____________________________________________________________________________________________________

Development Team
Prof. Vinay Gupta, Department of Physics and Astrophysics,
Principal Investigator University of Delhi, Delhi

Prof. V. S. Bhasin( Retired) from Department of Physics &

Paper Coordinator Astrophysics, University ofDelhi, Delhi-110007

Content Writer Prof. V.S.Bhasin (Retired) ,Department of Physics &

Astrophysics, University of Delhi,Delhi-110007

Content Reviewer

S ubject Physics

Paper No and Title Quantum Mechanics I

Module No and Title 1 Origin of Quantum Mechanics—Inadequacy of

Classical Laws of Mechanics and Electromagnetic
Radiation

Module Tag V S Bhasin

Subject Physics

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TABLE OF CONTENTS
1. Learning Outcomes

2. Introduction

3. Origin of Quantum Mechanics: Prominent Phenomena laying the

Foundations of Quantum Mechanics

3.1 Energy Spectrum in Black Body Radiation

3.2 Specific Heat of Solids at Very Low Temperatures

3.3 Photoelectric Effect

3.4 The Compton Effect

4. Summary

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1. Learning Outcomes (Times New Roman , size 14)

After studying this module, you shall be able to

 Learn how Planck proposed his idea of quantization of energy from the study of
spectral distribution of black body radiation
 Know Einstein’s extension of Planck’s hypothesis to resolve the paradox of the
behavior of specific heat of solids at very low temperatures
 Study Einstein’s generalization of photon picture of light to explain photo-
electric effect
 Learn how to deduce the expression for shift in wave length in Compton
Scattering of hard X-rays by elements of low atomic number

2. Introduction

Quantum Mechanics is considered as the fundamental theory describing the

phenomena of molecules, atoms and subatomic particles of matter. This subject evolved
as a result of striking observations from a number of experimental investigations carried
out in different areas of physics from the end of 19th century to the beginning of 20th
century. These observations could not be adequately explained on the basis of classical
laws of physics. Historically, by the end of 19th century, classical mechanics as
formulated by Newton and later developed by Hamilton and Lagrange was widely
believed and universally accepted as the ultimate theory of dynamics. Similar was the
status regarding the wave nature of light as established from the experiments on
interference, diffraction and polarization and later developed in the form of
electromagnetic theory of light by Clark Maxwell and confirmed by Hertz in 1887 as
electromagnetic waves produced by oscillating electric charges.
However, by the end of 19th century these classical theories were found inadequate to
explain a growing number of atomic phenomena. Attempts were being made to explore
the structure of matter and the nature of radiation and the interaction of radiation with
matter. As a result, the first quarter of the 20th century witnessed how the foundations of
physics were radically reexamined. In the present module we shall trace the history of
some prominent phenomena which point out the limitations of the laws of classical
mechanics when used to study microscopic phenomena in physics and show how these
were overcome first by Planck, Einstein and Bohr and later by Schrodinger and others.

3 Prominent Phenomena laying the Foundations of Quantum Mechanics

3.1 Energy Spectrum in Black Body Radiation

One of the earliest phenomena for which classical theory was unable to offer any
satisfactory explanation till the end of nineteenth century was the nature of the
continuous spectrum of black body radiation. We all know that when an object is heated
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up sufficiently so that it gets red hot, it emits light at the red end of the spectrum. Further
heating it causes the colour of the emitted light to change towards shorter wavelengths or
higher frequencies. Recall that a black body, by definition, is one which absorbs all the
electromagnetic radiation which is incident on it and reflects none. Such a body is a better
radiator at every frequency than any other at the same temperature. A perfect black body
does not exist. However, for practical purposes a black body is realized by creating a
small hole in the wall of the cavity in which radiation is admitted from outside. The
cavity contains radiation which is emitted by the walls of the cavity. The amount of
radiant energy in the cavity does not increase indefinitely with time. In fact, the process
of emission is opposed by the process of absorption. In the state of thermodynamic
equilibrium, the amount of energy, E(ν) dν in the frequency range between ν and ν+dν is
determined by the condition at which the rate of emission is balanced by the rate of
absorption for a given frequency. It has been demonstrated both experimentally and
𝒄
theoretically that at equilibrium the intensity distribution, I(ν)= E(ν), depends only on
𝟒𝝅
the temperature of the walls and is independent of the material of back body. Figure (1.1),
given below shows a plot of intensity distribution as a function of wavelength λ plotted
at different temperatures.

