Module-I I Dept.

of Physics, BIET, DVG Quantum Mechanics

Module- II
Quantum Mechanics
Syllabus: de Broglie Hypothesis and Matter Waves and their propeties, de Broglie wavelength and
derivation of expression by analogy, Phase Velocity and Group Velocity, Heisenberg’s Uncertainty Principle
and its application (Non-existence of electron inside the nucleus - Non Relativistic), Principle of
Complementarity, Wave Function, Time independent Schrödinger wave equation (Derivation), Physical
Significance of a wave function and Born Interpretation, Expectation value, Eigen functions and Eigen
Values, Particle inside one dimensional infinite potential well, Quantization of Energy States, Waveforms
and Probabilities.

Numerical problems- on de Broglie Hypothesis, Heisenberg’s Uncertainty Principle, Energy Eigen Values
for a particle in 1D infinite potential well

History: At the end of 19th century, scientists felt that all the laws of physics (which were known at that period of time)
are enough to explain all the events occur in nature. It was believed that there are only two kinds in nature. First the bodies
which are made up of particles and second radiation. All particles obey Newton’s laws of motion and radiation obey
Maxwell’s equations of electromagnetism. These laws are now a days known as classical physics.
Fortunately, at the same time some experiments were performed and the experimental results were not in
comparison with so called classical theory. Some of them are Black body radiation, Photo electric effect and Compton
Effect etc. In order to overcome the drawbacks of Classical Physics, a new types of laws of physics have been introduced
which are now known as Quantum Physics. Black body radiation is one of the great effects which has led to the concept
of Modern Physics/Quantum Physics.

Need of Quantum Mechanics: One of the interesting areas of research in Physics during latter part of 19 th century was
about emission of radiation from black body (It is an object, which absorbs all radiations incident on it and emit those
radiations on heating). Theoretical investigations were individually carried out by Wien (in German) and Rayleigh &
Jeans (in England) to account for the energy emitted by black body and partially succeeded. While, the equation given by
Wien was fitted well with experimental curve at shorter wavelengths but failed at longer side. Conversely, Rayleigh-Jeans
formula was fitted well with experimental curve at longer wavelengths and failed at shorter side. Finally, Max Planck
worked out an empirical equation that fitted the entire curve completely. Following the success, Planck analyzed how his
equation could be interpreted and realized that energy emitted by black body was quantized. Earlier, it was thought as
continuous as predicted by traditional mechanics (i.e., classical mechanics), ⸫ failed to explain experimental observations.
This quantization signified the need for new mechanics (i.e., Quantum Mechanics). Thus, it was with Planck’s Eqn., for
energy density of the black body radiation, quantum mechanics was originated.

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
de Broglie Hypothesis:
The origin of quantization of energy lies in the dual nature behavior observed in particle and wave
aspects. For example, Compton observed that X-rays are scattered like particle by an electron and Brag
observed that X-rays get diffracted by a crystal like a wave. By observing such a dual nature of light, Louis
de Broglie in 1924 put forward a bold hypothesis that:

Statement: “Just like an electromagnetic radiation (light) which behaves as a wave and as a particle at
different circumstances, matter entities like electron proton, neutron, atom etc., inherited the same dual
character i.e., particles are also associated with the wave nature in their motion under certain
circumstances. Thus matter waves exists.

“Material particles associated with waves in their motion are called matter waves or deBroglie waves” and
the wavelength is called de Broglie wavelength.

Experimental proof-Wave nature of electron:- Davisson & Germer of USA (in 1927) accidentally
conducted an experiment to show diffraction of accelerated electrons from nickel crystal just like the
waye. This diffraction of elctrons confirms their wave nature.

Derivation of expression for de Broglie wavelength (λ) by analogy:

The concept of matter waves is well understood by combining Planck’s quantum theory and
Einstein’s theory. Consider a photon of frequency ‘ν’ moving with velocity ‘c’ & wavelength ′𝝀′, its energy
‘E’ is

By Einstein’s mass-energy relation, 𝐸 = 𝑚𝑐 2 (1)

By Plank’s theory of radiation, 𝐸 = ℎν (2)

⸪ ν= 𝝀
𝒄 𝒄
Equating eqn. (1) and (2), we have, 𝑚𝑐 2 = ℎν  𝑚𝑐 2 = ℎ 𝝀

𝒉
Or, 𝝀 = 𝒎𝒄

where, 𝑃 = 𝒎𝒄 , 𝒘𝒉𝒆𝒓𝒆 ′𝒄′ 𝒊𝒔 𝒕𝒉𝒆 𝒗𝒆𝒍𝒐𝒄𝒊𝒕𝒚 𝒐𝒇 𝒍𝒊𝒈𝒉𝒕.

By analogy, for deBroglie waves, the deBroglie wavelength is given by

𝒉
𝝀= -------------(1)
𝒑

where 𝑃 = 𝒎𝒗, 𝒊𝒏𝒘𝒉𝒊𝒄𝒉 ′𝒗′ 𝒊𝒔 𝒕𝒉𝒆 𝒗𝒆𝒍𝒐𝒄𝒊𝒕𝒚 𝒐𝒇 𝒕𝒉𝒆 𝒑𝒂𝒓𝒕𝒊𝒄𝒍𝒆.

