Introduction to Quantum Mechanics Unit I 2018

Dual nature of radiation

Radiation is part of the electromagnetic spectrum and can be described as electromagnetic waves.
Electromagnetic waves are construed as mutually perpendicular sinusoidal electric and magnetic
fields and perpendicular to the direction of propagation of the waves. The classical concept assumed
that the energy content of the wave is proportional to the square of the amplitude of the waves. The
wavelength (and hence the frequency) are not of any consequence with regard to the energy of the
wave. Conventional wave theory of radiation explains the phenomena of reflection, refraction,
interference, diffraction and polarization of light. Interference and diffraction though stands out as an
exclusive wave property.

Black body radiation in equilibrium

Gustav Robert Kirchhoff studied the absorption properties of materials and found materials which
absorb all incident rays. They concluded that when such a material is heated then it would emit all
wavelengths of radiation as it absorbed. Such a material is defined as a black body.

A black body is also modeled as a cavity which does not allow any
incident radiation to escape due to multiple reflections inside the
cavity. This cavity when heated radiates emit radiation of every
possible frequency at a rate which increases with temperature of the
body. The amount of radiant energy does not increase monotonically
with time but is limited by the rate at which the radiation is also
absorbed by the cavity. The amount of energy emitted at a frequency
shall be limited by the thermodynamic equilibrium of the absorption
and emission processes. It was also observed that the radiation
density in an equilibrium state depends only on the temperature of
the walls of the cavity and does not depend on the material
or structure of the wall.

The energy density of radiations can be estimated if the

number oscillators and their average energy can be
estimated. In the case of a spherical cavity we can estimate
the number of oscillators with frequencies between
𝟖𝝅𝑽 𝟐
𝝂 𝒂𝒏𝒅 𝝂 + 𝜹𝝂 as 𝒅𝑵 = 𝝂 𝒅𝝂 .
𝒄𝟑

The average energy of the oscillators can be evaluated

using the Maxwell Boltzmann distribution law for the large
number of harmonic oscillators with different frequencies.

The estimate by Rayleigh and Jeans of this resulted in an average energy 𝐸 = 𝑘𝐵 𝑇.

This results in the expression for the energy density (energy per unit volume) of radiations with
𝟖𝝅
frequencies between 𝝂 𝒂𝒏𝒅 𝝂 + 𝜹𝝂 as 𝝆 𝝂 𝒅𝝂 = 𝑬 𝒅𝑵 = 𝟑 𝝂𝟐 𝒅𝝂𝑘𝐵 𝑇 .
𝒄

This is the Rayleigh Jeans law which is in contradiction with the experimental observations. Thus
treating EM waves as classical oscillators fails to explain the experimental observations where the
intensity of radiations were found to increase with increase in wavelength upto a certain value and
decrease on further increase in the wavelength. The wavelength at which the intensity becomes a

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maximum is found to shift to lower temperatures as the temperature of the blackbody increase.
(which is the Wien’s displacement law).

A solution to this problem was provided by Max Planck in 1900 when he proposed that the energy of
the harmonic oscillator are restricted to multiples of the fundamental natural frequency 𝜈 times a
constant (𝑕 = 6.6𝑥10−34 𝐽𝑠) ie., 𝑬 = 𝒏𝒉𝝂. Thus the radiations are from a collection of harmonic
oscillators of different frequencies and the energy of the radiations from the oscillators has to be
packets of 𝒉𝝂.

With this concept of energy of the radiations the average energy of the oscillators can be evaluated
−𝒉𝒗
𝒉𝝂∗𝒆 𝒌𝑻
as 𝐸 = −𝒉𝒗 and the energy density of radiations can be evaluated as
𝟏− 𝒆 𝒌𝑻

𝟖𝝅 𝟐 𝒉𝝂 𝟖𝝅𝒉𝝂𝟑 𝟏
𝝆 𝝂 𝒅𝝂 = 𝑬 𝒅𝑵 = 𝟑
𝝂 𝒅𝝂 𝒉𝒗
= 𝟑 𝒉𝒗
𝒅𝝂
𝒄 𝒆 𝒌𝑻 − 𝟏 𝒄 𝒆 𝒌𝑻 − 𝟏
The decrease in the intensity at higher frequencies (smaller wavelengths) can be attributed to the fact
that the excitation of the oscillators to the higher energy states is less probable at lower temperatures.
At higher temperatures the thermal energy 𝑘𝑇 enables oscillations at higher frequency 𝑛𝝂. This
expression gives excellent co-relation with experimental results which was a milestone. At very low
frequencies this expression reduces to the Rayleigh Jeans expression.

