( 3)
dx dx dx
2mE 2m(V0 − E ) 2mE
k2 = 2 2 = k2 = 2
 2 
The general solution of Equation (1), (2), and (3) are
 1 ( x) = Ae ikx + Be −ikx in Region I
 2 ( x) = Cex + De −x in region II
 3 ( x) = Fe ikx + Ge −ikx in Region III

Ge −ikx represents a particle wave going from right to left.But we assumed the
particle is incident from left.So, there can not be any matter wave
coming from right in Region III. So G = 0. Therefore the solutions are -
 1 ( x) = Ae ikx + Be −ikx in Region I
 2 ( x) = Cex + De −x in region II
 3 ( x) = Fe ikx
in Region III

Classically, A particle of energy E  V0 can not penetrate the barrier of height V0 .

Using Quantum mechanics we see that the wave function 3 is nonzero in region
III, which shows that the probability of finding the particle in region III is fintite.
So a particle incident from left on the barrier with E  V0 can penetrate through
the barrier and appear on the other side of the barrier. This phenomenon is called quantum mechanical
tunneling or simply tunneling.

The coefficients A, B, C, D, and F are determined from the boundary condition that
d
 and should be finite and continuous at the boundaries x = 0 and x = a.
dx
d 1 d 2
 1 x =0 =  2 x =0 and = .......( 4)
dx x =0 dx x =0
d 2 d 3
2 x=a
= 3 x=a
and = ......( 5)
dx x=a dx x =a

Transmission Coefficient :
The probability of transmission of a particle through t he potential energy barrier
is defined by transmission coefficient T
For a very wide and high potential barrier, The transmission probability can be
approximat ed as
16  16 
T= e −2a  e −2a ......(6)   1
4 + / k
2 2
 4 + / k
2 2

Examples of Quantum mechanical Tunneling

(i) Emission of a particle from radioactive nuclei: The a particle inside the nucleus is under
attractive nuclear force. It is under a potential well. The energy of the alpha particle is less
than the potential well. But the a particle comes out of the nucleus through tunneling.

(ii) Nuclear Fusion: Two light nuclei comes close to each other and undergo fusion. The
coulomb repulsion acts as a barrier as the particles come close to each other. The particles
can undergo fusion at lower energies because they tunnel through the coulomb barrier.

Devices developed using tunneling effect: Tunnel diode, Josephson Junction, Field emission
devices, Scanning tunneling microscope etc.