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
P

Different forms of de Broglie Wavelength ():

de Broglie wavelength of an electron of kinetic energy E

For a particle of mass ‘m’ & velocity ‘v’ its kinetic energy ‘E’ is given by,
1
𝐸 = 𝑚𝑣 2
2
1 𝑚
𝐸 = 𝑚𝑣 2
2 𝑚
2
𝑝
𝐸=
2𝑚
⟹ 𝑝 = √𝟐𝒎𝑬 -------------------- (2)

𝒉
⸫ eqn. (1) becomes 𝝀= ------------(3)
√𝟐𝒎𝑬

de Broglie wavelength of an electron accelerated under Potential (V):

If an electron accelerated under a potential difference V then the kinetic energy is given by
E = eV
𝒉
⸫ eqn. (3) becomes 𝝀= -------(4)
√𝟐𝒎𝒆𝑽

This is the equation for wavelength accelerated electron under the potential V.

Since ‘h’, ‘m’ & ‘e’ are constants, i.e., 𝒉 = 6.626 × 10−34 JS, 𝒎 = 9.1 × 10−31 kg & 𝒆 = 1.6 × 10−19 C,
substituting these values in above eqn. we get,
𝟏.𝟐𝟐𝟔
𝝀= 𝑛𝑚
√𝑽
𝒉
Note: Instead of electron, if a particle of charge ‘q’ is accelerated under potential V, then 𝝀=
√𝟐𝒎𝒒𝑽

Properties of matter waves or de-Broglie waves:

𝒉
1. 𝝀 = 𝒎𝒗 shows that lighter is the particle and lower is the velocity greater is the wavelength

associated with it.

2. For v = 0, λ = ∞ and v = ∞, λ = 0 indicates that matter waves are generated by the motion of the particles
whether they are charged or uncharged. Hence they are not electromagnetic waves
3. The velocity of matter waves is different for different materials and it depends upon the mass &
velocity, whereas an e.m. wave travels with a constant velocity ‘c’.
4. The wave and particle aspects of a moving body can never be appear in the same experiment i.e.,
both are separably linked.
5. The wave nature of particle introduces an uncertainty in the location of a particle whereas it represents only
the probability of finding the particle over the small region of space. (wave packet)

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics

Wave Packet:
Defn: A wave packet refers to the case where two (or more) waves exist simultaneously.
A wave packet is often referred to as a wave group. This situation is permitted by the principle of
superposition.
In physics, a wave packet is a short ‘envelop’ of
localized waves that travel as a group. A wave packet can be
analyzed into, or can be synthesized form of group of sinusoidal
waves of different wave numbers, phase and amplitudes such
that they interfere constructively or destructively in the space.

Schrodinger postulated that a moving particle (electron etc.,) is equivalent to a wave

packet rather than a single wave.

Heisenberg’s Uncertainty Principle:

State:-“The position and momentum of a particle cannot be determined accurately and simultaneously. The
product of uncertainty involved in the measurement of position and momentum is always greater than or
ℏ h
equal to (where, ℏ = 2π)”.
2
𝐡
i.e., ∆𝒙 ∙ ∆𝒑 ≥
𝟒𝛑

where, ∆𝑷 and ∆𝒙 are the uncertainties in the measured values of the momentum and position of the particle,
respectively.
Similar to Position - Momentum uncertainty, there are other two uncertainty relations also present. They
are: Angular momentum - Angular displacement uncertainty
h
i.e., ∆𝑳 ∙ ∆𝜽 ≥ 4π

and Energy - Time uncertainty

h
i.e., ∆𝑬 ∙ ∆𝒕 ≥ 4π

Application of Uncertainty Principle:

Non-existence of electron in the nucleus (Non-relativistic case): This is related to the -ray emission
in nuclear physics. We know that the -rays are actually streams of negatively charged particles, having
kinetic energies in the range 3 to 4 MeV.
“Is it possible that electrons exist inside the nucleus with certain energy…….!!???”.
It can be answered by applying Uncertainty Principle as follows:

Proof: The energy of a body of mass m, moving with momentum P can be expressed as,

𝑃2
𝐸= (1)
2𝑚

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
𝒉
by Uncertainty Principle, ∆𝒑𝒙 ∙ ∆𝒙 ≥
𝟒𝝅

𝒉
 ∆𝒑𝒙 ≥ (2)
𝟒𝝅 ∆𝒙

We know that the diameter of nucleus is of the order of 10-14 m. Thus, if an electron is to exist inside
the nucleus, then the uncertainty in its position ∆𝒙 must not exceed 10-14 m.

i.e., ∆𝑥 ≤ 10−14 𝑚

Using this in eqn. (2), we have,

6.626×10−34
∆𝑝𝑥 ≥
4×3.142×10−14

or, ∆𝒑𝒙 ≥ 0.5 × 10−20 N-s (3)

This is the uncertainty in the momentum of the electron. Now, by making use of this inequality
(i.e., eqn. 3) in (1), we can say that, in order that electron may exist inside the nucleus, its energy E must be
such that,
2
(0.5×10−20 )
𝐸≥ using eqn. (1) and 𝒎 = 9.1 × 10−31 kg
2(9.1×10−31 )

 𝐸 ≥ 1.372 × 10−11 J
1
or, 𝐸 ≥ 1.372 × 6.24 × 1018 𝑒𝑉 ⸪ 𝟏 𝑱 = 𝑒𝑉
1.6×10−19

⸫ 𝑬 ≥ 𝟗𝟓 𝑴𝒆𝑽

It indicates that if electron exists inside the nucleus, then its energy must be greater than 𝟗𝟓 𝑴𝒆𝑽. But, the
experimental investigations on -decay reveal that, the kinetic energy of -particle emitted due to conversion
of nucleons during -decay is of the order of 𝟑 to 𝟒 𝑴𝒆𝑽.
This clearly indicates that, the emitted electrons cannot be the ones, which existed inside the nucleus.
{

Wave Function:
In quantum mechanics, it is postulated that every particle is associated with a function determined by
the physical situation. This function is called ‘wave function’. It contains all possible information about the
system. Hence, wave function is also called as state function.
The wave function may vary with respect to both space (x) and time (t). It is then called total wave
function and it is represented by capital Greek letter 𝚿 (psi). If the wave function varies only with respect
to position then it is represented by lowercase Greek letter ‘𝜓’.

