Module 2: Quantum Mechanics

Dr. Sankarshan B. M.
Assistant Professor
Department of Physics
The National Institue of Engineering
Mysuru - 570 008

Contents
Syllabus 3

1 Compton effect 4
1.1 Physical significance of Compton effect . . . . . . . . . . . . . . . . . . 5

2 Wave nature of Particle (Wave-Particle Dualism) 5

2.1 de Broglie hypothesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.2 de Broglie wavelength . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3 de Broglie wavelength of an accelerated electron . . . . . . . . . . . . . 6

3 Matter Waves 7
3.1 Phase velocity of de Broglie waves . . . . . . . . . . . . . . . . . . . . . 7

4 Phase and group velocity 8

5 Expression for group velocity 8

Contents
6 Relation between group velocity and particle velocity 10

7 Characteristic properties of matter waves 12

8 Heisneberg’s uncertainty principle 12

8.1 Statement: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
8.2 Explanation: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
8.3 Physical significance: . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
8.4 Application of uncertainty principle . . . . . . . . . . . . . . . . . . . . 13
8.4.1 Non-existence of electron in the nucleus . . . . . . . . . . . . . . 13

9 Wave function 15

10 Properties of the wavefunction: 15

11 Physical significance of wave function 16

11.1 Probability density: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

12 Normalization 17

13 Time independent Schrödinger wave equation 17

Module 2: Quantum Mechanics

14 Eigenfunctions and Eigenvalues 18

14.1 Eigenfunctions: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
14.2 Eigenvalues: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Contents
15 Applications of Schrödinger wave equation
15.1 Energy eigenvalues of a Particle in one-dimensional, infinite potential
19

well (Potential well of infinite depth): . . . . . . . . . . . . . . . . . . . 19

16 Energy eigenvalues for a free particle: 23

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Module 2: Quantum Mechanics

Syllabus: Module 2 - Quantum Mechanics

de Broglie hypothesis – de Broglie wavelength, Matter waves, Compton effect,

Phase velocity, group velocity, expression for group velocity, Relation between
group velocity and particle velocity (relativistic method), Characteristic
properties of Matter waves.

Heisenberg’s uncertainty principle and its physical significance (with deriva-

tion), Application of uncertainty principle (Non - existence of electron in the
nucleus), Numerical problems.

Wave function: Properties and Physical significance (including Probability

density and Normalization of wave function), Setting up of one dimensional
time independent Schrödinger wave equation, Energy Eigen values and Eigen
functions of a particle in a potential well of infinite depth, Numerical problems

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 Module 2: Quantum Mechanics

1 Compton effect
The scattering of a photon by an electron is called Compton effect. The Compton effect
can be defined as “The effect due to which there is an increase in wavelength accompanied
by a change in the direction of the scattered x-rays compared to that of the incident x-rays
consequent to the exchange of energy between the x-ray photons and the electrons in the
target material.”

Figure 1: The scattering of a photon by an electron

X-rays are incident on a suitable target material (graphite in Compton’s original experi-
ment). The incident x-rays undergoes scattering in many directions spanning through 0° to
180°. Let an x-ray of the photon of energy E = hν collide with an electron initially at rest.
The photon scattered through an angle θ with its energy E 0 = hν 0 and the electron itself re-
coils in a direction making an angle φ with the direction of the incident photon (Fig 1). The
scattered x-rays contain two wavelengths one is same wavelength λ as that of the incident
ray and other is a wavelength λ0 , which is always greater than λ. The difference (λ0 − λ)
which indicates the enhancement in the wavelength is called the Compton shift. It is
found that λ0 is independent of the target material but dependent only on the angle through
which the scattering occurs. Applying the laws of conservation of energy and conservation
of momentum, expression for change in wavelength ∆λ is given by

h
∆λ = (λ0 − λ) = (1 − cos θ)
m0 c
where m0 is the rest mass of the electron and c is the velocity of light
This equation is known as Compton’s equation for Compton shift. The quantity (h/m0 c)
has the dimensions of length and is called Compton wavelength whose value is 2.42 × 10−12 m.
The change in wavelength of the scattered x-ray photon, when it is scattered through
different angles is as follows
ˆ Case I: When θ = 0°
∆λ = λc (1 − cos θ) = λc (1 − 1) = 0
λ0 − λ = 0 =⇒ λ0 = λ
ˆ Case II: When θ = 90°
h
∆λ = λc (1 − cos θ) = λc (1 − 0) =
mc
λ0 − λ = λc

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 Module 2: Quantum Mechanics

ˆ Case III: When θ = 180°

h
∆λ = λc (1 − cos(180°)) = λc (1 − (−1)) = 2
mc
λ0 − λ = 2λc

∴ The change in wavelength ranges from 0 at θ = 0° to twice the Compton wavelength at

θ = 180°.

