BITS Pilani

Pilani Campus

CHEM F111 General Chemistry

Lecture 7
QUANTUM THEORY- ORIGINS
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 Quantum Theory
Review of Lecture 6
Energy (power) profile of the radiation wave emitted from a blackbody
at given temperature
Energy Density (range λ to λ+d λ): dE =
(No. density of the oscillators within
range λ to λ+d λ) * (Energy of
Oscillators)

Rayleigh-Jeans: Average energy of the

oscillators: kT [UV Catastrophe]

Planck (Quantization Hypothesis)

(hc/λ) {exp(hc/λkT) -1}-1
Expt. Plot; Wein Displacement Law and
Stefan-Boltzmann Law -obtained using
Planck’s Formula
Quantization of energy levels of oscillators (assumed) of Light
(Electromagnetic field) 2
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Heat Capacity of Monoatomic Solids
Dulong and Petit: Molar heat capacity of all monoatomic solids are the
same and is equal to 25JK-1 mol-1 [Experimental Observation in 19th
century]
Justifying Dulong and Petit’s Law [Classical Physics]
Equipartition Principle – the mean energy of an atom as it oscillates about
its mean position in a solid is kT for each direction of displacement

Average Energy = 3kT (for one atom)

and 3NAkT (for one mole of atoms)
=> Internal Energy U = 3NAkT
Cv,m = 3R = 24.9 JK-1mol-1

Deviations from Dulong & Petit Law:

(advances in refrigeration techniques)
At low temp., Cv,m is less
than 3R and approaches
zero as T →0
Internal Energy, U = Total energy of the particles
making up a sample of matter
Const. Vol. Heat Capacity, Cv = (δU/ δ T)v

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Heat Capacity of Monoatomic Solids
Explanation: (Einstein in 1905)
-Each atom were assumed to oscillate about its equilibrium
position with a single frequency ν
[A crystal with NA atoms considered as a collection of 3NA
harmonic oscillators, each of frequency ν]
-Planck’s Quantization Hypothesis- Energy of oscillation is
confined to discrete values

-Total Internal Energy (Molar) Um = 3NA h ν/{exp(h ν/kT)-1}

-Cv,m = 3NAk(h ν/kT)2exp(h ν/kT)/{exp(h ν/kT)-1}2

-An expression which qualitatively agrees with the experiment
-Reduces to Dulong and Petit Law at high T

-At low T, the strongly decaying exponential function goes to zero

more rapidly so Cv,m →0
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Heat Capacity of Monoatomic Solids

-Qualitatively agrees with the

experiment [Einstein’s
assumption that all the atoms
oscillate with the same frequency]

-Debye formula: Atoms oscillate

over a range of frequencies from
0 to a max. value of νD

Quantization: A crucial assumption required to explain thermal

properties of solids

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 Atomic And Molecular Spectra

What caused spectra of atoms to

contain discrete “lines”?