The total wave function can be represented as: 𝚿 = 𝐀𝒆𝒊(𝒌𝒙−𝝎𝒕)

where ‘A’ is constant (i.e., amplitude), ′𝝎′ is the angular frequency, ‘k’ is propagation wave vector.

Separating the space and time dependent parts: 𝚿 = 𝐀𝒆𝒊𝒌𝒙 𝒆−𝒊𝝎𝒕

 𝚿 = 𝜓 𝒆−𝒊𝝎𝒕 𝜓 = 𝑨𝒆𝒊𝒌𝒙 Space dependent wave function

In quantum mechanics, the wave function actually accounts for the wave like properties of a particle. It is
obtained by solving fundamental eqn. called Schrodinger Equation.

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
Schrodinger Equation:
It can be setup in two different contexts. One, which is general and takes care of both space and the
time variations of the wave function, is called time dependent Schrodinger’s equation. The other one is
applicable to steady state conditions in which wave function is only the function of space not the time, is
called time independent Schrodinger’s equation.

1-D Time independent Schrodinger equation:

According to de Broglie theory, for a particle of mass ‘m’ moving with a momentum ‘P’, associated
with a wave of wavelength,
ℎ ℎ
𝜆=
𝑝
 𝑃=
𝜆
(1)
The wave function describing the de Broglie wave travelling in positive ‘x’ direction (i.e., 1-D) can be written
using complex notation as,

𝚿 = A 𝑒 𝑖(𝑘𝑥−𝜔𝑡) (2)

where, 𝚿 is the total wave function, A is a constant and 𝝎 is the angular frequency of the wave.

On differentiating eqn. (2) twice w.r.t. ‘x’, we get,

𝑑2𝜓
= A 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑖 2 𝑘 2
𝑑𝑥 2

𝑑2𝜓
= −A 𝑒 𝑖(𝑘𝑥−𝜔𝑡) 𝑘 2
𝑑𝑥 2

𝑑2𝜓 −4𝜋2 𝜓 2𝜋
= [from eqn. (2) & k = ]
𝑑𝑥 2 𝜆2 𝜆

𝟏 1 𝑑2𝜓
 𝝀𝟐
= −
4𝜋2 𝜓 𝑑𝑥 2
------------ (3)

For a particle of mass ‘m’ moving with velocity ‘v’, the kinetic energy (KE) is;

1 𝑝2
𝑲𝑬 = 𝑚𝑣 2 =
2 2𝑚

ℎ
But, from eqn. (1), we know that, 𝑷 = then above eqn. becomes,
𝜆

ℎ2 1
𝑲𝑬 = (4)
2𝑚 𝜆2

𝟏
Substitute the value of from eqn. (7) in (8), we get,
𝝀𝟐

−ℎ 2 1 𝑑2𝜓
𝑲𝑬 = (5)
8𝜋 2 𝑚 𝜓 𝑑𝑥 2

If the particle’s potential energy is ‘V’, then the total energy (E) becomes,

𝑬 = 𝑲𝑬 + 𝑽

−ℎ 2 1 𝑑2 𝜓
⸫ 𝑬= +𝑽  ⸪Using eqn. (5)
8𝜋 2 𝑚 𝜓 𝑑𝑥 2

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
−ℎ 2 1 𝑑2 𝜓
or, =𝐸−𝑉
8𝜋 2 𝑚 𝜓 𝑑𝑥 2

𝒅𝟐 𝝍 𝟖𝝅𝟐 𝒎
or, + (𝑬 − 𝑽)𝜓 = 𝟎
𝒅𝒙𝟐 𝒉𝟐

This is the time-independent Schrödinger equation in 1-Dimension.

Note: Time-independent Schrödinger equation in 3-Dimension:

𝒅𝟐 𝝍 𝒅𝟐 𝝍 𝒅𝟐 𝝍 𝟖𝝅𝟐 𝒎
( 𝟐+ + ) + (𝑬 − 𝑽)𝜓(𝑥, 𝑦, 𝑧) = 𝟎
𝒅𝒙 𝒅𝒚𝟐 𝒅𝒛𝟐 𝒉𝟐

Physical significance of Wave function & its Properties:

Max Born interpretation of wave function is probability density |𝚿|𝟐

Probability density: If 𝚿 is the wave function associated with the particle, then |𝚿|𝟐 is the probability of
finding the particle in a given volume at a given instant.

If 𝝉 be volume of certain region, inside which a particle is known to be present, but where exactly is not
known (see Fig.). Then the probability of finding the particle in certain element of volume d𝝉 of 𝝉 is always
equal to "|𝚿|𝟐 𝒅𝝉". For this reason |𝚿|𝟐 is called as probability density or probability function.
Since, probability of occurrence of any event is a real and positive quantity. However, 𝚿 is complex
& has no considerable physical significance. Hence, in order to get real and positive value of |𝚿|𝟐 , the wave
function is multiplied with its complex conjugate. The product 𝚿 𝚿 ∗ is always a positive real quantity.

⸫ |𝚿|𝟐 = 𝚿 𝚿 ∗
Normalization / Expectation Value: If we are certain that, the particle is definitely present
inside the volume 𝝉 then, as per the statistical rule,
𝝉
∫𝟎 |𝚿|𝟐 𝒅𝝉 = 𝟏
Here, the value 1 for probability means, it is clear that particle is certainly present in the volume 𝝉. If we are
not at all certain about presence of particle in a finite volume then, the ‘particle must exist somewhere in the
space’.
∞
⸫ ∫−∞ |𝚿|𝟐 𝒅𝝉 = 𝟏
This interpretation was first given by Max Born in 1926.