1.1 Physical significance of Compton effect

In the Compton effect, the Compton shift is explained on the basis that the X-ray photons
collide with electrons and during the collision the energy exchange between the two occurs as
though it is a kind of particle-particle collision. Thus it demonstrates the particle nature
of X-rays (electromagnetic waves) or in other words it signifies the particle nature of waves
in general.

2 Wave nature of Particle (Wave-Particle Dualism)

By the end of nineteenth century, energy was considered something different from matter.
Energy was propagated in progressive undulations or waves while matter was essentially
discontinuous. Phenomena like interference, diffraction and Polarization could be explained
on the basis of the wave theory of light. However, phenomena like photoelectric effect,
thermionic emission and energy spectrum of a black body could not be explained based on
wave theory. In 1900, Max Planck proposed the quantum theory, according to which, energy
transmission was taken to be discontinuous in the form of packets or quanta called photons.
The energy of each photon is hν, where h is a constant called Planck’s constant and ν is the
frequency of radiation. Hence, the dual nature of energy has been established.

2.1 de Broglie hypothesis

Having established the dual nature of energy, it did not take much longer to realise that
matter can also exhibit a dual nature. Louis de Broglie in 1924 extended the wave-particle
dualism of light to the material particles. He reasoned out that nature loves symmetry and
the two forms in which nature manifests are matter and energy. If one form namely energy
could exhibit a dual nature the other form namely matter should also exhibit a dual nature.
This is known as de Broglie hypothesis. According to this hypothesis, all material particles
in motion posses wave character also. The waves associated with material particles in motion
are called matter waves or de Broglie waves.

2.2 de Broglie wavelength

According to Planck’s hypothesis, this energy is propagated as a quantum of frequency ν,
given by
hc
E = hν = = pc (1)
λ
hc
= pc
λ

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Module 2: Quantum Mechanics

or
hc
λ=
pc
h
λ= (2)
p
For a particle moving with a velocity v, the de Broglie wavelength is

h
λ=
mv

This is the de Broglie wavelength.

2.3 de Broglie wavelength of an accelerated electron

If a charged particle, say an electron is accelerated by a potential difference of v volts, then
its kinetic energy is given by

Ek = eV
1 2
mv = eV
2
2eV
v2 =
m
or r
2eV
v=
m
Then the wavelength of the charged particle is given by
h
λ=
mv
or r
h h m
λ= q =
m 2eV m 2eV
m

Thus
h
λ= √ (3)
2meV

Question 2.1
Show that the de Broglie wavelength
√ associated with an electron of energy V electron
volts is approximately (1.227/ V ) nm.

Answer
The de Broglie wavelength λ associated with an electron of mass m and energy E is
given by
h
λ= √
2mEk

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 Module 2: Quantum Mechanics

Here, kinetic energy,

Ek = V eV = 1.610−19 V J

6.62 × 10−34
λ= √
2 × 91 × 10−31 × 1.6 × 10−19 V
1.227 × 10−9
= √
V
1.227
λ = √ nm
V

3 Matter Waves
The waves associated with material particles in motion are called matter waves or de
Broglie waves.

3.1 Phase velocity of de Broglie waves

If we call the de Broglie wave velocity vp , we can apply the usual formula

vp = νλ

The wavelength λ is simply the de Broglie wavelength

h
λ=
mv
Let E be the total energy of the particle. Let ν be the frequency of the associated wave.
We equate the quantum expression E = hν with the relativistic formula for total energy
E = mc2 . So we get
hν = mc2
or
mc2
ν=
h
The de Broglie wave velocity is therefore
 2 
mc h
vp = νλ =
h mv

c2
vp = (4)
v
Because the particle velocity v must be less than the velocity of light c, the de Broglie
waves always travel faster than light!!
In order to understand this unexpected result, we must look into the distinction between
phase velocity and group velocity.

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 Module 2: Quantum Mechanics

4 Phase and group velocity

In terms of ω and k equation equation of a wave is represented by

y = A cos(ωt − kx) (5)

The amplitude of the de Broglie waves that correspond to a moving body reflects the
probability that it will be found at a particular place at a particular time. It is clear that
de Broglie waves cannot be represented simply by a formula resembling (5), which describes
an indefinite series of waves all with the same amplitude A. Instead, we expect the wave
representation of a moving body to correspond to a wave packet or wave group, like that
shown in figure, whose waves have amplitudes upon which the likelihood of detecting the
body depends.
A familiar example of how wave groups come into being is the case of beats. When
two sound waves of the same amplitude but of slightly different frequencies are produced
simultaneously, the sound we hear has a frequency equal to the average of the two original
frequencies and its amplitude rises and falls periodically. The amplitude fluctuations occur as
many times per second as the difference between the two original frequencies. If the original
sounds have frequencies of say, 440 and 442 Hz, we hear a fluctuating sound of frequency
441 Hz with two loudness peaks, called beats per second. The product of beats is illustrated
in figure.