Thus Max Planck had unknowingly laid the foundation for quantization of energy states of a system
though not in the currently understood terminologies.

Atomic Spectra

Atoms of different elements have distinct spectra and therefore atomic spectroscopy allows for the
identification and quantization of a sample's elemental composition. Robert Bunsen and Gustav
Kirchhoff discovered new elements by observing their emission spectra. Atomic absorption lines are
observed in the solar spectrum and referred to as Fraunhofer lines after their discoverer. Classical
physics tried to model the emission from atoms as that due to the orbiting electron, since an
accelerated charge should emit electromagnetic radiation --- light. However according to this model
the electron should be continually losing energy and fall into the atom.

(The explanation of the line spectrum of atoms in terms of transition between energy states of an
atom evolved after the quantum model of the atom evolved.)

Compton effect :

Arthur H Compton while studying the scattering of X rays by materials observed that in addition to the
emission of an electron, the scattered beam has a different wavelength as compared to the incident
wavelength.

The scattering of X rays (the high energy end of the

electromagnetic spectrum) if treated classically would not
explain the origin of X rays of higher wavelength.

Compton treated the problem as a particle -particle collision

𝑕
in which photons of momentum 𝑝𝑖 = 𝜆 are scattered with an
𝑖
electron at rest. This results in a transfer of momentum and
energy to the electron which is scattered. The photon loses
energy and momentum which results in an gain in
momentum and energy for the electrons. The scattered X-
ray photon has reduced energy which results in an increase

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in the wavelength.

The analysis of the conservation of energy and momentum conservation before and after the collision
(taking into consideration the relativistic effects for the energy and momentum of the electron) gives
the increase in the wavelength of the scattered photon.
𝑕
The change is the wavelength was calculated as 𝜆𝑓 − 𝜆𝑖 = Δ𝜆 = 𝑚 1 − cos 𝜃 . It is obvious that the
𝑒𝑐
Compton shift Δ𝜆 is independent of the incident wavelength of X rays and dependents only on the
scattering angle.
𝑕
The term is termed as the Compton wavelength and is a constant =2.42 x 10-12 m.
𝑚𝑒𝑐

These results were verified with the experimental observations. Thus the Compton Effect also proved
the particle nature of radiation.

These two experiments led to the conclusion that radiation can behave like a particle at times and
show the normal wave characteristics at other times.

Single photon scattering at a double slit

A double slit experiment with a particles incident on

the slits one at a time reveal some interesting
outcomes. Experiments show that electrons (or
photons) as particles are expected to arrive at some
definite location on a screen, unlike a wave. But if a
second electron (or photons) is incident at the slit,
the second electron reaches a different location,
often far outside any experimental uncertainty. If
many electrons (or photons) are incident on the slit
but one at a time then the measurements will display
a statistical distribution of locations that appears like
an interference pattern.

The building up of the diffraction pattern of electrons

scattered from a crystal surface. Each electron arrives
at a definite location, which cannot be precisely
predicted. The overall distribution shown at the bottom
can be predicted as the diffraction of waves having
the de Broglie wavelength of the electrons.

This experiment leads to concept of probabilities that

are inherent in quantum mechanical systems. A
quantum particle exhibits probabilistic behavior when
there is no effort to detect the particle.

Dual nature of matter

De Broglie put forward the hypothesis that matter (form of energy) when in motion can display wave
characteristics and the wavelength associated with the moving particle
𝑕
𝜆= 𝑚𝑣
where mv is the momentum of the particle.

Common heavier particles have a wavelength that is beyond the measurement capabilities with the
best of techniques available. For example the wavelength of a carbon atom moving with a velocity of

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100m per second could possess a wavelength of the order of 10-10m. This has to be measured with
an experiment characteristic of waves such as diffraction or interference.

The wavelength of the associated waves has to be in the measureable range of an interference or
diffraction experiment.

This concept was verified by Davisson and Germer who observed unusual scattering characteristics
for electrons scattered by a Ni crystal when the accelerating potential was 54V and angle of
scattering 50o.

The de Broglie wavelength of electrons accelerated by 54V can be estimated to be 1.67 x 10-10m. If
the electron wave possess such a wavelength, it should be possible to diffract the waves with a
known crystal.

If the scattering has to be explained as a diffraction phenomena (characteristics of waves) following

Bragg’s law, then 2𝑑 sin 𝜃 = 𝑛𝜆 where d in the interplanar distance of the Ni crystal, 𝜃 the glancing
angle (angle between the incident ray and the surface of the crystal) and 𝜆 is the wavelength of the
“waves”.