Each atom has a distinct

“fingerprint”; Light only comes off
at very specific wavelengths

Note that hydrogen (bottom), with

only one electron and one proton,
emits several wavelengths
Spectroscopy: Detection and Analysis of the
electromagnetic Radiation absorbed, emitted or
scattered by a substance
The record of the intensity of light transmitted or
scattered by a molecule as a function of
frequency, wavelength or wavenumber is called
its spectrum
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 Line Spectra of Hydrogen Atom
J. J. Balmer (1885) showed that wavenumber, ṽ, at which lines
occur in the spectrum of hydrogen :
ṽ = 1/ = RH(1/22  1/n2), where n = 3, 4, 5 …
where RH (Rydberg constant )= 109677 cm-1
Ritz (1908) introduced his combination principle (generalization of
the Balmer formula) ṽ = 1/ = RH(1/n12  1/n22),
where n = n1 and n2 (n2>n1) are positive
integers, the various series corresponding to Lyman (n1 = 1),
Balmer (n1 = 2), Paschen (n1 = 3), Brackett (n1 = 4), Pfund (n1 =
5).
The theoretical basis for the Ritz Combination Principle was
provided by the Bohr Theory of hydrogen Atom
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 Bohr’s Model of Hydrogen-like Atom
Neil Bohr (1913)
Electron (mass m and charge –e) moving in circular orbit of radius r
about nucleus of charge Ze;
mv2/r = Ze2/4πε0r2
[Semi-Classical Model]
Electron must radiate energy, fall into the nucleus [Classical Concept]
• Bohr postulated that an electron can revolve around the nucleus only in
certain stable orbits without emitting any electromagnetic radiation
• Only those orbits are stable for which the magnitude of L (orbital
angular momentum of the electron) is quantized
mvr = nh/2π =nħ, n=1,2,3,… - quantization of angular momentum
• Combining, one finds r = (n2/Z)a0, where a0 = 4πε0ħ2/me2 is the Bohr
radius
• Also the energy E = p2/2m – Ze2/4πε0r = – Ze2/8πε0r
• E = -mZ2e4/32π2ε02ħ2n2 = -RhcZ2/n2 where R is the Rydberg constant
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 Bohr’s Model of Hydrogen-like Atom
When the electron in the hydrogen atom
undergoes a transition from energy level E2
to E1, the transition is accompanied by the
emission of a photon of frequency
ν = (E2 – E1)/h, or in terms of the wave
number ṽ = 1/λ = (E2 – E1)/hc = R(1/n12 –
1/n22) Lyman, Balmer, Paschen, Brackett,
Pfund series!

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 Photoelectric Effect

• No electrons are ejected if the frequency of radiation is below a

threshold value characteristic of the metal.
• Kinetic energy of emitted electrons varies linearly with the
frequency, and is independent of light intensity.
• For frequencies above the threshold value, emission of
electrons is instantaneous, no matter how low the intensity of the
light.

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Failure of Classical Physics to Explain
Photoelectric Effect
• Existence of Threshold frequency:
Wave theory- electron emitted should depend on intensity and not
on frequency
• Kinetic energy is independent of light intensity:
According to electromagnetic theory, oscillating electric vector of
the incident radiation should cause an electron in the metal surface
to oscillate; K.E. should depend on the amplitude of the oscillation
of the incident radiation
• Absence of time lag between the irradiation of a surface and
the start of the emission of electrons
According to the wave theory, the energy of the incident light is
spread over as a wave front and so some time will be required by
an electron to absorb enough energy to escape from the surface
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 Photoelectric Effect: Explanation
(Einstein 1905)
•Light of frequency  may be considered as a collection of
particles, called photons, each of energy h.
•When a photon of energy h  is incident on a metal surface, the
entire energy is absorbed by an electron without any time lag

Particle Character of Light

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Photoelectric Effect: Explanation: Contd…
(Einstein 1905)
• If the minimum energy required to remove an electron from
the metal surface is  (work function), then if h < , no
emission of electrons occurs
• Threshold frequency 0 given by  = h0
Kinetic energy of
emitted electrons K =
hν – , where the work
function  is the
energy required to just
overcome the binding
energy of the electron,
and with  = hν0, one
obtains K = hν - hν0
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 Wave Properties of Matter

If light (radiation) can be viewed as a collection of particles, then can

entities considered as particles also be seen as waves?
A quantum having the isolated energy hν is a concept of a particle
[Frequency/wavelength is a concept relevant to a wave]
Radiation possess dual character

Matter evidently has particle properties- So by analogy should also

have wave properties under suitable conditions

This was first postulated by French theoretical physicist Louis de

Broglie in 1924

He suggested that any particle travelling with a linear momentum, p,

should have a wavelength λ=h/p
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Wave Nature of Electrons

“…The electron can no longer be conceived as a single, small

granule of electricity; it must be associated with a wave and this
wave is no myth; its wavelength can be measured and its interference
predicted. It has been possible to predict a whole group of
phenomena without their actually having been discovered. And it is
on this concept of the duality of waves and corpuscles in Nature,
expressed in a more or less abstract form, that all future development
of this science will apparently have to be founded.”

LOUIS DE BROGLIE
Nobel Lecture, December 12, 1929

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Davisson and Germer’s Experiment (1927)
The wave property of particles, together with the de Broglie relation,
were demonstrated first in electron diffraction experiments (Clinton
J. Davisson and Lester H. Germer, 1927)

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Wave-Particle Duality

Are electrons, protons, atoms, photons etc., particles or waves?

The answer is ‘neither’ or ‘both’.