Figure 2: A wave group

A way to mathematically describe a wave group, then is in terms of a superposition

of individual waves of different wavelengths whose interference with one another results in
the variation in amplitude that defines the group shape. If the velocities of the waves are
the same, the velocity with which the wave group travels is the common phase velocity.
However, if the phase velocity varies with wavelength, the different individual waves do not
proceed together. This situation is called dispersion. As a result the wave group has a
velocity different from the phase velocities of the waves that make it up. This is the case of
de Broglie waves.
Phase velocity: The velocity with which a definite phase of each individual monochro-
matic wave travels is called the ‘Phase velocity’.
Group velocity: The velocity with which the resultant envelop of the group of waves
travels is called group velocity, denoted by vg .
Note: A group of waves need not have same velocity as the waves themselves.

5 Expression for group velocity

Let us suppose that the wave group arises from the combination of two waves that have the
same amplitude A but differ by an amount ∆ω in angular frequency and an amount ∆k in
wave number. We may represent the original waves by the formula

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Module 2: Quantum Mechanics

Figure 3: Superposition of two waves with different frequencies.

y1 = A cos(ωt − kx)

y2 = A cos[(ω + ∆ω)t − (k + ∆k)x]

The superposition of the two waves will yield a single wave packet or wave group.
Let us find the velocity vg with which the wave group travels.
The resultant displacement y at any time t and any position x is the sum of y1 and y2

y = y1 + y2

y = A cos(ωt − kx) + A cos[(ω + ∆ω)t − (k + ∆k)x]

Let us use the trigonometric identity
   
α+β α−β
cos α + cos β = 2 cos cos
2 2

and
cos(−θ) = cos θ
we find that
y = y1 + y2
y = A cos(ωt − kx) + A cos[(ω + ∆ω)t − (k + ∆k)x]

1 1
y = 2A cos [(ωt − kx) + ωt + ∆ωt − kx − ∆kx] cos [ωt − kx − ωt − ∆ωt + kx − ∆kx]
2 2

1 1
y = 2A cos [(2ω + ∆ω)t − (2k + ∆k)x] cos (∆ωt − ∆kx)
2 2
Since ∆ω and ∆k are small compared with ω and k respectively

2ω + ∆ω ≈ 2ω

2k + ∆k ≈ 2k

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 Module 2: Quantum Mechanics

and so  
∆ω ∆k
y = 2A cos(ωt − kx) cos t− x (6)
2 2
This can be represented as
y = A cos(ωt − kx)
where A represents the amplitude of a wave with angular frequency ω and wave number k.
Equation (6) represents a wave of angular frequency ω and wave number k that has
superimposed upon it a modulation of angular frequency 12 ∆ω and of wave number 12 ∆k.
The effect of modulation is thus to produce successive wave groups.
The phase velocity vp is
ω
vp = (7)
k
and the velocity vg of the wave groups is
∆ω
vg = (8)
∆k
when ω and k have continuous spreads instead of the two values in the preceding discussion,
the group velocity instead is given by

dω
vg = (9)
dk

Depending on how phase velocity varies with wave number in a particular situation, the
group velocity may be less or greater than the phase velocities of its member waves. If the
phase velocity is the same for all wavelengths, as is true for light waves in empty space, the
group and phase velocities are the same.

6 Relation between group velocity and particle velocity

A particle moving with a velocity v is supposed to consist of a group of waves, according to
a de Broglie hypothesis.
The group velocity is given by
dω
vg =
dk
The angular frequency and wave number of the de Broglie waves associated with a particle
of rest mass m0 moving with the velocity v are given by

2πmc2
ω = 2πν =
h
∵ E = mc2 and E = hν
mc2
mc2 = hν and hence ν =
h
2πm0 c2
ω= q (10)
2
h 1 − vc2
and
2π 2πmv
k= =
λ h

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Module 2: Quantum Mechanics

h 1 mv
∵λ= or =
mv λ h
2πm0 v
k= q (11)
2
h 1 − vc2
By differentiation, we obtain

dω 2πm0 c2 (−2v)
= 3 2
dv −2h 1 − vc2 2 c
2

dω 2πm0 v
= 3 (12)
dv 2

h 1 − vc2 2
  1
2 −2
"  
2
 −3  #
dk 2πm0 v 2πm0 v 1 v 2
−2v
= 1− 2 + − 1− 2
dv h c h 2 c c2
h  i
v2 v2
dk 2πm0 1 − c 2 + c 2
= 3
dv h 1− v 2
 2 
c2

dk 2m0 π
= 3 (13)
dv 2

h 1 − vc2 2
dω
dω dv
∴ vg = = dk
dk dv
2m0 π
 2
3
h 1− v2 2
c
vg = 2m0 π v=v
 2
3
h 1− v2 2
c

vg = v (14)
Hence, the de Broglie wave group associated with a moving body travels with the same
velocity as the body.
The phase velocity vp of de Broglie waves is, as found earlier