This yields a wavelength which is close to the value obtained using de Broglie’s hypothesis (matter
waves). Since diffraction is characteristic of waves, it was concluded that electrons undergo
diffraction under the set experimental conditions.

Thus it is concluded that matter display dual characteristics at appropriate conditions of interaction.
This concept has been further confirmed by diffraction experiments using heavier particles such as
the neutrons.

Wave packets

The concept of matter waves requires a wave like (mathematical) representation of the moving
particle where position and momentum of the particle can be estimated with reasonable accuracy.
Sinusoidal representations result in a gross uncertainty in the position while providing an highly
accurate estimation of the momentum.

The superposition of two waves of very close frequency and

propagation constant results in a wave packet, frequency 𝜔 + 𝛥𝜔
and propagation constant 𝑘 + 𝛥𝑘. Let y1 be a sinusoidal wave
with angular frequency ω and propagation constant k and y2 be a

wave with frequency 𝜔 + 𝛥𝜔 and propagation constant k+Δk.

𝑦1 = 𝐴sin⁡
(𝜔𝑡 + 𝑘𝑥) and

𝑦2 = 𝐴 sin{ 𝜔 + Δ𝜔 𝑡 + 𝑘 + Δ𝑘 𝑥}

The superposition of the two waves gives a resultant

Δ𝑤𝑡 +Δ𝑘𝑥
𝑦 = 𝑦1 + 𝑦2 = 2𝐴𝑠𝑖𝑛 𝑤𝑡 + 𝑘𝑥 . cos⁡
{ }
2

The first part is the original high frequency component and the second term is a low frequency
component. This is the case of an amplitude modulated wave where the amplitude of the high
frequency component is modulated according to the amplitude of the low frequency component.

This forms a wave packet which gives a reasonably accurate value of both momentum and position.
The momentum is derived from the wavelength of the high frequency component and the position
from the region of maximum amplitude.

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We can define both a phase and group velocity for the wave packet.

The phase velocity of the waves is defined as the velocity of an arbitrary point marked on the wave
𝝎
and is given be 𝒗𝒑 = 𝒌

𝒅𝝎
Group velocity is defined as the velocity of the wave packet (wave group) and is given by 𝒗𝒈 = .
𝒅𝒌

Relation between group velocity and particle velocity

𝑑𝜔
Group velocity of waves = 𝑣𝑔 =
𝑑𝑘
𝐸 𝑑𝐸
The angular frequency 𝜔 = where E is the energy of the wave and hence 𝑑𝜔 =
ℏ ℏ
𝑝 𝑑𝑝
The wave vector 𝑘 = where p is the momentum and hence 𝑑𝑘 =
ℏ ℏ
𝑑𝜔 𝑑𝐸
Therefore the group velocity 𝑣𝑔 = =
𝑑𝑘 𝑑𝑝
𝑝2 𝑑𝐸 𝑝
Since 𝐸 = the group velocity 𝑣𝑔 = = = 𝑣 where v is the particle velocity.
2𝑚 𝑑𝑝 𝑚

Relation between group velocity and phase velocity

𝑑𝜔 𝑑 𝑑𝑣𝑝
The group velocity of the particle is given by 𝑣𝑔 = 𝑑𝑘
= 𝑑𝑘
𝑣𝑝 . 𝑘 = 𝑣𝑝 + 𝑘 𝑑𝑘

𝑑𝑣𝑝 𝑑𝑣𝑝 𝑑𝜆
However
𝑑𝑘
= . .
𝑑𝜆 𝑑𝑘

𝑑𝜆 2𝜋 2𝜋 𝑑𝑣𝑝 𝑑𝑣𝑝
And = − hence 𝑣𝑔 = 𝑣𝑝𝑕 − = 𝑣𝑝𝑕 − 𝜆
𝑑𝑘 𝑘2 𝑘 𝑑𝜆 𝑑𝜆

Thus the group velocity of the wave packet is different in a dispersive medium (where the velocity of
the waves depends on the wavelength) and is equal to the phase velocity in a non dispersive
medium.