1.4
5000K

1.2 Classical Theory

(5000K)
1.0

Inten 0.8
sity
0.6

4000K
0.4

0.2 3000K

0.0
500 1000 1500 2000 2500 3000
Wavelength (nm)

Fig.(1.1): Plot of Intensity Distribution vs wavelength λ radiated by a black body at different

temperatures.

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The figure clearly depicts that intensity distribution first rises to a maximum and then
falls off as the wavelength is increased,- maxima of the distribution curves slightly
shifting towards the lower end of the wavelength as temperature increases.
These observations could not be completely accounted for by the attempts based
on classical ideas. Classically, the absorption and emission of radiation was considered to
be due to oscillating charges within the black body. It was assumed that in a black body
there are a large number of linear harmonic oscillators of all possible frequencies in
equilibrium with radiation at a given temperature. Based on these considerations, while
Wien suggested a semi-empirical theory which agreed only in the short wavelength limit,
Raleigh and Jeans, on the other hand, obtained a law which agreed at long wavelengths
limit but was in complete disagreement for short wavelengths. Thus, according to
classical electromagnetic theory, the expression for the energy density distribution, E(ν),
of a black body radiation can be expressed as
8 2
E ( )  u ( ) , (1.1)
c 3
2 3
where 8 / c is the number of electromagnetic oscillators per unit volume at
frequency ν in the range dν in equilibrium with the radiation in a black body cavity and
u(ν) represents the average energy of the oscillators. By ‘Law of Equi-partition of
Energy’, the mean energy of the oscillators with frequency ν is
u(ν)=k T , where k is the Boltzmann’s constant, and T is the absolute temperature. Thus
we get
8 2
E ( ) d  kT d
c3
or
8
E ( )d  k Td
 4
(1.2)

This is known as Rayleigh-Jean’s law, according to which the energy radiated in a given
wavelength range dλ increases indefinitely. This is depicted on the right hand side in the
plot in (Fig.1.1) for comparison. It also becomes clear from the above expression that the
total energy, E, becomes i.e.,

∞ 𝟖𝝅 ∞
E= ∫𝟎 𝑬(𝝂)𝒅𝝂 = 𝒌𝑻 ∫𝟎 𝝂𝟐 𝒅𝝂 (1.3)
𝒄𝟑

which goes to infinity as ν approaches infinite. This basic draw-back in classical theory is
often referred to as ‘ultra-violet catastrophe’.

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In 1900, Max Planck, the German physicist, came out with the revolutionary idea that
matter absorbs or emits radiation energy not continuously but rather in discrete quanta.
Assuming, as in classical theory, that a black body is composed of oscillators in
equilibrium with the radiation field, Planck postulated that an oscillator with
frequency ν can only take discrete values of energy quanta,∈𝒏 = 𝒏𝒉𝝂, where
n=0,1,2…….. and h is a constant which is now known as Planck’s constant having value
6.63 x𝟏𝟎−𝟑𝟒 joule sec.

To obtain the Planck’s expression for the intensity distribution, we start by writing
the mean energy per oscillator of frequency ν as

𝒖(𝝂) = ∑∞
𝒏=𝟎 ∈𝒏 𝑵𝝂 , (1.4)

where 𝑵𝝂 is the number of oscillators with energy ∈𝒏 in equilibrium with temperature T,

given by the classical Boltzmann expression, viz.,


N  exp(  n / kT ) /  exp( n / kT ),
n 0 (1.5)

Substituting this expression in the above equation for u, we have

 
u(ν)=  n exp( n / kT ) /  exp( n / kT ),
n 0 n 0 (1.6)

Note that


 exp( n / kT )  1  exp(h / kT )  exp(2h / kT )  ........
n 0
 [1  exp( h / kT )]1

Similarly, one can show that

 h exp( h / kT )
 n exp( n / kT ) 
n 0 [1  exp( h / kT )]2

Thus the expression for the mean energy per oscillator of frequency ν reduces to

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h exp( h / kT ) h
u ( )  
[1  exp( h / kT )] [exp(h / kT )  1]
(1.7)