Properties of Wave function:

 𝚿 is single valued everywhere.

 𝚿 is finite everywhere.
 𝚿 and its first derivative with respect to its variable are continuous.
 𝚿 vanish at infinity and for bound states,

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
Eigen Functions & Eigen values:

Defn: “The wave functions that possess all the 4 properties 𝚿 are called as Eigen functions”.

Operator: It is a mathematical entity, which converts one function/state to other function/state.

The information of a wave function 𝚿 can be extracted by performing certain mathematical operations on 𝚿 .

Eigen values: If an operator is applied on Eigen function and produce Eigen function back along with a
constant multiplied it, then such constant values obtained for a physical observable are called as Eigen
values. 𝒅
Eg:- (𝒊) 𝒅𝒙 (𝒆𝒂𝒙 ) = 𝒂 𝒆𝒂𝒙 ,
̂ acts on eigen function 𝚿 and gives back 𝚿 along
An operator 𝑨
with Eigen value ′𝝀′ , i.e., 𝒅𝟐
(𝒊𝒊) (𝐬𝐢𝐧 𝟐𝒙) = −𝟒 (𝐬𝐢𝐧 𝟐𝒙), etc.
𝒅𝒙𝟐
̂𝚿 = 𝝀 𝚿
𝑨

Application of Schrödinger wave equation:

Particle (electron) in 1-D potential well of infinite height & finite width or Particle bounded between
two walls of infinite height & finite width:

Consider a particle of mass ‘m’ is free to move in the X-direction only from
region 𝑥 = 0 𝑡𝑜 𝑥 = 𝑎 as shown in Fig. In this region, its potential is 𝑉 =
0. Outside this region, the potential 𝑉 = ∞. Such configuration of potential
is called as infinite potential well.

Outside the well, the Schrödinger equation is given by,

𝑑2 𝜓 8𝜋 2 𝑚
+ (E − ∞)𝜓 = 0 (1)  Since, 𝑉 = ∞.
𝑑𝑥 2 ℎ2

The above eqn. holds good only if 𝝍 = 0.

⸫ the only possible solution is 𝝍 = 0 at the walls and also everywhere outside the well. ….. (Condn -I)

 |𝝍|𝟐 = 𝟎 It indicates that particle cannot be found at all outside the well.

Inside the well, the Schrödinger equation is given by,

𝑑2𝜓 8𝜋 2 𝑚
+ E𝜓 = 0 (2)  Since, 𝑉 = 0
𝑑𝑥 2 ℎ2

8𝜋 2 𝑚
In eqn. (2), putting E = 𝐾2 (3)
ℎ2

𝑑2 𝜓
We have, + 𝐾2𝜓 = 0
𝑑𝑥 2

The solution of the above equation is given by,

𝝍 = 𝑪 𝐜𝐨𝐬 𝑲𝒙 + 𝐃 𝐬𝐢𝐧 𝑲𝒙 --------------- (4)

Apply I boundary condition, i.e., 𝜓 = 0 at 𝑥 = 𝟎

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
⸫ eqn. (4) becomes, 0 = 𝐶 𝑐𝑜𝑠 𝐾 ∙ 0 + 𝐷 𝑠𝑖𝑛 𝐾 ∙ 0

 𝑪 = 𝟎 − − − − − (5)

Apply II boundary condition, i.e., 𝜓 = 0 at 𝑥 = 𝒂

⸫ eqn. (4) becomes, 0 = 𝐶 𝑐𝑜𝑠 𝐾𝑎 + 𝐷 𝑠𝑖𝑛 𝐾𝑎

 𝐷 𝑠𝑖𝑛 𝐾𝑎 = 0  ⸪ C = 0, using eqn. (5)

⸪ 𝑫 ≠𝟎  𝑠𝑖𝑛 𝐾𝑎 = 0

 𝑠𝑖𝑛 𝐾𝑎 = sin 𝑛 𝜋

 𝑲𝒂 = 𝒏𝝅
𝒏𝝅
 𝑲=
𝒂
-------------(6)

where, 𝒏 = 𝟎, 𝟏, 𝟐, 𝟑, 𝟒, … is known as quantum number.

Substituting the values of eqn. (5) and (6) in eqn. (4), we get,

𝒏𝝅
𝝍 = 𝑫 𝐬𝐢𝐧 𝒙 ------------(7)
𝒂

And, substituting the value of eqn. (6) in eqn. (3), we get,

8𝜋2 𝑚 𝒏𝝅 2
E=( )
ℎ2 𝒂

𝒏𝟐 𝒉𝟐
 𝑬=
𝟖𝒎𝒂𝟐
---------------(8)

This is the required Energy Eigen value eqn. for the electron in 1-D potential well of infinite height.
Since, 𝒏 = 𝟎, 𝟏, 𝟐, 𝟑, 𝟒, … then corresponding values that E takes are the quantized energy Eigen values.

In eqn. (7), the value 𝑛 = 0 is not acceptable, as 𝝍 = 𝟎 at 𝒏 = 𝟎 by eqn. (7). Hence the lowest value for n
is 1. Consequently, the lowest allowed energy corresponding to 𝒏 = 𝟏 is called as ‘zero point energy’ or ground
state energy. The energy states corresponding to n>1 are known as excited states energies.