Evalute the condition under which the group velocity of a wave packet is

i) half the phase velocity and ii) twice the phase velocity
𝑑𝑣𝑝
The group velocity of a wave packet is given by 𝑣𝑔 = 𝑣𝑝𝑕 − 𝜆
𝑑𝜆

Case 1. 𝑣𝑔 = 𝑣𝑝𝑕 /2
𝑑𝑣𝑝 1 𝑑𝜆
𝑣𝑝 𝑕
= 2 𝜆
This on integration yields ln 𝑣𝑝𝑕 ∞ ln 𝜆 or 𝑣𝑝𝑕 ∞ 𝜆

This implies that the phase velocity is proportional to the square root of the wavelength

Case 2. 𝑣𝑔 = 2𝑣𝑝𝑕
𝑑𝑣𝑝 𝑑𝜆 1
𝑣𝑝 𝑕
= − 𝜆
This on integration yields ln 𝑣𝑝𝑕 ∞ ln λ
or 𝑣𝑝𝑕 ∞ 𝜆−1

This implies that the phase velocity is inversely proportional to the wavelength.

Uncertainty principle

Heisenberg’s analysis of the wave packet revealed the spread in the estimation of the position and
the spread in the propagation constant of the wave is intrinsically related. A Fourier transform of the
wave functions gives the distribution of the propagation constant. In summary he product of the
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standard deviations in the estimates of the position and the propagation constant was shown to be
1
greater than or at the most equal to 2. 𝑖𝑒. , ∆𝑥. ∆𝑘 ≥ 1/2
This then translates to the standard form of the uncertainty principle when the propagation constant is
transformed to the momentum through the relation
𝑝 = ℏ𝑘
The position and momentum of a particle cannot be determined
simultaneously with unlimited precision. If one of the parameter
is determined with high precision then the other must
necessarily be imprecise, such that the product of the
uncertainties is greater than or equal to ℏ/2 ie.,
∆𝑥. ∆𝑝 ≥ ℏ/2 The more precisely
where ∆𝑥 is the uncertainty in the position and ∆𝑝 is the the position is determined, the
uncertainty in the momentum determined simultaneously. less precisely the momentum is
known in this instant, and vice
The uncertainty relation for energy E and time t for a physical versa.
system can be written as Heisenberg, uncertainty paper,
∆𝐸. ∆𝑡 ≥ ℏ/2
1927
Where ∆𝐸 is the uncertainty in the energy E of a system and ∆𝑡
is the uncertainty in the time in which this energy is estimated.

In the case of rotational motion the uncertainty relation between the angular position θ and the
angular momentum L can be written as
∆𝜃. ∆𝐿 ≥ ℏ/2
where ∆𝜃 is the uncertainty in the angular position and ∆𝐿 is the uncertainty in the angular momentum
determined simultaneously.

Electron’s existence inside the nucleus

The uncertainty principle can be used to illustrate the impossibilities in physical systems or the
correctness of assumptions. Beta particle emission from radioactive nuclei is one such example.
Experiments show that the beta emission is the emission of an electron with a high energy of about
4MeV by radioactive nuclei. If we assume the electron to be an integral part of the nucleus then we
may be able to estimate the minimum energy of the electron using the uncertainty principle.

If the electron is part of the nuclei, then the position of the electron is uncertain to the extent of the
nuclear diameter. The the uncertainty in the position of an the electron
∆𝑥 ≈ 10−14 𝑚
The minimum uncertainty in the momentum of the electron then can be estimated as
ℏ
∆𝑝 = = 5.28 × 10−21 𝑘𝑔𝑚𝑠 −1
2. ∆𝑥
Hence the minimum momentum of the electron p has to be at least the uncertainty ∆𝒑 and hence

𝑝2 ∆𝑝 2 1 ℏ 2
The kinetic energy of the electron 𝐸 = = = ≈ 96 𝑀𝑒𝑉
2𝑚 2𝑚 2𝑚 2.∆𝑥

This implies that the energy of the electron emitted by the radioactive nuclei should be quite high if
electron had to be integral member of the nuclei. Since the energies of the electron emitted by
radioactive nuclei are very less compared to the estimate, we conclude that the electron cannot be a
permanent part of the nuclei, thus illustrating the power of the uncertainty principle.

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Heisenberg’s Gamma ray microscope:

Heisenberg proposed the gamma ray microscope (as a thought experiment

to illustrate the uncertainty principle) to locate the position of an electron. To
be able to “observe” the electron, it should be “illuminated” by a radiation
whose wavelength is comparable to the size of the scattering object. Hence
it is evident that one should use 𝛾 rays to observe electrons, which in turn
scatter the radiation onto the objective lens of the microscope. In order that
we “see” the electron, the limit of resolution of the microscope should be
comparable to the position uncertainty Δ𝑥.
𝜆
Thus we get Δ𝑥 ≈ sin 𝜃
.

