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CHEM F111 General Chemistry Lecture 01

Quantum Theory - Origins
(Classical) mechanics – Developments
by early 19th Century

Sir Issac Newton (1642-1726)

Newtonian Mechanics
(17th century and beyond)

Joseph Louis Lagrange (1736-1813)

Sir William Rowan Hamilton (1805-1865)
Lagrangian Mechanics (1788)
Hamiltonian Mechanics (1833)
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Some developments in physics from the
19th century

John Dalton – Concept of atoms (1803)

Amedeo Avogadro – Concept of molecules (1811)

Sir J. J. Thomson – Concept of electron (1897)

Millikan – Charge of elementary particles (1909)

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Objectives and outcome of learning

In the light of the topics:

●
Black-body radiation
●
Photo-electric effect
●
Atomic emission spectrum of hydrogen

we will learn that

●
Classical physics fails to describe certain experimental
observations
●
Satisfactory explanation to the observed phenomena can
only be possible by introduction of quantization

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Black-body radiation

Perfectly black-body: A body that absorbs and emits radiations of all

frequencies
Black-body when sufficiently hot relative to the surrounding emits
electromagnetic radiations of various frequencies
Was first studied in late 19th century
●
William Herschel (1800) thermal radiation
●
Balfour Stewart (1858) compared the radiations from lamp-black with
radiations from non-black bodies
●
Gustav Kirchoff (1859) independently discovered Stewart’s finding and
expanded further to his theory of thermal emission
●
Lummer and Pringsheim (1899) plotted the dependence of intensity
(energy density, emissive power) with radiation wavelength/frequency and
temperature
●
Planck (1900) successfully explained the behavior of BBR using his
quantum hypothesis
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Black-body radiation (BBR)

• Heated body emits radiation. The energy emitted per unit area per second,
called the emissive power, is a function of the wavelength (or frequency),
and temperature
• Black body – one which absorbs all the radiation that falls on it (and emits
it all back when sufficiently hot)
• Let J(λ, T) be the emissive power of a black body.
What is the form of J(λ, T)?

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BBR: Experimental findings by Lummer
and Pringsheim (1899)
• Conveniently studied by analyzing the radiation energy density in cavity
whose walls are at T
• Can show that the energy density ρ(λ,T) = J(λ,T)/c
• ρ(λ,T)dλ is the energy per unit volume associated with energy of radiation
of wavelength λ to λ+dλ
• Maximum in ρ(λ,T), position of maximum shifts to lower wavelength
(higher frequency) with increasing temperature

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BBR: Verifiable observations

Emittance M: Total power emitted per unit area

M = σT4, (Stefan-Boltzmann law);
where, σ=5.67×10-8 Wm-2K-4; (Stefan-Boltzmann constant)

Weins’ displacement law:

λmaxT = 2.9 mm·K OR νmax/T = αk/h (where α≈2.821439…)

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BBR: Failed attempts in explaining the
trends
Why does the curve go through a maximum?

Attempts to explain BBR:

●
Rayleigh and Jeans pictured the radiation energy in the cavity as a collection of
oscillators. Using the classical physics and empirical observations, they derived the
formula:
8πk T
ρ(λ , T )d λ= 4
dλ
λ
Does well at long wavelength (low frequency), but fails miserably at short
wavelengths (ultraviolet catastrophe)

●
Wien, in his formulation guessed the qualitative trend at short wavelengths (high
frequencies), but failed quantitatively at long wavelengths.
e−β c /λ T
ρ(λ , T )d λ ∝ 5
dλ
λ

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BBR: Planck’s quantum hypothesis
explained it all
Assumption: Molecules of the black-body behave like simple harmonic oscillators
and have characteristic vibrational frequency
Crucial assumption: The energy exchange between the walls of the black-body and
the interior could only occur in integral multiples of a quantum of energy.
Δ E=n h ν ; n=0,1,2,…; ν=c /λ
Using this, Planck derived radiation formula:
8πhc dλ
ρ(λ , T )d λ= ( λ 5 )
e h c /λ kT
−1
; where, k is the Boltzmann constant.

Planck found that with h=6.626 x 10-34Js,

Js the above expression gives perfect
agreement with experiment
●
Reduces to Rayleigh and Jeans law at larger wavelengths (lower frequencies)
●
Reduces to Wein’s formula at shorter wavelengths (higher frequencies)
●
Differentiate in order to get Wein’s displacement law
●
Integrate in order to get Stefan-Boltzmann law

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BBR: Planck’s quantum hypothesis
explained it all

8πhc dλ
ρ(λ , T )d λ=( )
λ 5 e h c /λ kT −1

DIY: Plot the energy density as a function of wavelength for different

values of temperature, using libreoffice calc or msoffice excel or any
graph plotting software available with you.
Set all the constants in the expression to unity for your convenience.

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The photo-electric effect

• Threshold frequency ν0 characteristic of the metal below which there

is no emission
• The kinetic energy of the emitted electrons increases linearly with the
frequency of the incident radiation, but is independent of the incident
intensity
●
For frequency above the threshold, even at very low intensity, the
emission is instantaneous
●
Photoelectric current is proportional to the intensity, but not dependent
on frequency
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Einstein proposed particle nature of light
and explained the photoelectric effect
●
Einstein postulated that light may be
considered as a collection of particles, each of
energy hν
●
Kinetic energy of emitted electrons is given by
K = hν – φ, where the work function φ is the
energy required to just overcome the binding
energy of the electron, and with φ = hν0, (ν0 is
threshold frequency) one obtains K = hν – hν0

Intensity being proportional to the number of photons cannot bring about

photoelectric effect if the frequency is less than the threshold frequency.
Photoelectric current is proportional to number of photoelectrons, which is in
turn proportional to intensity.
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