To find D in eqn. (7): Consider the normalized wave function for the particle from 𝒙 = 𝟎 𝑡𝑜 𝒂, as,
𝑎
∫0 |𝛹𝑛 |2 𝑑𝜏 = 1

Substituting 𝜳 from eqn. (7), we have,

𝑎 𝑛𝜋
∫0 𝐷 2 𝑠𝑖𝑛2 ( 𝑎 ) 𝑥 𝑑𝑥 = 1

𝑎1 𝑛𝜋 1
 D2 [∫0 [1 − 𝑐𝑜𝑠2 ( ) 𝑥] 𝑑𝑥 ] = 1  ⸪ sin2 𝜃 = [1 − cos 2𝜃]
2 𝑎 2

𝐷2 𝑎 𝑎 2𝑛𝜋
i.e., [∫0 𝑑𝑥 − ∫0 𝑐𝑜𝑠 ( ) 𝑥 𝑑𝑥 ] = 1
2 𝑎

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics
𝐷2 𝑎 2𝑛𝜋𝑥 𝑎
or, [[𝑥]𝑎0 − 𝑠𝑖𝑛 | ]=1
2 2𝑛𝜋 𝑎 0

𝐷2 𝑎
 [𝑎 − sin 2𝑛𝜋] = 1
2 2𝑛𝜋

𝐷2
or, [𝑎 ] = 1 ⸪ sin 2𝑛𝜋 = 0
2

𝟐
⸫ 𝑫=√
𝒂

𝟐 𝒏𝝅
Putting the value of ‘D’ in eqn. (7), we get, 𝝍𝒏 = √𝒂 𝐬𝐢𝐧 ( 𝒂 ) 𝒙

This is the Eigen function for a particle in an infinite potential well.

Eigen Functions, Probability densities and Energy Eigen values for a particle in Potential well:

Case (i): 𝒏 = 𝟏:- This is the ground state and the particle is normally found in this state.
2 𝜋
Eigen function becomes; 𝝍𝟏 = √𝑎 sin (𝑎) 𝑥

𝜓1 = 0 at 𝑥 = 𝟎 and 𝑥 = 𝒂
𝑎
But, 𝜓1 = 𝒎𝒂𝒙 at 𝑥 =
2

𝑎
|𝝍𝟏 |2 plot indicates that probability of finding the particle is maximum at the center i.e., 𝑥 = .
2

ℎ2
The ground state energy for n=1 will be; 𝑬𝟏 = = 𝑬𝟎 for , nth state, 𝑬𝒏 = 𝑛2 𝑬𝟎
8𝑚𝑎2

Case (ii): 𝒏 = 𝟐:- This is the first excited state

2 2𝜋
Eigen function becomes: 𝝍𝟐 = √𝑎 sin ( 𝑎 ) 𝑥
𝒂
𝜓2 = 0 at 𝑥 = 𝟎, 𝟐
, and 𝒂

𝑎 3𝑎
But, 𝜓2 = 𝒎𝒂𝒙 at 𝑥 = 4 and 4

4ℎ 2
The first excited state energy for n=2 will be; 𝐸2 = 𝑜𝑟 𝑬𝟐 = 𝟒𝑬𝟎
8𝑚𝑎 2

Case (iii): 𝒏 = 𝟑:- This is the second excited state

2 3𝜋
Eigen function becomes: 𝝍𝟑 = √𝑎 sin ( 𝑎 ) 𝑥
𝒂 𝟐𝒂
𝜓3 = 0 at 𝑥 = 𝟎, 𝟑
, 𝟑
and 𝒂

𝑎 𝑎 5𝑎
But, 𝜓3 = 𝒎𝒂𝒙 at 𝑥 = , and
6 2 6

9ℎ 2
The second excited state energy for n=3 will be; 𝐸3 = 8𝑚𝑎2 𝑜𝑟 𝑬𝟑 = 𝟗𝑬𝟎

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Module-I I Dept. of Physics, BIET, DVG Quantum Mechanics

Solved Examples
Example 1. Calculate the de Broglie Further, substituting the above in eqn. (1),
wavelength associated with an electron
having a kinetic energy of 100 eV. 6.63 1034

2.09 1023
Data: Kinetic energy of the electron, E=100 eV
λ = 3.17 X 10-11 m
To find : de Broglie wavelength of electron, λ = ?

Solution: We have the equation, Example 3. The velocity of an electron of a

h hydrogen atom in the ground state is 2.19 X
 106 m/sec. Calculate the wavelength of the de
2mE
Broglie waves associated with its motion.
From data, E= 100 eV= 100 x 1.602 x 10-19 J Data: Velocity of electron, v=2.19 X 106 m/s
Substituting the values for various parameters, To find : de Broglie wavelength, λ = ?
h
 Solution: de Broglie wavelength of electron is;
31 19
2  9.12 10 100 1.602 10
h h
 or 
  1.227 10 m10
p mv
6.62 1034
Example 2. Calculate the momentum of an 
electron and the de Broglie wavelength (9.111031 )(2.19 106 )
associated with it if its KE is 1.5 keV.
  3.31 10 10 m or, λ = 3.17 Å
Data: Kinetic energy of electron, E = 1.5 keV
Example 4. Compute the de Broglie
To find : Momentum of the electron p=?
wavelength for a neutron moving with one
De Broglie wavelength of electron, λ = ? tenth part of the velocity of light, given, mass
of neutron = 1.674 X 10-27 kg.
Solution: We have the de Broglie relation,
Data: Mass of neutron m = 1.674 X 10-27 kg
h
 (1) 1
p Velocity of neutron; v  c  3  107 m/sec
10
We also have the relation between the kinetic
energy and de Broglie wavelength, To find : de Broglie wavelength; λ = ?
h Solution: de Broglie wavelength for neutron is;
 (2)
2mE
h h
Comparing the equations (1) and (2), we have,  or 
h h p mv
 or, p  2mE (3)
p 2mE 6.6 1034

(1.074 1027 )  (3 107 )
From data, E= 1.5 x103 eV = 1.5 x103(1.6 x10-19) J
  1.314 1014 m
or, E = 2.4 X 10-16 J
Example 5. Estimate the potential difference
Substituting this value in eqn. (3), we have
through which a proton is needed to be
accelerated so that its de Broglie wavelength
p  2  9.11 1031  2.4  10 16
becomes equal to 1 Å. Given that it’s mass is
p = 2.09 X 10-23 kgms-1 1.673 X 10-27 kg.