However when the high energy 𝛾 rays can impart momentum to the electrons (following the principles
of Compton Effect).

The maximum momentum imparted to the electron can be estimated from the maximum shift in the
scattered photon momentum. If the momentum of the photons entering the microscope at a half cone
angle 𝜃 is 𝜆 then the maximum momentum gained by the electron in the x direction would be
𝑕
𝑝𝑥 ≈ ± sin 𝜃.
𝜆

𝑕
Thus the minimum momentum of the electron would be uncertain by a factor ∆𝑝𝑥 ≈ 2 sin 𝜃
𝜆
𝜆 𝑕 𝑕
Thus the product of the uncertainties ∆𝑥. ∆𝑝𝑥 ≈ sin 𝜃
∗ 2 𝜆 sin 𝜃 ≈ 2𝑕 > 4𝜋 which conforms to the
uncertainty principle.
This illustrates that in the simultaneous determination of the position and momentum of an electron
results in an inherent uncertainty.
Wave function

A moving particle can be represented by a wave packet. The wave packet can be described by a
function 𝜓(𝑥, 𝑦, 𝑧, 𝑡). All mathematical functions are not acceptable functions. The functions should
have the following characteristics:

(1)  must be finite, continuous and single valued in the regions of interest.

(2) The derivatives of the wave function must be finite, continuous and single valued in the regions of
interest.
+∞
(3)  must be normalisable. i.e. . −∞
 𝑑𝑉 = 1

The wave function 𝜓 satisfying the above conditions are called as well behaved functions.

Probability density

The function 𝜓 𝑥 though contains information about the physical state of the system has no physical
meaning. However since the amplitude of the wave gives information on the probable position of the
particle, 𝜓 𝑥 can be termed as the probability amplitude.

The square of the amplitude of the wave packet gives the intensity of the wave which in turn gives the
probability of finding the particle represented by the wave function. Thus the product 𝜓 ∗ 𝜓 gives the
probability density for any given x. The integration of the probability density over the entire interval
gives the total probability of finding the particle which should be equal to one.

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Linear superposition of wave functions

The classical Young’s double slit experiment with

light waves demonstrates the diffraction of light.
The experiment conceived photons passing
through two closely space slits diffract and forms
an interference pattern at the screen.

If the photon beam is replaced by an electron bean

then it is interesting to note that the electrons going
through the slit behaves as waves, and form an
interference pattern on the screen. If one on the
slit is closed, the electron wave still diffracts and the P1 gives the probability distribution of electrons
arriving from slit 1. Similarly with slit 1 closed and slit 2 open P2 gives the probability distribution of
electrons arriving from slit 2. When both slits are open and electrons arrive at the screen, an
interference pattern is observed as against the simple addition of the probability distributions. This
clearly demonstrates the wave behavior of electrons. If 𝜓1 represents the electrons passing through
slit 1 and 𝜓2 represents the electrons passing through slit 2, then

P1 = 𝜓1 2 𝑎𝑛𝑑 P2 = 𝜓2 2 . It is obvious that 𝜓3 = 𝜓1 + 𝜓2 represents the super imposition of the

two states or super imposition of the two wave functions. Thus P3 = 𝜓1 + 𝜓2 2 is not equal
to 𝜓1 2 + 𝜓2 2 .

Another interesting observation is that any attempt to observe the events of which or how many
electrons pass through each slit with a detector result in a collapse of the wave function 𝜓3 .

Observables,

The physical parameters associated with the particle such as energy, momentum, kinetic energy,
spin, etc are observables of the state of a system. Experimental results can give us values of
observables, and multiple measurements on the system at the same state should result in the same
value for the observables if the state of the system is not modified by the measurement. Observables
have real values and would be limited by the principles of uncertainty.

Operators
𝑖
The wave function describing a system in one dimension can be written as 𝜓 𝑥, 𝑡 = 𝑒 ℏ(𝑝𝑥 −𝐸𝑡) .
𝑑𝜓 𝑖𝑝
Differentiating 𝜓 with respect to position yields 𝑑𝑥
= ( ℏ )𝜓

𝑑 𝑑
Or the operation −𝑖ℏ 𝑑𝑥 𝑜𝑛 𝜓 yields the momentum of the system. 𝑝 = −𝑖ℏ 𝑑𝑥 is the momentum
operator.
𝑑2𝜓 𝑖𝑝
Differentiating the above yields = ( )2 𝜓
𝑑𝑥2 ℏ