ω c2
vp = = (15)
k v
This exceeds both the velocity of the body v and the velocity of light c, since v < c.
However, vp has no physical significance because the motion of the wave group, not the
motion of the individual waves that make up the group, corresponds to the motion of the
body, and vg < c as it should be. The fact that vp > c for de Broglie waves therefore does
not violate special theory of relativity.

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 Module 2: Quantum Mechanics

7 Characteristic properties of matter waves

The Characteristic properties of matter waves are as follows:

1. Matter waves are the waves that are associated with moving particle. It is only observed
for subatomic particles.

2. The wavelength λ of the matter waves depends on the mass m and velocity v of the
particle and is given by
h h
λ= =
mv p
where h is the Planck’s constant, p is the momentum of the particle.

3. Energy of matter waves are quantized.

4. The amplitude of the matter waves at a particular region and time depends on the
probability of finding the particle at the same region and time.

5. The wave velocity or the phase velocity of the matter waves is given by

c2
vp =
vg

Here vg is same as the particle velocity which is always lesser than than c, the velocity
of light. Thus the velocity of matter waves is always greater than c. This also indicates
that matter waves are not physical waves.

6. Unlike any electromagnetic wave which always travel with a constant velocity the wave
velocity (or phase velocity) of different matter waves may differ depending on the mass
and velocity of the particle.

8 Heisneberg’s uncertainty principle

8.1 Statement:
The product of uncertainties in determination of canonically conjugate pairs such as position
and momentum, energy and time, angular displacement and angular momentum is of the
order of Planck’s constant h.

8.2 Explanation:
It is impossible to determine both position and momentum of a particle simultaneously
and accurately. The product of uncertainties involved in the determination of position and
h
momentum simultaneously is greater or equal to 4π .
If ∆x is error (uncertainty) involved in the measurement of position and ∆p is the error
involved in the measurement of momentum, then according to Heisenberg’s uncertainty
principle,
~
∆x · ∆p ≥
2
or
h
∆x · ∆p ≥
4π

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Module 2: Quantum Mechanics

The product of the uncertainties is of the order of Planck’s constant. If one quantity is
measured with high accuracy, then the simultaneous measurement of the other quantity be
less accurate.
The uncertainty principle also restricts the precision in the measurement of the particle
energy. If E is the energy of a quantum system at time t, then the uncertainty ∆E and ∆t
are related by the equation,
h
∆E · ∆t ≥
4π
Similarly, in terms of angular momentum L and angular displacement θ, we have,
h
∆L · ∆θ ≥
4π

8.3 Physical significance:

According to classical mechanics, if we know the position and momentum of a particle at
some instant of time, its position and momentum at any later instant of time can be deter-
mined accurately. But according to Heisenberg’s uncertainty principle, if we try to measure
position accurately, error in the measurement of momentum increases and viceversa. Thus,
in quantum mechanics there is no place for the word exactness, and is replaced by the word
probability. Heisenberg’s uncertainty principle implies that an event, which is impossible
to occur according to classical physics, has finite probability of occurrence according to
quantum mechanics.

8.4 Application of uncertainty principle

8.4.1 Non-existence of electron in the nucleus
As an application of uncertainty principle, we consider the case of “non-existence of electron
in the nucleus”. In 1900, Becqueral demonstrated that β-rays are actually streams of elec-
trons. Later it was found that the electrons which constitute the β-rays are emitted with
different velocities. It can be argued on the basis of Heisenberg’s uncertainty principle that
it is impossible that electrons exist inside the nucleus. For this deduction, the experimen-
tal observation that the maximum energy of the β-particles is about 3 to 4 MeV becomes
essential for the argument.
The proof is as follows.
We know that
E 2 = p2 c2 + m20 c4
or
E 2 = c2 (p2 + m20 c2 ) (16)
Heisenberg’s uncertainty principle states that
~
∆px .∆x ≥
2
which can also be written as
h
∆px ≥ (17)
4π∆x
We know that the typical value of diameter of nucleus is of the order of 5 × 10−15 m.
We can take this value to be approximately the maximum space of confinement. Thus, if

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Module 2: Quantum Mechanics

an electron is to exist inside the nucleus, then the uncertainty in its position ∆x must not
exceed this value. Allowing maximum uncertainty value, we can write

