Introduction to Quantum Mechanics Unit I & II 2016

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.

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
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.

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 looses
energy and momentum which results in an increased wavelength
for the electrons.
𝑕
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 𝑚𝑒𝑐
is termed as the Compton wavelength and is a constant =2.42 x 10-12 m.

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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.

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= where mv is the momentum of the particle.
𝑚𝑣

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
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”. If the unusual scattering at 50 degrees from the incident direction has to be explained

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 representation (mathematical) 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

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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.

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 𝑑 𝑣𝑝
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 can be

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

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𝑑𝑣𝑝 1 𝑑𝜆
= This on integration yields ln 𝑣𝑝𝑕 ∞ ln 𝜆 or 𝑣𝑝𝑕 ∞ 𝜆
𝑣𝑝 𝑕 2 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

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

where ∆𝑥 is the uncertainty in the position and ∆𝑝 is the uncertainty in the momentum determined
simultaneously.

The uncertainty relation for energy E and time t for a physical system can be written as

∆𝐸. ∆𝑡 ≥ ℏ/2

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

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

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.

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 light 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 minimum momentum gained by the electron in the x direction would be
𝑕
𝑝𝑥 ≈ ± 𝜆 sin 𝜃.

𝑕
Thus the minimum momentum of the electron would be uncertain by a factor ∆𝑝𝑥 ≈ 2 𝜆 sin 𝜃

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 using a well behaved function 𝜓(𝑥, 𝑦, 𝑧, 𝑡). Acceptable
functions 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 normalizable. i.e . −∞
 𝑑𝑉 = 1

Probability density

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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.

Young’s double slit experiment with electrons

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(𝐸𝑡−𝑘𝑥 ) .
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.

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𝑑2𝜓 𝑖𝑝
Differentiating the above yields 𝑑𝑥2
= (− ℏ )2 𝜓

ℏ2 𝑑 2 𝜓 𝑝2
Rearranging the terms and dividing by 2m we get − 2𝑚 𝑑 𝑥 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

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(𝐸𝑡−𝑝𝑥 )

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 𝑑 2
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

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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(𝑘𝑥 ) 𝐴𝑒 ℏ(𝐸𝑡) = 𝜓 𝑥 . 𝜙(𝑡)
𝑖 𝑖
where 𝜓 𝑥 = 𝐴𝑒 −ℏ(𝑘𝑥 ) 𝑎𝑛𝑑 𝜙 𝑡 = 𝑒 ℏ(𝐸𝑡)
ℏ2 𝑑 2 𝜓 𝑥 .𝜙(𝑡) 𝑑𝜓 𝑥 .𝜙(𝑡)
substituting in eqn (2) we get − 𝑖ℏ − 𝑉𝜓 𝑥 . 𝜙(𝑡) = 0
2𝑚 𝑑𝑥 2 𝑑𝑡

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.
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.

Numericals

1. Find the de Broglie wavelength of electrons moving with a speed of 107 m/s
2. Compare the momenta and energy of an electron and photon whose de Broglie wavelenth is
540nm
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.
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
the average kinetic energy of hydrogen atoms under thermal equilibrium at 293K?
6. In the Davisson & Germer experiment electrons accelerated at 180V are found to undergo
fourth order diffraction at 55o. Find the inter planar distance which produces the diffraction
maximum.
7. The frequency of Surface tension waves in shallow water is given by ν= (2πT/ρλ3)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.
8. 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.
9. 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.
10. 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.
11. 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.

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12. Electrons with energies of 0.400 eV are incident on a barrier 3.0 eV high and 0.100 nm wide.
Find the probability for these electrons to penetrate the barrier.
13. A beam of electrons is incident on a barrier 6.0 eV high and 2 nm wide. Find the energy of the
electrons if 1% of the electrons are to get through the barrier.
14. An electron and a proton with the same energy E approach a potential barrier whose height U
is greater than E. Comment on their tunneling probability.
15. Find the normalisation constant B for the wave function Ψ - B[sin(πx/L)+sin(2πx/L)]
16. Show that the probability of finding a particle trapped in an infinite potential well between x
and x+Δx is approx Δx/L and is independent of x.
17. Find the probability that a particle in a box of width L can be found between 0 and L/n when
the particle is in the nth state
18. A particle in an infinite potential well of width a. Find the probability of finding the particle
between a/3 and 2a/3 in the ground and third excited states.
19. What is the minimum energy of an electron trapped in a one dimensional region the size of an
atomic nucleus (1 x 10-14 m)
20. Find the energy required to excite a particle in a box of width a from the second excited state
to the fifth excited state

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