ℏ2 𝑑 2 𝜓 𝑝2
Rearranging the terms and dividing by 2m we get − 2𝑚 𝑑𝑥 2 = 2𝑚 𝜓 = 𝐾𝐸𝜓

ℏ2 𝑑 2 ℏ2 𝑑 2
Thus the operation{− 2𝑚 𝑑𝑥 2 } on 𝜓 yields the kinetic energy. 𝐾𝐸 = {− 2𝑚 𝑑𝑥 2 } is the kinetic energy
operator
𝑑𝜓 𝑖𝐸
Differentiating 𝜓 with respect to time yields 𝑑𝑡
= (− ℏ )𝜓

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𝑑
Or the operation 𝑖ℏ 𝑑𝑡 𝑜𝑛 𝜓 yields the total energy of the system and 𝐸 is the total energy operator.

Expectation values:

Quantum mechanics deals with probabilities and hence predicts only the most probable values of the
observables of a physical system which are the expectation values. These expectation values could
be verified with repeated measurements on the system.

Let 𝑝 be an operator that gives the value of the momentum p when it operates on the wave function
𝜓.

The operation 𝜓 ∗ 𝑝𝜓 = 𝜓 ∗ 𝑝𝜓 = 𝑝𝜓 ∗ 𝜓 where p is the value of the observable extracted from 𝜓. If the
many values of p are extracted and the most probable value is expressed as an average, the same
can be obtained by integrating the expression which gives

𝜓 ∗ 𝑝𝜓 𝑑𝑉 = 𝜓 ∗ 𝑝𝜓 𝑑𝑉 = 𝑝 𝜓 ∗ 𝜓 𝑑𝑉 where 𝐴 is the most probable value of the parameter A.

𝜓 ∗ 𝑝 𝜓 𝑑𝑉
This can be written as 𝑝 = .
𝜓 ∗ 𝜓 𝑑𝑉

In the general case for an operator 𝐴 when the integration is from -∞ 𝑡𝑜 + ∞ the denominator is equal
to 1 and hence the expectation value of the parameter 𝐴 can be written as
𝜓 ∗ 𝐴 𝜓 𝑑𝑉
𝐴 = 𝜓 ∗ 𝜓 𝑑𝑉
.

Schrodinger’s Wave equation

𝑖
The general form of the wave function is give by Ψ(𝑥, 𝑡) = 𝐴𝑒 ℏ(𝑝𝑥 −𝐸𝑡)
The total energy of the system = kinetic energy + potential energy
Ie E= KE + V
Multiplying throughout with 𝜓 𝑤𝑒 𝑔𝑒𝑡 𝐸Ψ = 𝐾𝐸Ψ + 𝑉Ψ ……… (1)
𝑑 ℏ2 𝑑2
The total energy operator is 𝑖ℏ 𝑑𝑡 , the kinetic energy operator is {− 2𝑚 𝑑𝑥 2 }.

replacing the terms with the respective operators we can rewrite the expression (1) as
𝑑Ψ ℏ2 𝑑2 Ψ
𝑖ℏ = − + 𝑉Ψ
𝑑𝑡 2𝑚 𝑑𝑥 2
ℏ2 𝑑 2 Ψ 𝑑Ψ
or + 𝑖ℏ − 𝑉Ψ = 0 ….(2)
2𝑚 𝑑𝑥 2 𝑑𝑡
which is the Schrödinger’s time dependent wave function since Ψ is a function of both position and
time. The solution of the differential equation yields the wave function which is the state function of
the system.
It the system is in the steady state then the wave function could be independent of time. In such a
𝑖 𝑖
case we can write the wave function as Ψ 𝑥, 𝑡 = 𝐴𝑒 ℏ(𝑝𝑥 ) 𝐴𝑒 −ℏ(𝐸𝑡) = 𝜓 𝑥 . 𝜙(𝑡)
𝑖 𝑖
where 𝜓 𝑥 = 𝐴𝑒 ℏ(𝑝𝑥 ) 𝑎𝑛𝑑 𝜙 𝑡 = 𝑒 −ℏ(𝐸𝑡)
ℏ2 𝜕 2 𝜓 𝑥 .𝜙(𝑡) 𝜕𝜓 𝑥 .𝜙(𝑡)
substituting in equation (2) we get + 𝑖ℏ 𝜕𝑡 − 𝑉𝜓 𝑥 . 𝜙(𝑡) = 0
2𝑚 𝜕𝑥 2
The total energy E of the system being a constant, the total energy operator can be replaced by the
value E with no loss of sense.