∆x ≤ 5 × 10−15 m

Using this in inequality (17), we have

6.63 × 10−34
∆px ≥
4 × π × 5 × 10−15

∆px ≥ 1.1 × 10−20 N s

which is the uncertainty in the momentum of the electron. But since the momentum of the
electron must at least be equal to the uncertainty in the momentum, we can state,

px ≥ 1.1 × 10−20 N s (18)

We know, the rest mass of the electron

m0 = 9.11 × 10−31 kg

Now, by making use of the inequality (18) in equation (16), we can say that in order that
the electron may exist within the nucleus, its energy E must be such that

E 2 ≥ c2 [(1.1 × 10−20 )2 + m20 c2 ]

i.e.,
E 2 ≥ (3 × 108 )2 [(1.1 × 10−20 )2 + {(9.11 × 10−31 )2 (3 × 108 )2 }]
i.e.,
E 2 ≥ (3 × 108 )2 [1.21 × 10−40 + 7.469 × 10−44 ]
Since the second term in the bracket is smaller by more than 3 orders of magnitude
compared to the first term, it is negleced

∴ E 2 ≥ 1.09 × 10−23

Taking the square roots on both sides and simplifying, we get the condition

E ≥ 3.3 × 10−12 J

Expressing in eV, we get

E ≥ 20.6 MeV
This means to say that, in order that an electron may exist inside the nucleus its energy
must be greater than or equal to 20.6 MeV. But, the experimental investigations on beta-
decay reveal that, the kinetic energy of the beta particles is of the order of 3 to 4 MeV. This
clearly indicates that, electrons cannot exist within the nucleus.

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 Module 2: Quantum Mechanics

9 Wave function
In quantum mechanics it is postulated that there exists a function determined by the physical
situation. The function is called wave function. It is also postulated to contain all possible
informations about the system. Hence it is also called as state function.
The wave function may vary with respect to both the position coordinates of the physical
system and the time. It is then called the total wave function, and is represented by the
capital form of the Greek letter Ψ. If the wave function has variation only with position
(i.e., space) and not with time, it is repsresented by the lower case Greek letter Ψ.
The total wave function can be represented by the equation,
Ψ = Aei(kx−ωt)
where, A is a constant, and ω is the angular frequency of the wave.

10 Properties of the wavefunction:

A system is defined by its energy, momentum, position etc. Once the wavefunction 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 the system changes its state. To be an
acceptable wavefunction, it has to possess the following properties.

Property 1: Ψ is single valued everywhere.

Any physical quantity can have only one value at a point. For this reason the function
related to a physical quantity cannot have more than one value at that point. If it has more
than one value at a point, it means that there is more than one value of probability of finding
the particle at that point.
A function f (x) which is not single values over cer-
tain interval is shown in figure. Here, f (x) has 3 val-
ues, f1 , f2 and f3 for the same value of P at x = P .
Since f1 6= f2 6= f3 , it means to say that, if f (x)
were to be a wave-function, then the probabilities of find-
ing the particle has 3 different values at the same location
which is absurd. Hence the wavefunction is not accept-
able.

Property 2: Ψ is finite everywhere.

The wave function must be finite everywhere. Even if x → ∞,
or −∞, the wave function should not tend to infinity. It must
remain finite for all values of x. If Ψ is infinite, it would imply
an infinitely large probability of finding the particle at that
point. This would violate the uncertainty principle.
A function f (x) which is not finite at x = R is shown in
Figure. At x = R, f (x) = ∞. Thus, if f (x) were to be
a wavefunction, it signifies a large probability of finding the
particle at a single location (x = R), which violates the uncertainty principle. Hence the
wavefunction becomes unacceptable.

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 Module 2: Quantum Mechanics

Property 3: Ψ and its first derivatives with respect to its variable

are continuous everywhere.
Since Ψ is related to a physical quantity, it cannot have a discontinuity at any point. There-
fore, the wave function Ψ and its derivatives should be continuous across any boundary.
A function f (x) which is discontinuous at Q is shown in
figure. At x = Q, f (x) is truncated at A, and restarts at
B. Between A and B, it is not defined. If f (x) were to be
wavefunction, then the state of the system at x = Q cannot be
ascertained. Hence, the wavefunction is not acceptable.
Also, when Ψ is not continuous, its first derivatives will not
be finite. As a requirement, apart from being finite, the first
derivatives should also be continuous, because, if they are not
continuous, the second derivatives of Ψ will not be finite. But we need the second derivatives
in evaluating the Schrödinger’s equation.

Property 4: For bound states, Ψ must vanish at infinity. If Ψ is a

complex function, then Ψ∗ Ψ must vanish at infinity.
The wave functions that posses these 4 properties are named in quantum mechanics as
Eigenfunctions.