𝟖𝝅𝝂𝟐
and the number of oscillators per unit volume, N(ν),being equal to we finally get
𝒄𝟑
Planck’s expression for the energy density of radiation,

8 2 h
E ( ) 
c 3 [exp(h / kT )  1] (1.8)

This expression not only explains the observed spectral distribution of a black body but
can also reproduce in the limiting case the Rayleigh-Jean’s law. One can also show that
the well-known Stefan’s law can also be obtained from this general result. Thus, for
example, in the low frequency or long wavelength limit, one can write

h
e h / kT  1 
kT

Substituting this in the above expression, Planck’s result reduces to the Rayleigh-Jean’s
expression. Also the total radiation density arising from all frequencies can be obtained
by integrating Planck’s energy distribution. i.e.,


8  5k 4 4
E   E ( ) d  T
15 c 3h3
0 (1.9)

which shows that energy density is proportional to the fourth power of absolute
temperature T. This is the result which was first suggested by Stefan in 1879 and is
known as Stefan’s law of radiation.

The success of the Planck’s distribution law based on the quantum hypothesis may
be regarded as the first step to look beyond classical laws for the understanding of
processes in at least some areas of physics.

It may be remarked here that for quantum effects to show an observable departure
of the mean energy u(ν) from its classical value kT ( Note here that from classical
considerations Boltzmann’s expression,

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  exp( ) d d 

 1
u ( )    exp(   ) d    kT
0

d  0  
 exp( ) d
0

reduces to kT) , the frequency should be high enough to get hν/kT comparable to unity.
For example at room temperature where T=𝟑𝟎𝟎 𝑲, the term hν/kT turns out to be of the
order of 1/5 for the value of ν= 𝟏𝟎𝟏𝟐 𝑯𝒛.

3.2 Specific Heats of Solids at Very Low Temperatures

In 1906 Einstein applied Planck’s hypothesis to another problem of classical

physics – the theory of specific heat of solids. It is well known that atoms in solids
execute oscillations about their mean positions due to thermal agitation. Each atom may
therefore be regarded as a three dimensional harmonic oscillator. The classical law of
‘Equi-partition of Energy’ demands that the mean thermal energy of such a three
dimensional oscillator in equilibrium at temperature T is 3kT per atom, or 3RT=3NkT
per gm atom ( comtaining N atoms where N is the Avagadro’s number; for one mol
N=6.025x𝟏𝟎𝟐𝟑 . Thus the mean energy of the solid, u=3NkT=3RT. This means that lattice
 u 
contribution to molar specific heat capacity is CV     3R  6cal / deg mole . Thus
 T V
classical theory predicts that the heat capacity per mole is the same for all
substances at all temperatures. Many solids obey this law at room temperature and
above but this prediction fails entirely at low temperatures. It is experimentally found
that heat capacity approaches zero as T→ 𝟎., as is shown in Fig.(1.2).

Fig.1.2 Plot of Specific Heat at constant volune vs. Temperature

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This puzzling problem of classical physics was resolved by Einstein following

Planck’s hypothesis. Assuming that a solid can be represented by a collection of
harmonic oscillators which can take only discrete energy values (nhν), where n is an
imteger and ν is the oscillator frequency, Einstein considered the simplest model where
all the oscillators have the same frequency, 𝝂𝟎 . Thus the internal energy of the solid is

3h 0
uN (1.10)
[exp(h 0 / kT )  1]

And the lattice heat capacity at constant value is

u 3h 0 exp( h 0 / kT ) h 0
CV  N
T [exp(h 0 / kT )  1]2 kT 2 (1.11)

This can be expressed as

  exp( E / T )
2

CV  3Nk  E 
 T  [exp( E / T )  1]
2
(1.12)

h 0
where  E  is defined as Einstein temperature.
k

The above expression may be used to obtain a reasonable fit to the experimental data
for a given material by choosing an appropriate value for Einstein temperature, which is
found to be of the order of a few hundred degrees absolute. Einstein’s formula is found to
be in fair agreement with experiment for 𝑻 ≫ 𝚯𝑬 but at low twmperatures, the
agreement is poor. For non metals, the heat capacity approaches zero as 𝑻𝟑 whereas
Einstein’s formula predicts