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ℏ2 𝑑 2 𝜓 𝑥 .𝜙 (𝑡)
+ 𝐸𝜓 𝑥 . 𝜙(𝑡) − 𝑉𝜓 𝑥 . 𝜙(𝑡) = 0
2𝑚 𝑑𝑥 2
ℏ2 𝑑2 𝜓 𝑥 .
or { 2𝑚 𝑑𝑥2
+ 𝐸𝜓 𝑥 − 𝑉𝜓 𝑥 }. 𝜙(𝑡) = 0
We recognize that 𝜙(𝑡) ≠ 0 and hence
ℏ2 𝑑 2 𝜓 𝑥 .
+ 𝐸𝜓 𝑥 − 𝑉𝜓 𝑥 = 0 ………………….(3)
2𝑚 𝑑𝑥 2
This is the Schrödinger’s time independent one dimensional wave equation. The solutions of the
Schrodinger’s wave equation yield the wave function 𝜓 𝑥 which has to be checked for continuities
at the boundaries and be normalized to get the exact wave function of the system.
[Three dimensional Schrodinger’s wave equation.
The Schrodinger’s wave equation for a 3D can be evolved by looking at the problem as three one
dimensional problem in the independent variables x,y and z. The wave function of such a system can
be written as
Ψ 𝑥, 𝑦, 𝑧 = 𝜓 𝑥 𝜓 𝑦 𝜓 𝑧 where 𝜓 𝑥 , 𝜓 𝑦 𝑎𝑛𝑑 𝜓 𝑧 are the three mutually independent wave
functions of the particles in the orthogonal co-ordinate system.
The derivatives of the wave function can be written as partial derivatives of the wave function.
The SWE then can be written as
ℏ2 𝜕 2 𝜕2 𝜕2
+ + Ψ 𝑥, 𝑦, 𝑧 + 𝐸 – 𝑉 Ψ 𝑥, 𝑦, 𝑧 = 0
2𝑚 𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2
which can be simplified as
ℏ2 2
∇ Ψ 𝑥, 𝑦, 𝑧 + 𝐸 – 𝑉 Ψ 𝑥, 𝑦, 𝑧 = 0
2𝑚
𝜕2 𝜕2 𝜕2
where ∇2 = 𝜕𝑥 2
+ 𝜕𝑦 2 + 𝜕𝑧 2 is the Laplacian operator
𝜕 𝜕 𝜕
∇2 = ∇. ∇ and the operator ∇= 𝑖 𝜕𝑥 + 𝑗 𝜕𝑦 + 𝑘 𝜕𝑧

]
[Linear superposition of wave functions from SWE.
ℏ2 d 2 ψ x .
The wave function 𝜓 𝑥 which is the solution of the differential equation 2m dx 2 + Eψ x − Vψ x =
0 is a state function. Since a system could have multiple states the solution of the wave equation
can give us multiple wave functions 𝜓 𝑥 . If 𝜓1 𝑥 represents a state 1 andf 𝜓2 𝑥 represents a state
2 of the system then it can be seen that a linear combination of 𝜓1 𝑥 and 𝜓2 𝑥 is also a solution of
the SWE. Thus 𝜓12 𝑥 = n. 𝜓1 𝑥 +m. 𝜓2 𝑥 will also be a solution of the SWE. It is obvious that the
superposition of two waves is a wave packet and can represent the state of a system.
It is also evident that the probability densities however do not add to give the probability density of the
new state and has to be estimated from the new wave function ]

[ Photo electric effect – an experiment in which radiation (electromagnetic waves) interact with
matter where emission of electron from the metal when radiation of wavelengths lesser than a cutoff
wavelength. The electron emission was instantaneous and the kinetic energy of the emitted
electrons depended only on the wavelength of the incident radiation and not on the intensity.

These results could not be explained on the basis of the classical EM wave theory. The classical
theory suggests that electrons accumulate of energy from the incident waves on continuous
irradiation and when the energy of the electrons is more than the work function of the material it is

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emitted from the metal after a delayed time. According to the classical theory the kinetic energy of
the electrons emitted should be dependent on the intensity of the radiation and independent of the
wavelength. All these explanations were in contradiction to the experimental results.

Einstein explained the effect considering light to behave as particles called Photons and the
interaction of the photons with the electrons in the metal can result in transfer of energy to the
electron. If the energy gained by the electron is greater than the work function of the metal, then the
electron can be emitted and the kinetic energy of the photo electron would depend on the energy of
the incident photon. This was a classic example of radiation displaying a particle nature when the
interaction is at atomic / sub atomic particles.]