Questions discussions
Short Questions

1. Mention two differences between classical physics and quantum physics.

2. What is wave function in quantum physics? Write its physical significance.
3. Write the Schrodinger’s time independent wave equation for a free particle
moving along z- axis with low speed.
4. Write the Schrodinger’s time dependent wave equation for a particle moving
along x- axis with low speed.
5. State and explain the superposition principle for a wave function.
6. What do you mean by normalization of wave function?
7. What is probability density? Derive an expression for it.
8. Write the dimension of wave function of matter wave in 1-d, 2-d and 3-d.
9. What do you mean by eigenfunctions of physical system?
10. What do you mean by eigenvalues of physical quantity?
11. Derive an expression for energy operator in quantum physics.
12. Write the expression for energy and momentum operator in 3D.
13. Derive an expression for momentum operator in quantum physics.
14. What do you mean by expectation value of a physical quantity in quantum
physics? Write an expression for position expectation value.
15. Prove that the momentum of a particle in a one-dimensional well of infinite height
is quantized.
16. Prove that the de-Broglie wavelength of a particle in an infinite deep potential well
is quantized.
17. A particle of mass 'm' is enclosed inside a potential well of infinite height. Show
that de-Broglie wave length of the particle in the first excited state is equal to the
width of the well.
18. A particle of mass 'm' is enclosed inside a potential well of infinite height.
Show that maximum de-Broglie wave length of the particle is twice the width of
the well.
19. A particle of mass 'm' is enclosed inside a potential well of infinite height. Find the
maximum de-Broglie wave length of the particle?
20. If a particle trapped in infinitely deep potential well has de-Broglie’s wavelength
‘λ’ in the ground state then what is its wavelength in the first excited state?
 21. Why the ground state energy of a free particle moving in a one dimensional
potential box is non zero?
22. What is the eigenfunction of a particle trapped in an infinite deep potential well in
its second excited state?
23. An electron confined in a one dimensional box of width L is known to be in its first
excited state. Determine the probability density of electron in the central half.
24. Define a potential barrier.
25. Write the potential function of a potential barrier of width 'a' and height V 0.
26. What is quantum mechanical tunneling? Give two examples of it.
Long Questions
1. A particle of mass ‘m’ and energy ‘E’ is moving non-relativistically along X-axis, under
the action of potential energy ‘V’. Develop the Schrodinger’s time dependent wave
equation for the particle. Discuss the above equation for a free particle.
2. What do you mean by wave function of a matter wave? Write its important
characteristics. A particle trapped in a one-dimensional box of length L is described by
the wave function Ψ = x. Normalize the wave function between a and b.
3. (i) Define probability density. What is the total probability of a system in different
states? (ii) The normalized wave function for certain particle is ψ(x)= 3/π cosx , in the
region –π/2<x<π/2. Calculate the probability of finding the particle in the
region 0<x<π/4.
4. Describe operators, eigen functions and igen values in relation to quantum mechanics.
Write down the expression for linear momentum operator and energy operator in
quantum mechanics.
5. Write the Schrodinger's equation for a particle confined in a one dimensional box of
infinite height. Show that the energy of the particle is quantized.
6. Derive an expression for the normalized wave function of a particle trapped in an
infinite deep potential well.
7. Define a potential barrier? Set up Schrodinger's time independent equation in
different regions of a potential barrier, when energy of the incident particle is less
than the height of the potential barrier. Explain how quantum physics differs from
classical physics in this problem.
8. What is quantum mechanical tunneling? Write some examples of it.
(ii) A beam of electrons are incident on a barrier of height 6.0 eV and 0.2 nm wide.
Find the energy they have, if 1.0% of them are tunnel through the barrier.
Numerical
1. A particle can exist in the states ψ 1, ψ2 and ψ 3 with probabilities
1/2, 1/3 and 1/6 respectively. Write the wave function of the particle. If the energy
eigen values in the three states are E1 = 2eV, E2 = 4 eV and E3 = 8 eV respectively,
then find the expectation value of the energy of the particle.
2. Calculate the probability of finding a particle in the region 2≤x≤4, if the wave function
for the particle is given by ψ(x)=0.25 e 2ix.
3. The wave function for certain particle is Ψ = A cos2x for -π/2 < x < π/2. Find the
normalized wave function for the particle.
4. Normalize the wave function in one-dimension
ψ (x) = A e -α x , for x > 0
ψ (x) = A e α x, for x < 0

here, α is a positive constant.

2 𝑛𝜋𝑥
5. If the wave function of a quantum particle ψ(x) = √ sin ., find the probability
𝐿 𝐿
𝐿
of the particle between x=0 and x= in the first excited state.
2
6. A particle trapped in a one dimensional box of length 1 cm, is described by the
normalized wave function ψ = x. What is the expectation value of the particle’s
position < x >?
7. A particle of mass m is trapped in a one-dimensional infinite potential well of length L
𝑛𝜋𝑥
is described the wave function ψ(x) = A sin . Normalize the wave function.
𝐿
8. Energy of an electron confined in a one dimensional potential box of 0.2 nm size is 151
eV. What is the order of the state in which the electron exists? h= 6.6 X 10 -34 Js.
9. The ground state energy of a particle in an infinite one-dimensional potential well is 8
eV. If the width of the well is halved, what is the new ground state energy?
10. The ground state energy of a particle, trapped in a one-dimensional infinite potential
well is 4 x 10-19 J. Find the energy of the particle in second excited state.
11. An electron is constrained to a one-dimensional potential box of 0.1nm side. Find the
energy eigenvalue for 2nd excited state.
12. The energy of an electron in a one dimensional potential box of length 4 Å is 9.664 X
10-17 J. Find the order of the state and the momentum of the electron in this state.
13. If the energy in the second excited state of an electron trapped in a 1-D box is 77.4 eV,
find the width of the box. h= 6.6 X 10 -34 Js.
14. An electron is trapped in a one-dimensional box (with perfectly rigid walls) of length
2 Å. How much energy is required to excite the electron from the first excited state to
the second excited state?
15. The ground state energy of a particle, trapped in a one-dimensional infinite potential
well is 3 x 10-19 J. Find the energy of the particle in second excited state.
16. Find out the energy gap between the 2nd and 3rd excited states of an electron
confined in a potential box of length 4Å.
17. 1.2 million electrons with energy 3.0 eV are incident on a potential barrier of 9.0
eV high and 0.5 nm width. How many electrons can tunnel through the barrier?
18. A beam of electrons are incident on a barrier of height 6.0 eV and 0.2 nm wide. Find
the energy they should have if 1% of them are to tunnel through the barrier.
19. Electrons with energy 3 eV are incident on a potential barrier of 10 eV high and
4 Å wide. Find the transmission probability.