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Module-I Quantum Mechanics
Data: de Broglie wavelength attained, λ = 10-10 m ℎ
𝜆=
√2𝑚𝐸

Mass of the proton, m = 1.673 X 10-27 kg 6.63×10−34

𝜆 = √2×8.9×10−31
×100× 1.6×10−19
To find : Potential difference needed, V = ?
𝝀 = 1.24× 𝟏𝟎−𝟏𝟎 𝒎
Solution: We have the equation,
ℎ h2 Example 8. The KE of an electron is equal to
𝜆= or, V the energy of a photon with a wavelength of
√2𝑚𝑒𝑉 2me 2
560 nm. Calculate the de-broglie wavelength
(6.63 1034 ) 2 of the electron. (Model QP2)
V
2 1.673 1027 1.6 1019  (1010 ) 2
V  0.082V Data: Energy of photon is given by,
ℎ𝑐 6.625×10−34 ×3×108
Example 6. Evaluate de Broglie wavelength 𝑬= 𝜆
= 560×10−9
= 0.0354 × 10−17 J
of He nucleus that is accelerated through 500
V. Given mass of proton=mass of To find: de-broglie wavelength of electron, λ = ?
neutron=1.67x10 -27
kg (May 2022).
Solution: The de Broglie wavelength of an
Data: Mass of proton=Mass of neutron=1.67 x 10-27 kg electron is;
ℎ
Potential difference V = 500 V 𝜆=
√2𝑚𝐸
To find : de Broglie wavelength; λ = ? 6.63×10−34
𝜆 = √2×9.1×10−31
×0.0354×10−17
Solution: ‘He’ nucleus has 2 proton & 2
neutrons. 𝝀 = 𝟖. 𝟐𝟔 × 𝟏𝟎−𝟏𝟎 𝒎
⸫ mass of nucleus, m = 4m’= 4 X 1.67 X 10-27 kg
Heisenberg’s Uncertainty Principle
Since there are 2 protons, the charge on nucleus,
Example 9. Infer the Heisenberg’s
e = 2 x q = 2 x (1.6 X 10-19) Uncertainty Principle for quantum and
classical mechanical measurements.
We have the equation for de Broglie wavelength,
ℎ Solution: Let us consider the following
𝜆=
√2𝑚𝑒𝑉 example to infer this (i.e., uncertainties for
6.63×10−34
𝜆= microscopic and macroscopic systems).
√2×(4×1.67×10−27 )(2×1.6×10−19 )×500
Let us estimate the uncertainty in the position of;
𝝀 = 𝟒. 𝟓𝟑 × 𝟏𝟎−𝟏𝟑 𝒎
(a) A neutron moving at velocity 5 × 106 m/s
Example 7. A particle having mass of (Quantum mechanical measurement).
0.5MeV/c2 has a kinetic energy of 100 eV.
(b) A 50 kg person moving at velocity 2 m/s
Calculate the de-broglie wavelength, where c
(Classical mechanical measurement).
is velocity of light. (Model QP1)
Given: Mass of neutron is 1.67 × 10−27 kg,
Data: Mass of the particle, h = 6.623 × 10−34 J s.
0.5×106 ×1.6×10−19
m=0.5MeV/C2= =8.9 × 10−31 kg The Heisenberg’s Uncertainty in position and
(3×108 )2
momentum is;
Kinetic Energy, E = 100 eV = 100 × 1.6 × 10−19 J ℎ
∆𝑥 ∆𝑝 ≥ 4𝜋
To find : De Broglie wavelength of electron, λ = ? ℎ ℎ
∆𝑥 ≥ or ∆𝑥 ≥
4𝜋∆𝑝 4𝜋𝑚𝑣
Solution: From de- Broglie wavelength equation,

Dr. Vinay Parol, Assistant Professsor, BIET, Davangere 12

Module-I Quantum Mechanics
(a) For quantum mechanical measurement; ⸫ Uncertainty in momentum is 1.06 × 10−24 m/s

m = 1.67 × 10−27 kg, v = 5 × 106 m/s We have the equation for momentum,
6.623 × 10−34 𝑝 = √2𝑚𝐸
∴ ∆𝑥 ≥
4 × 3.142 × 1.67 × 10−27 × 5 × 106
𝑝 = √2 × 9.1 × 10−31 × 0.5 × 103 × 1.6 × 10−19

∆𝒙 ≥ 𝟔. 𝟒 × 𝟏𝟎−𝟏𝟓 m ⸫𝒑 = 𝟏. 𝟐𝟎𝟕 × 𝟏𝟎−𝟐𝟑 Ns

This distance is comparable to the size of the Now,

nucleus; hence, it can be accepted. ∆𝒑
% of uncertainty in momentum = × 100
𝒑
(b) For classical mechanical measurement; 1.06×10−24
= 1.207×10−23
× 100
m = 50 kg, v = 2 m/s
= 𝟖. 𝟖%
6.623 × 10−34
∆𝑥 ≥
4 × 3.142 × 50 × 2 Example 11. In a measurement of position
and momentum that involved an uncertainty
∆𝑥 ≥ 5.26 × 10−37 m
of 0.003%, the speed of an electron was
An uncertainty of this magnitude is beyond found to be 800 m/s. Calculate the
human detection; therefore, it can be corresponding uncertainty that arises in
neglected. determining its position.