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 Introduction to Quantum Mechanics Unit I 2018

Numericals

1. Find the de Broglie wavelength of electrons moving with a speed of 107 m/s (Ans 7.28 x 10-11 m)
2. Compare the momenta and energy of an electron and photon whose de Broglie wavelenth is
𝒉
650nm (Ans Ratio of momenta =1; ratio of energy of electron to energy of photon =𝟐𝒎𝝀𝒄 = 𝟏. 𝟖𝟔𝟕𝒙𝟏𝟎−𝟔 )
3. Calculate the de Broglie wavelength of electrons and protons if their kinetic energies are
i) 1% and ii) 5% of their rest mass energies. (Ans Rest mass energy of electron = 8.19x 10-14 J; rest
-10 𝒉
mass energy of protons = 1.503 x 10 J. The de Broglie wavelength 𝝀 = Electron 1%
𝟐𝒎𝑬
𝝀= 𝟒. 𝟎𝟎𝒙𝟏𝟎−𝟏𝟑 𝒎 Electron 5% 𝝀 = 𝟏. 𝟕𝟗𝒙𝟏𝟎−𝟏𝟑 𝒎 Proton 1% 𝝀 = 𝟐. 𝟏𝟕𝒙𝟏𝟎−𝟏𝟔 𝒎 Proton 5% 𝝀 =
𝟗. 𝟕𝟐𝒙𝟏𝟎−𝟏𝟕 𝒎)
4. An electron and a photon have a wavelength of 2.0 A. Calculate their momenta and total
energies.
5. What is the wavelength of an hydrogen atom moving with a mean velocity corresponding to
𝒉
the average kinetic energy of hydrogen atoms under thermal equilibrium at 293K? ( 𝝀 = 𝟑𝒎𝒌𝑻 =
𝟏. 𝟒𝟕𝒙𝟏𝟎−𝟏𝟎 𝒎 )
6. The frequency of Surface tension waves in shallow water is given by ν= (2πT/ρλ 3)½, where T
is the surface tension, ρ is the density of the medium and λ the wavelength of the waves. Find
the group velocity of the waves.
7. The relation between the wavelength λ and frequency ν of electromagnetic waves in a wave
guide is given by λ=c/√(ν2 - νo2). Find the group velocity of the waves.
8. The speed of an electron is measured to be 1 km/s with an accuracy of 0.005%. Estimate the
uncertainty in the position of the particle.
9. The spectral line of Hg green is 546.1 nm has a width of 10-5 nm. Evaluate the minimum time
spent by the electrons in the upper state before de excitation to the lower state .
ℏ 𝝀𝟐
(Ans: ∆𝒕 = = = 𝟕. 𝟗𝟏𝒙𝟏𝟎−𝟗 𝒔 )
𝟐.∆𝑬 𝟒𝝅𝒄𝚫𝝀

10. The uncertainty in the location of a particle is equal to it's de Broglie wavelength. Show that
the corresponding uncertainty in its velocity is approx one tenth of it's velocity. (Ans: ∆𝒑 =
ℏ 𝒉 𝒑 𝒗 𝒗 𝒗
= = Hence ∆𝒗 = = ≈ )
𝟐.∆𝒙 𝟒𝝅𝝀 𝟒𝝅 𝟒𝝅 𝟏𝟐.𝟓𝟔 𝟏𝟎
11. Determine the maximum wavelength shift in the Compton scattering of photons from protons.
(Ans = 2.64×10−5 Å)
𝜆2
12. Show that for a free particle the uncertainty relation can also be written as ∆𝑥. ∆𝜆 = | 4𝜋 |
where Δx is the uncertainty in location of the wave and Δλ the simultaneous uncertainty
in wavelength.
13. Discuss the following functions to be taken as acceptable wave functions:
2
2 2 𝑁𝑒 −𝑎 𝑥
i: 𝑁𝑒 𝑎𝑥 ii: 𝑁𝑒 𝑎𝑥 iii: 𝑁𝑒 −𝑎𝑥 iv: 5−𝑥
14. A wave function is given by 𝜓 𝑥 = 𝑁𝑒 𝑖𝑘𝑥 in the region 0 < 𝑥 < 𝑎 . Find the normalization constant
N.

https://www.youtube.com/watch?v=yy6TV9Dntlw

https://www.youtube.com/watch?v=EA-wcFtUBE4

https://www.youtube.com/watch?v=vkVnnN0MjIE

https://www.youtube.com/watch?v=cugu4iW4W54

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