11 Physical significance of wave function

The physical significance of Ψ could be realized through its probabilistic nature which is well
depicted in quantum mechanics in terms of probability density.

11.1 Probability density:

In classical mechanics, the square of a wave amplitude associated with electromagnetic radi-
ation is interpreted as a measure of radiation intensity. This suggests that we should make
a similar interpretation for de Broglie waves associated with electron or any particle. Let us
consider time independent situation for the particle.
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
region. It can also be stated in the following manner.
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 given equal to |Ψ|2 dV . For this reason |Ψ|2 is called the probability
density. It is also called probability function.
But the basic function Ψ as such has no attributable physical signif-
icance.
Probability of occurrence of an event in real and positive quantity.
But wavefunctions may be complex. Hence in order to get a value
that is positive and real while evaluating |Ψ|2 , the wavefunction Ψ is multiplied with its
ocmplex conjugate Ψ∗ . The product Ψ∗ Ψ is always a positive real quantity and corresponds
meaningfully to the definition of probability.

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 Module 2: Quantum Mechanics

∴ Probability density is given by

|Ψ|2 = Ψ∗ Ψ

Wave Packet and Probability of finding electron:

De Broglie waves are associated with a moving electron. The
square of the amplitude of the de Broglie waves in a particular
place is a measure of the probability of finding the electron at
the same place. The amplitude of the waves is negligible in
the region outside the wave packet. Thus the probability of
finding the electron is also negligible outside the wave packet
and is maximum where the wave amplitude is maximum inside
the wave packet. For a wave packet which is symmetric, the
probability is maximum at the center.

12 Normalization
If Ψ is the wave function associated with a particle, then we have |Ψ|2 dV as the probability
of finding the particle in a volume dV . Further, if we are certain to the extent that the
particle is definitely present in a particular region or space of volume V then, as per the
statistical rule, Z V
|Ψ|2 dτ = 1 (19)
0
However, in the above case, if we are not at all certain about locating the particle in
a finite volume anywhere in space, then the expectation will become limited to the extent
that ‘it exists somewhere in space’. Then the limits in Eq (19) from −∞ to ∞, and the
probability becomes, Z ∞
|Ψ|2 dτ = 1 (20)
−∞
R∞
But in most cases, the result of evaluation of −∞ |Ψ|2 dτ will not be unity but involves a
constant that existed in the equation for Ψ. However, the actual result whatever obtained
is equated to unity and the value of the constant is determined. It is then substituted in the
equation for Ψ which becomes the working equation for the wave function. This process is
called normalization.

13 Time independent Schrödinger wave equation

Let ψ(x) be a wave function which is independent of time t given by

ψ(x) = ψ = Aei(kx−ωt) (21)

where A is a constant and ω is the angular frequency of the wave.

Differentiating equation (21) w.r.t. x twice we get
dψ
= (ik)Aei(kx−ωt)
dx

d2 ψ
= (ik)(ik)Aei(kx−ωt) = −k 2 ψ
dx2

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 Module 2: Quantum Mechanics

Substituting
2π
k=
λ
we get
d2 ψ 4π 2
 
=− ψ (22)
dx2 λ2
For a particle of mass m moving with velocity v, Total energy

p2
E = KE + P E = +V
2m
m2 v 2
[∵ KE = 21 mv 2 = 2m
]
h2
E= +V
2mλ2
[∵ λ = hp =⇒ p = λh ]
Rearranging,
1 2m(E − V )
2
= (23)
λ h2
1
Substituting λ2
in equation (22),

d2 ψ 8π 2 m
 
=− (E − V )ψ
dx2 h2
or
d2 ψ 8π 2 m
 
+ (E − V )ψ = 0 (24)
dx2 h2
Equation (24) is called Time independent Schrödinger wave equation in one dimension.

14 Eigenfunctions and Eigenvalues

14.1 Eigenfunctions:
Eigenfunctions are those wave functions of quantum mechanics which possess the properties
that they are single valued and finite everywhere, and also their first derivatives with respect
to their variables are continuous everywhere.

14.2 Eigenvalues:
Once the eigenfunctions are known, quantum mechanical operators could be used to evaluate
the physical observables such as energy in which case each of the eigenfunctions provide one
energy value. Since there is only a restricted set of eigenfunctions, there is also restricted
set of energy values.
But all eigenfunctions when operated by the operators may not give proper result or value
for that physical observable. Because, it is also postulated in Quantum Mechanics that the
only possible values that can be observed of a physical quantity like angular momentum,
energy etc., of a system are the values λ in the operator equation

Âψ = λψ

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 Module 2: Quantum Mechanics

d ax
where  is the operator for the physical quantity and ψ is eigenfunction (for e.g. dx e = aeax ,
d2
dx2
(sin 2x) = −4(sin 2x) etc.,) i.e., the eigenfunction should be such that, the operator
operating on it produces back the wavefunction multiplied by a constant (here it is λ). such
values obtained for a physical observable are called eigenvalues. If it is energy operator
operating on ψ, then they are called energy eigenvalues1 . If it is momentum operator that
operates on ψ, then they are called momentum eigenvalues... so on.