 
2

CV  3R  E  exp(  E / T )
 T 

Debye in 1912 successfully explained the 𝑻𝟑 variation at low temperatures by

considering the presence of a spectrum of frequencies. Indeed, Einstein’s derivation was
by no means the last word, but it was sufficient to demonstrate the inadequacy of
classical concepts, namely that material oscillators, like radiation oscillators, can take
only discrete energy values in limiting situations.

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3.3 Photoelectric Effect

The phenomenon of photoelectric effect was observed for the first time in 1887 by
Heinrich Hertz while he was carrying out experimental investigations to establish the
existence of electromagnetic waves in order to confirm Maxwell’s theory. He noticed that
ultraviolet light falling on metallic electrodes produced high voltage sparks across the
detector loop. Light shining on the metal surface facilitated to release free charged
particles which were identified y as electrons. Later, this phenomenon was studied in
detail by W Hallwachs and Phillip Lenard. The detailed investigations carried out by
Lenard revealed the following striking features which can not be explained by classical
electromagnetic theory.

1. There exists a minimum, called threshold frequency of the radiation characteristic

of the surface below which no emission of electrons can take place. It does not
matter what the intensity of incident radiation is and for how long it falls on the
surface. This observation is in contradiction with the classical wave theory
according to which photoelectric effect should occur for any frequency of incident
radiation provided the intensity of radiation is large enough for ejecting the
electrons.
2. The maximum kinetic energy of electrons emitted by the surface is found to
depend linearly on the frequency but is independent of the intensity of incident
radiation. According to classical electromagnetic theory, the maximum kinetic
energy of the electrons should increase with the increase in intensity but should be
independent of frequency.
3. Experimentally, the photoelectric emission is an instantaneous process without
any apparent time lag (less than or of the order of 10−9 s ). In wave picture, the
absorption of energy takes place continuously. The energy absorbed per electron
per unit time turns out to be small. Explicit calculations show that it can take a
sufficient long time for a single electron to pick up sufficient energy in order to
come out of the metal.
In 1905, Einstein proposed a radically different picture by suggesting that
electromagnetic radiation only exists in discrete energy corpuscles or quanta, called
photons, each photon having an energy E=hν=hc/λ He thus advanced the idea by
generalizing Planck’s postulate of quantization of energy to postulate that
electromagnetic radiation by itself exists in the form of light quanta.
According to Einstein, when a photon falls on a metallic surface, its entire
energy hν is used to eject an electron from the atom. If hν exceeds the amount of
energy, called the work function (W), required to escape the electron from the surface
of the metal, the electrons would move out of the surface with energies upto a
maximum value, 𝐸𝑚𝑎𝑥 = ℎ𝜈 − 𝑊. This result was verified in a series of experiments
carried out using sodium and potassium as photoelectric surfaces. According to the

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Einstein equation, plot of maximum kinetic energy, 𝐸𝑚𝑎𝑥 , (which is experimentally

observed in terms of the stopping potential ,𝑉0 , just sufficient to stop the fastest
electrons) with frequency ν of incident radiation gives a linear fit showing that there
exists a threshold frequency below which no electron emission takes place( See
Fig.1.3(a)..

Fig. 1.3(a) Plot of Stopping Potential vs Frequency of incident radiation for two
metals (A) and (B). Note that slope of the linear plot is same for different metallic
surfaces. It is, in fact, proportional to Planck‘s constant and charge of the electron.

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Fig.1.3(b) Plot of Photocurrent vs collector Potential for different intensity of

radiation but having same frequency

Indeed experimental data obtained by Millikan provide further

confirmation of Einstein’s theory as shown in Figures 1.3(a) and 1.3(b) .