Conclusion: From above inference we Data: Speed of electron, v = 800 m/s

conclude that, uncertainties are important for
Uncertainty in measurement of v = 0.003%
microscopic system, but negligible for
macroscopic system. To find: Uncertainty in the measurement of
position of electron, ∆𝑥 = ?
Example 10. The position and momentum of
an electron with energy 0.5 keV are Solution: Uncertainty in speed,
determined. What is the minimum 0.003
∆𝒗 = 800 × = 0.024 m/s
100
percentage of uncertainty in its momentum if
the uncertainty in measurement of its & uncertainty in momentum,
position is 0.5Å? (May 2022) ∆𝒑 = 𝑚 × ∆𝑣 = 9.1 × 10−31 × 0.024

Data: Energy of electron, = 2.184 × 10−32 kg m/s

E = 0.5 × 103 eV = 0.5 × 103 × 1.6 × 10−19 J As per Heisenberg's uncertainty principle,
ℎ
Maximum uncertainty in position, ∆𝑥 ≥
4𝜋∆𝑝
∆𝒙 = 0.5Å = 0.5 × 10−10 m 6.623 × 10−34
∆𝑥 ≥
To find: Minimum percentage of uncertainty 4 × 3.142 × 2.184 × 10−32
in momentum = ?
∆𝒙 ≥ 𝟐. 𝟒 × 𝟏𝟎−𝟑 m
Solution: We have the uncertainty principle as,
ℎ ℎ Example 12. In a measurement of position
∆𝑥 ∆𝑝 ≥ or ∆𝑝 ≥
4𝜋 4𝜋∆𝑥 and velocity of an electron moving with a
6.623 × 10−34 speed of 𝟔 × 𝟏𝟎𝟓 m/s, calculate the highest
→ ∆𝑝 ≥
4 × 3.142 × 0.5 × 10−10 accuracy with which its position could be
determined if the inherent error in the
∆𝒑 ≥ 𝟏. 𝟎𝟔 × 𝟏𝟎−𝟐𝟒

Dr. Vinay Parol, Assistant Professsor, BIET, Davangere 13

Module-I Quantum Mechanics
measurement of its velocity is 0.01% for the Width of the spectral line (also means
speed stated. uncertainty in the wavelength value),
𝜟𝝀 = 5461 × 10−10 × 10−4 ≈ 10−14
Data: Speed of electron, v = 6 × 105 m/s
Uncertainty involved in measurement of v = 0.01% To find: The minimum time spent by the
electrons in the upper state, = ?
To find: Best accuracy with which the position ℎ𝑐
Solution: We have equation, 𝐸 = ℎ𝜗 =
could be measured, ∆𝒙 = ? 𝜆
1 𝛥𝜆
Solution: Uncertainty in speed, 𝛥𝐸 = ℎ𝑐 𝛥 (𝜆) = ℎ𝑐 ( 𝜆2 ) (1)
0.01
∆𝒗 = 6 × 105 × 100 = 60 m/s (Ignore negative sign)

From Heisenberg’s Uncertainty principle, As per uncertainty principle,

ℎ ℎ
ℎ ∆𝐸 ∆𝑡 ≥ → ∆𝑡 ≥ (2)
∆𝑥 ≥ 4𝜋 4𝜋∆𝐸
4𝜋𝑚∆𝑣
Using eqn (1), the eqn (2) becomes,
6.623 × 10−34
∆𝑥 ≥
4 × 3.142 × 9.1 × 10−31 × 60 ℎ𝜆2 𝜆2
∆𝑡 ≥ =
4𝜋ℎ𝑐𝛥𝜆 4𝜋𝑐𝛥𝜆
∆𝒙 ≥ 𝟗. 𝟔𝟓 × 𝟏𝟎−𝟕 m
(5461 × 10−10 )2
∆𝑡 ≥
Example 13. The inherent uncertainty in the 4 × 3.142 × 3 × 108 × 10−14
measurement of time spent by Iridium-191
nuclei in the excited state is found to be ∆𝒕 ≥ 𝟎. 𝟖 × 𝟏𝟎−𝟖 sec
𝟏. 𝟒 × 𝟏𝟎−𝟏𝟎 s. Estimate the uncertainty that Example 15. The speed of electron is
results in its energy a in the excited state.
measured to within an uncertainty of 2 × 104
Data: Uncertainty in life time in the excited ms−1 in one dimension. What is the minimum
width required by the electron to be confined
state, ∆𝑡 = 1.4 × 10−10 𝑠
in an atom? (Model QP2)
To find: Uncertainty in the energy of the nuclei
Solution: From Heisenberg’s uncertainty
in the excited state, ∆𝑬 = ?
principle,
Solution: We have the equation for ℎ
∆𝑥 ∆𝑃𝑥 ≥
uncertainty in energy and time as, 4𝜋
ℎ ℎ
∆𝐸 ∆𝑡 ≥ or ∆𝐸 ≥ But, P = mv → ∆𝑃𝑥 = 𝑚 ∆𝑣
4𝜋 4𝜋∆𝑡

6.623 × 10−34 ℎ
∆𝐸 ≥ ∴ ∆𝑃𝑥 ≥
4 × 3.142 × 1.4 × 10−10 4𝜋 𝑚 ∆𝑣
6.625 × 10−34
3.77×10−25 ≥
∆𝐸 ≥ 3.77 × 10−25 J ≥ 4𝜋 × 9.1 × 10−31 × 2 × 104
1.6×10−19

∆𝑬 ≥ 𝟐. 𝟑𝟓 × 𝟏𝟎𝟔 𝐞𝐕 ≥ 𝟐. 𝟑𝟓 MeV ∆𝑥 = 0.028 × 10−7 𝑚

∆𝒙 = 𝟐. 𝟖 × 𝟏𝟎−𝟗 𝒎 = 2.8 nm
Example 14. A spectral line of wavelength
5461 Å has a width of 𝟏𝟎−𝟒 . Evaluate the
minimum time spent by an electron in the
upper energy state.