Whether the ‘particle’ or ‘wave’ aspect or behavior is observed

depends on the nature of the measurement being made.

The two are complementary

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Young’s Double Slit Experiment
The same physical system can exhibit under different
circumstances, either particle or wave-like properties.
This experiment will illustrate this mystery of quantum
mechanics…
Experiment with Bullets:
Arrive in identical discrete
lumps – particles
Distribution with both slits
open is the sum of that with
slit 1 alone open and that
with slit 2 alone open –
No interference.

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Young’s Double Slit Experiment Contd…

Experiment with water

waves:
Intensity can be varied by
changing amplitude of source
(Intensity proportional to
square of amplitude) – no
lumps.
Intensities don’t add, the
amplitudes do –
there is interference - waves

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Young’s Double Slit Experiment Contd…

Experiment with electrons/photons etc. :

Arrive in identical lumps – particles, but distribution shows
interference – wave behavior
Any experiment that can be devised that attempts to determine which
slit electron passes through always results in the disappearance of the
interference pattern
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Young’s Double Slit Experiment Contd…

Detector On
No Interference

Detector Off

Interference

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Young’s Double Slit Experiment Contd…
Experiment with electrons/photons etc. :
If we do not look (or cannot look!!!) then we are left with the
uncomfortable thought that in some sense each electron passes
through both slits. [Interference Pattern]

System has a dual potential nature, but the observed nature is

particle-like or wave-like, depending on the nature of the
observation
Does the electron pass through hole 1 or hole 2?
Question needs to be answered only if the experiment being
performed is capable of answering. Else one may end up making
inconsistent predictions
•If the experiment capable of determining which alternative, then
interference is lost
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Principle of Complementarity

Bohr’s principle of complementarity: it is not possible to describe

physical observables simultaneously in terms of both particles and
waves

Consequence: once you measure the wave- (particle-) like behavior of

a phenomenon, you cannot measure a property linked to its particle-
(wave-) like behavior.
– e.g. once you determine that the photon/electron has made it
through a given slit, you reveal its particle-like behavior, therefore
you cannot observe the interference phenomenon anymore (linked to
the wave behavior) !

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De Broglie Matter Waves
Every particle has a wave associated with it.
What are these waves?
Wave in quantum mechanics are “Probability Waves”.

There are “entities or (objects)” which may behave like a wave or a

particle but never simultaneously as both.

A stronger manifestation of the particle nature leads to a weaker

manifestation of the wave nature and vice versa.

Does the experiment with bullets show interference?

Yes, but not seen due to the scale, tiny wavelength and hence fringes too
close, see only average. For macroscopic objects, the predictions of
classical and quantum mechanics are the same

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Wave-Particle Duality
Waves-Nature: Waves are spread out, like the pure sine wave shown
below

Particle-Nature: Particles are localized; they have a definite location, like

the particle shown below.

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Particle-Nature of an Entity

Adding together several pure sine waves with different wavelengths

produces a resultant wave that is somewhat localized. The more sine
waves you add together, the more the resultant wave will be localized,
and the less uncertainty there will be about the object's location.

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Wave-Particle Duality
Waves-Nature:
A pure sine wave has a precise wavelength, and so the object represented
by a sine wave has a precise momentum. But a pure sine wave keeps
going forever in both directions; it is not at all localized. Therefore we
are perfectly uncertain about where the object is!

Particle-Nature:
What is the momentum of the object represented by the resultant wave?
The resultant wave contains a spread of wavelengths (the wavelengths of
the sine waves), and it is not clear which wavelength goes into de
Broglie's formula. Thus there is some uncertainty about the object's
momentum. If you add more sine waves together, the resultant wave will
be more localized, but there will also be more of an uncertainty in the
wavelength and momentum of the object represented by the resultant
wave.
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Uncertainty Principle
Werner Heisenberg - Wave-particle duality of nature – “there is a
natural tradeoff between knowing an object's position and knowing
it's momentum”.

It is impossible to predict, measure, or know both the exact position of

an object and its exact momentum at the same time. In fact, an
object does not have an exact position and momentum at the same
time! Heisenberg uncertainty principle

px x  ħ/2

It is a natural consequence of the wave-particle duality of nature.

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