15 Applications of Schrödinger wave equation

15.1 Energy eigenvalues of a Particle in one-dimensional, infinite

potential well (Potential well of infinite depth):
Suppose a particle of mass m is free to move in the x-direction only in the region from x = 0
to x = a. In this region its potential V will be zero. Outside this region, it is taken to be
infinite, (which means that the particle is bound within the limits x = 0 to x = a). Such a
configuration of potential in space is called infinite potential well. A particle bound within
such an infinite potential defined in 3-dimensions is referred to as particle in a box.
Outside the well, the Schrödinger equation is,
d2 ψ 8π 2 m
+ (E − ∞)ψ = 0 ( since V = ∞) (25)
dx2 h2
This equation holds good only if ψ = 0. The only
possible solution for the above equation is that ψ =
0 at the wall and also everywhere outside the well.
.....condition I
Since ψ = 0 also means |ψ|2 = 0, the particle
cannot be found at all outside the well.
Inside the well, the Schrödinger’s equation is given
by
d2 ψ 8π 2 m
+ Eψ = 0 ( Since V = 0) (26)
dx2 h2
or
h2
 2 
dψ
− 2 = Eψ (27)
8π m dx2
This is of the form Ĥψ = Eψ
As per the postulate of Quantum Mechanics, this should be an eigenvalue equation,
In Eq. (26), putting

8π 2 m
2
E = K2 (28)
h
We have,
d2 ψ
+ K 2ψ = 0
dx2
Discussion of the solutions:
The solution for th above equation is given by,
ψ = C cos Kx + D sin Kx (29)
1
In German, eigen means proper or characteristic. Eigenfunction and eigenvalue are written in German
as eigenfunktion and eigenwert.

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Module 2: Quantum Mechanics

But ψ = 0 at x = 0, as per condition I.

∴ Eq (29) becomes,
0 = C cos 0 + D sin 0
∴C=0 (30)
Again as per condition I, ψ = 0 at x = a, for which Eq (29) becomes
0 = C cos Ka + D sin Ka
From Eq (30) we have C = 0. Hence the above equation becomes,
D sin Ka = 0
Here, D need not be = 0.
∴ sin Ka = 0
or
Ka = nπ
where n = 0, 1, 2, 3, . . . . . . n is called quantum number which is either zero or a positive
integer.
nπ
∴K= (31)
a
Substituting for C and K from Eqs (30) and (31), Eq (29) can now be written as,
nπ
ψn = D sin x (32)
a
From Eq (28),
K 2 h2
E= 2
8π m
Using Eq (31), the above equation becomes,
n2 h2
E= (33)
8ma2
As already mentioned, n can have only integer values 0, 1, 2, 3, . . . . . . The corresponding
values that E takes are the energy eigenvalues.
The lowest permitted state of energy is referred to as the ground state energy. Thus zero
point energy is taken as the ground state energy. The energy states, corresponding to n > 1
are called excited states.
In Eq (33), the value zero for n is not acceptable because, when n = 0, ψn = by Eq (32),
which means to say that the electron is not present inside the box which is not true. Hence
the lowest acceptable value for n is 1. Consequently the lowest allowed energy corresponds
to n = 1 which is called the zero point energy. The zero point energy of an electron in an
infinite potential well is given by,
h2
Ezero-point =
8ma2
which represent the permitted solution.
The lowest permitted stat of energy is referred to as the ground state energy. Thus zero
point energy is taken as the ground state energy. The energy states corresponding to n > 1
are called excited states.
To evaluate D in Eq (32) one has to perform the normalization of the wavefunction.

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Module 2: Quantum Mechanics

Normalization:
The integral of the square of the wave function over the entire space in the well must be
equal to unity because, there is only one particle and at any time it is present somewhere
inside the well only. Therefore, Z a
|ψ|2 ds = 1 (34)
0

Substituting for ψn from Eq (32), we have,

Z a
nπ
D2 sin2 xdx = 1
0 a
But, we know that,
1
sin2 θ = (1 − cos 2θ)
2
 Z a
1 a
Z 
2 1 2nπ
∴D dx − cos xdx = 1
2 0 2 0 a
a
D2
 
a 2nπx
x− sin =1
2 2nπ a 0
or
D2 h a i
a− sin(2nπ) = 1
a 2nπ
or
D2 a
=1
[ since sin(2nπ) = 0]
2
r
2
D=
a
Thus the normalized wavefunction of a particle in a one-dimensional infinite potential
well is given by r
2  nπ 
ψn = sin x (35)
a a

Eigenfunctions, Probability densities and energy eigenvalues for

particle in an infinite potential well:
Since the particle in an infinite well is a problem under quantum mechanical conditions, the
prime questions to be considered are, the most probable location of the particle in the well
and its energies, both to be evaluated for the different permitted states. let us analyze the
same here.
Following Eq (32), we can write the eigenfunctions ψ1 , ψ2 , ψ3 , . . . . . . for particle in the
well by putting 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.