Data: Wavelength, 𝝀 = 5461 𝑥 10−10 m

Dr. Vinay Parol, Assistant Professsor, BIET, Davangere 14

Module-I Quantum Mechanics
Energy Eigen value of Particle in 1-D 𝑛2 ℎ2
𝐸𝑛 =
Potential well 8𝑚𝑎2
for n = 1, 2 and 3 correspond to
Example 16. An electron is bound in a one-
𝐸1, 𝐸2 𝑎𝑛𝑑 𝐸3
dimensional potential well of the width 1 Å,
but of infinite wall height. Find its energy 𝑛2 ℎ 2 (6.63𝑥 10−34 )2
𝐸1 = =
values in the ground state, and also in the first 8𝑚𝑎2 8(9.11𝑥 10−31 )(0.12×10−9 )2

two exited states. 𝑬𝟏 = 𝟐𝟔. 𝟏𝟔 𝒆𝑽

Data: width of potential well, 𝒂 = 1 Å = 10−10 𝑚 𝑬𝟐 = 4 𝐸1 = 4 × 26.16 = 𝟏𝟎𝟒. 𝟔𝟏 𝐞𝐕

To find: Values of energy of the electron in the
𝑬𝟑 = 9 𝐸1 = 9 × 26.16 = 𝟐𝟑𝟓. 𝟒𝟒 𝒆𝑽
ground and the first two exited states
i.e., 𝑬𝟏 = ?, 𝑬𝟐 = ? , 𝑬𝟑 = ?, Example 18. An electron is trapped in a 1-
Solution: The energy of the electron in 1D dimensional potential well of infinite height
infinite potential well is, of width 0.5 nm. If transition takes place from
the first excited state to the ground state,
𝑛2 ℎ2 then find the wavelength of photon emitted.
𝐸𝑛 =
8𝑚𝑎2
Data: width, 𝒂 = 0.5𝑛𝑚 = 0.5 × 10−9 𝑚
where the values of E that we get for n = 1, 2
and 3 correspond to 𝐸1, 𝐸2 𝑎𝑛𝑑 𝐸3 To find: Wavelength of photon emitted, 𝝺=?

𝑛2 ℎ 2 (6.63𝑥 10−34 )2
Solution: The energy of the electron in 1D
𝐸1 = = infinite potential well is,
8𝑚𝑎2 8(9.11𝑥 10−31 ) (10−10 )2

𝑬𝟏 = 𝟔. 𝟎𝟑𝟏𝟒 × 𝟏𝟎−𝟏𝟖 𝑱 = 𝟑𝟕. 𝟔𝟒 𝒆𝑽 𝑛2 ℎ2

𝐸𝑛 =
22 ℎ2 ℎ2 8𝑚𝑎2
𝑬𝟐 = = 22 [ ] = 4 𝐸1
8𝑚𝑎2 8𝑚𝑎2 for n = 1, the ground state energy

𝑛2 ℎ 2 (6.625𝑥 10−34 )2
𝑬𝟐 = 𝟒 × 𝟔. 𝟎𝟑𝟏𝟒 × 𝟏𝟎−𝟏𝟖 𝑱 = 𝟏𝟓𝟎. 𝟓𝟒 𝐞𝐕 𝐸1 = =
8𝑚𝑎2 8(9.11𝑥 10−31 ) (0.5×10−9 )2

32 ℎ2 2
ℎ2 −19
𝐸3 = = 3 [ ] = 9 𝐸1 𝑬𝟏 = 2.41 × 10 = 𝟏. 𝟓𝟎𝟕 𝒆𝑽
8𝑚𝑎2 8𝑚𝑎2
𝑬𝟑 = 𝟗 × 𝟔. 𝟎𝟑𝟏𝟒 × 𝟏𝟎−𝟏𝟖 𝑱 = 338.7 eV for n = 2, the first excited state energy

Example 17. An electron is bound in a one- 𝑬𝟐 = 4 𝐸1 = 4 × 1.507 = 𝟔. 𝟎𝟐𝟓 𝐞𝐕

dimensional potential well of infinite height
of width 0.12 nm. Find its energy values in the Energy difference,
ground state, and also in the first two exited ∆𝑬 = 𝐸2 − 𝐸1 = 6.025 − 1.507 = 4.52 𝑒𝑉
states. ∆𝑬 = 𝟕. 𝟐𝟑 × 𝟏𝟎−𝟏𝟗 J
Data: width, 𝒂 = 0.12𝑛𝑚 = 0.12 × 10−10 𝑚
Wavelength of photon emitted,
To find: Values of energy of the electron in the
ℎ𝑐 6.625 × 10−34 × 3 × 108
ground and the first two exited states 𝜆 = =
∆𝑬 7.23 × 10−19
i.e., 𝑬𝟏 = ?, 𝑬𝟐 = ? , 𝑬𝟑 = ?,
𝝀 = 𝟐𝟕𝟒. 𝟖 𝒏𝒎
Solution: The energy of the electron in 1D
infinite potential well is,

Dr. Vinay Parol, Assistant Professsor, BIET, Davangere 15