3.4 The Compton Effect

About 20 years later, i.e., in 1924, Arthur Compton discovered that when
hard X-rays (of shorter wavelength) are scattered by atoms of an element of low atomic
number (such as graphite), the scattered radiation contains not only the original
wavelength but also softer X-rays of longer wavelength. Compton was able to explain
this phenomenon of scattering of X-rays by assuming that X-rays consist of a collection
of photons, each characterized by energy, E, and momentum, p. Assuming that X-rays of
wavelength  consist of a stream of photons of energy E  h  h c /  , Compton argued
that when one of these quanta hits a free or loosely bound electron, it would recoil. As a
result it would have an energy 𝐸 ’ < 𝐸 after the collision and therefore the corresponding
wavelength     . Based on this picture, quantitative calculations can be made, using the
laws of conservation of energy and momentum, to estimate the increase in the
wavelength of the scattered photon.

Consider an incident photon of energy 𝐸0 and momentum 𝑝0 , which collides with

an electron and is then scattered as shown in the figure ( Fig.1.2 ). The figure shows the
scattered photon of energy 𝐸1 𝑎𝑛𝑑 𝑚𝑜𝑚𝑒𝑛𝑡𝑢𝑚 𝑝1 = 𝐸1 /𝑐 making an angle 𝜃 and the
recoiling electron of momentum 𝑝2 making angle ϕ with the direction of the incident
photon.In case of metals having low atomic numbers, the binding energy of the electrons
in the atoms may be quite small as compared to the energy of the hard X-rays incident on
the metal. We may, therefore, assume the electrons to be at rest having the rest mass

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energy,
P1

Scattered photon

Incident photon
e 

P0 
Recoiling electron

P2

Fig.1.4
11.2

W0  m c 2 , where m is the mass of the electron. However, since the recoiling electron
from the collision may have velocity comparable to c, it would just be appropriate to use
the relativistic relation for the velocity v of the recoiling electron. Using the law of
conservation of energy during collision, we have
𝐸0 = 𝐸1 + 𝑇 (1.13)
where T is the kinetic energy of the recoiling electron given by
T  (m c 2  c 2 p22 )1 / 2  mc 2
. {1.14)
 c( p0  p1)

Now, the initial and final momenta of the photons is given by the relations

E h h E h h
p0  0   , and p1  1  1  . (1.15)
c c 0 c c 1
and applying the law of conservation of momentum, we have
p0  p1 cos  p2 cos
(1.16)
0  p1 sin   p2 sin 
Or p2 cos  p0  p1 cos (i) and p2 sin   p1 sin  (ii)
Squaring and adding the two equations we get
p 22  p02  p 21 2 p0 p1 cos

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By using the above relations, we rewrite Eq.(1.14) as

[c( p0  p1 )  mc 2 ]2  m 2 c 4  p 22 c 2  m 2 c 4  c 2 ( p02  p12  2 p 0 p1 cos )

On simplifying this equation we get

2mc 3 ( p0  p1 )  2c 2 p0 p1  2c 2 p0 p1 cos
h h h2
or mc (  )  p0 p1 (1  cos )  (1  cos )
0 1 0 1
h
or 1  0    (1  cos )  2C sin 2 ( / 2)
mc
(1.17)
ℎ
where 𝜆𝐶 = . is called the Compton wavelength. Equation (1.17) ) is known as
𝑚𝑐
Compton equation. The Compton wavelength is, in fact, the wavelength shift when
scattering takes place at 900 and can be experimentally observed which can be compared
with the calculated value. This is found to be in excellent agreement with the prediction
of Compton’s theory. The success of the theory presented above shows unambiguously
that electromagnetic radiation manifests itself as a stream of corpuscles or quanta during
scattering.

4. Smmary

In this module we have explored the nature of electromagnetic radiation by studying

some typical processes like Black Body Radiation, Specific Heat of Solids, The
Photoelectric Effect and Compton Scattering. These processes clearly show that
electromagnetic radiation manifests itself in the form of corpuscles or quanta of light.
From our earlier studies we also know that the phenomena of interference, diffraction
and polarization can only be explained on the basis of wave theory of light. It is
therefore clear that electromagnetic radiation plays a dual role: it exhibits both as
particles and waves. This ability of electromagnetic radiation to behave both as
waves and photons is referred to as wave-particle duality.

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