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Module 2: Quantum Mechanics

For n = 1, the eigenfunction is,

π 
ψ1 = D sin x, from Eq (32)
a
In the above equation ψ1 = 0 for both x = 0 and x = a.
But ψ1 has maximum value for x = (a/2).
Thus a plot of ψ1 versus x will be as shown in figure.
A plot of |ψ1 |2 is 0 both at x = 0 and at x = a. It is
maximum at x = (a/2). It means to say that, in ground state
the particle cannot be found at all at the walls of the well, and the probability of finding it
is maximum at the central region.
Regarding the energy of the particle, using Eq (33), the energy in the ground state (which
is the same as the zero point energy E0 ) is got by putting n = 1.

h2
E1 = = E0 (36)
8ma2
This is the energy eigenvalue for the ground state.
Further, if E0 is the energy in the nth excited state, then from Eqs (33) and (36),

En = n2 E0 (37)

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 eigenfunction for this state is,
 
2π
ψ2 = D sin x
a

Now, ψ2 = 0 for the values x = 0, a/2 and a. Also, ψ2

reaches maximum for x = a4 and 3a 4
. These facts are seen in
the plot of ψ2 versus x shown in figure.
The plot of |ψ2 |2 versus x is shown in figure. It is seen that
|ψ2 |2 = 0 at x = 0, a/2 and a. It means that in the first excited
state the particle cannot be observed either at the walls, or at
the center.
Further, from (37), for n = 2
 2 
h
E2 = 4
8ma2

This is the energy eigenvalue for the first excited state. Also,

E2 = 4E0

Thus the energy in the first excited state is 4 times the zero point energy.
Case (iii), n = 3:
This is the second excited state.

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 Module 2: Quantum Mechanics

Following the same analysis as carried out earlier, we have

the eigenfunction for the second excited state as,
 
3π
ψ3 = D sin x
a
ψ3 = 0 for x = 0, a/3, 2a/3 and a.
ψ3 will have maximum value for x = a/6, a/2 and 5a/6.
These facts are revealed in the plot ψ3 versus x.
The plot of |ψ3 |2 versus x is shown in figure has maxima at
x = a/6, a/2 and 5a/6 which also imply the locations at which
the particle is most likely to be found.
This case corresponds to the second excited state. As in the earlier cases, using Eq (37),
the energy in this state is given by,
 2 
h
E3 = 9
8ma2
This is the energy eigenvalue in the second excited state.
Thus,
E3 = 9E0

16 Energy eigenvalues for a free particle:

Free particle means, it is not under the influence of any kind of field or force. Thus it has
zero potential i.e., V = 0. Hence Schrödinger’s equation becomes,
d2 ψ 8π 2 m
+ Eψ = 0
dx2 h2
or
h2 d2 ψ
 
− 2 = Eψ
8π m dx2
The above equation holds good for a particle for a particle for which the potential V = 0
over the entire space (no boundaries at all).
We know that in the case of particle in an infinite potential well, the condition V = 0
holds good only over a finite width ‘a’ and outside this region, V = ∞.
Since for a free particle, V = 0 holds good everywhere, we can extend the case of particle
in an infinite potential well to the free particle’s case, by treating the width of the well to
be infinity, i.e., by allowing a = ∞.
We have the equation for energy for energy eigenvalues for a particle in an infinite po-
tential well as,
n2 h2
E=
8ma2
where n = 1, 2, 3, . . . . . .
Rearranging this equation, we have,
2a √
n= 2Em
h
Here, we see that, for a particle with constant energy E but confined in the well, n
depends solely on ‘a’. Hence, as a → ∞, n → ∞. In the limiting case when a = ∞, the

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Module 2: Quantum Mechanics

particle is no more confined in ay sort of well but free, at which time it also follows that,
n = ∞, which essentially means that a free particle can have any energy i.e., the energy
eigenvalues or the possible values of energy are infinite in number. Keeping in mind the
energy level representation, we say that the permitted energy values are continuous. all
these mean, there is no discreteness in the allowed energy values. In other words, there is
not quantization of energy in the case of a free particle and the problem is dealt in classical
mechanics. Thus a free particle is a ‘classical entity’.

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