Quantum Theory of Black Body Radiation

CHEM F213 : Physical Chemistry-II
Module-I:
Development of Quantum Theory
Failures of classical physics and origin of quantum

theory (Lectures 01, 02)
- Prashant Uday Manohar
On some physics in 19th Century
John Dalton Concept of atoms (1803)
BITSPilani, Pilani Campus

Amedeo Avogadro Concept of molecules (1811)

Sir J. J. Thompson Concept of electron (1897)

Sir J. J. Thompson Concept of electron (1897)
Millikan Charge of elementary particles (1909)

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




we will learn that

Classical physics fails to describe certain experimental
observations




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

Black body Radiation (BBR): History
Perfectly black-body: A body that absorbs and emits radiations of all
frequencies
Black-body when sufficiently hot with respect 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 Stewarts finding

and expanded further to his theory of thermal emission
Lummer and Pringsheim (1899) plotted the dependence of intensity

(energy density, emissive power) with wavelength/frequency and
temperature
Planck (1900) successfully explained the behavior of BBR using his

quantum hypothesis
Black body Radiation (BBR)
Emissive power (for a given frequency): J(, T) energy emitted per unit area per
unit time for a given frequency (or wavelength)
Energy density (, T) Can be proven that this equals to J(, T)/c

BBR: Verifiable Observations
Emittance M Total power emitted

M = T4, (Stefan-Boltzmann law);
where, =5.6710-8 Wm-2K-4; (Stefan-Boltzmann constant)

BBR: Verifiable Observations
Emittance M Total power emitted

M = T4, (Stefan-Boltzmann law);
where, =5.6710-8 Wm-2K-4; (Stefan-Boltzmann constant)
Weins displacement law:

maxT = 2.9 mmK OR max/T = k/h, where =2.821439

Dependence of energy density on
frequency
Why does the curve go through a maximum?
Attempts to explain BBR:

frequency

Rayleigh and Jeans using the classical physics and empirical
observations derived the formula:
8kT 2
( , T )d = 3
d
c
Fairly well for

smaller frequencies
Unphysical at higher
frequencies UV
catastrophe

frequency

Wein, from thermodynamic arguments obtained a formula for
energy density as:
3
2h
( , T )d = 2 eh / kT
c
Behaves well at
larger frequencies
(UV catastrophe
avoided)
Fails quantitatively
at lower frequencies

frequency

Rayleigh and Jeans using the classical physics and empirical
observations derived the formula: ( , T )d =
8kT 2
d
c3

Fairly well for smaller frequencies

Unphysical at higher frequencies UV catastrophe

Wein, from thermodynamic arguments obtained a formula for
3
energy density as: ( , T )d =
2h
eh / kT
c2

Behaves well at larger frequencies (UV catastrophe avoided)

Fails quantitatively at lower frequencies

BBR: Planck's hypothesis

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.
E=n h ; n=0,1,2,

energy.
E=n h ; n=0,1,2,
Using this, he Planck derived radiation formula:
8 h 3
(
( , T )d =
c )
3
e
d ; where, k is the Boltzmann constant.
h /kT
1
Planck found that with h=6.626 x 10-34Js,
Js the above expression gives
perfect agreement with experiment

8 h 3
( , T )d =
( c
3 )
e
d
h /kT
1
Reduces to Rayleigh and Jeans law at lower frequencies
8kT 2
( , T )d = 3
d
c

3
2h
( , T )d = 2 eh / kT
c
Reduces to Weins formula at higher frequencies
8 h 3
( , T )d =
( c
3
e) d
h /kT
1

3
2h
( , T )d = 2 eh / kT
c
8 h 3
( , T )d =
( c
3
e) d
h /kT
1
8kT 2
( , T )d = 3
d
c

8 h 3
( , T )d =
( c
3 )
e
d
h /kT
1
Set d =0; and solve for

d
Weins displacement law

Stefan-Boltzmann law
Integrate w.r.t.
8 h 3
( , T )d =
( c
3 )
e
d
h /kT
1

Stefan-Boltzmann law
Integrate w.r.t.
8 h 3
( , T )d =
( c
3 )
e
d
h /kT
1
Set d =0; and solve for

d
Weins displacement law

BBR: Planck's hypothesis revision
energy.
E=n h ; n=0,1,2,
Using this, he Planck derived radiation formula:
8 h 3
(
( , T )d =
c )
3
e
d ; where, k is the Boltzmann constant.
h /kT
1
Planck found that with h=6.626 x 10-34Js,
Js the above expression gives
perfect agreement with experiment
Differentiate in order to get Weins displacement law
Integrate in order to get Stefan-Boltzmann law

Photoelectric effect
No photoelectrons ejected if energy of radiation less than workfunction


Max. kinetic energy of photoelectrons increases linearly with frequency
but independent of intensity


Photoelectric current proportional to intensity but independent of
frequency


frequency
Einstein's explanation:
Light particle Photon quantum of
energy


frequency
energy
A photon can only be completely
absorbed by an electron.


frequency
energy
Probability that two photons can be
absorbed by an electron is highly
negligible


frequency
energy
Probability that two photons can be
absorbed by an electron is highly
negligible
Photoelectron is ejected only if the frequency of the absorbed photon is
greater than some threshold frequency.
H-atom: Line spectrum
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 = (E 2 E1)/h, or in terms of
the wave number
v = 1/ = (E2 E1)/hc = R(1/n12 1/n22)
Lyman, Balmer, Paschen, Brackett, Pfund series!

Bohr model of H-like atom
Electron (mass m and charge e) moving in a circular orbit of radius r

about nucleus of charge Ze


Coulombic force between the electron and the nucleus serves as the
centripetal force
mv2/r = Ze2/40r2
Bohr postulated stable orbits with radius given by mvr = nh/2 = n,
n=1,2,3, (quantization of angular momentum)


Coulombic force between the electron and the nucleus serves as the
centripetal force
mv2/r = Ze2/40r2
Bohr postulated stable orbits with radius given by mvr = nh/2 = n,
n=1,2,3, (quantization of angular momentum)
2 2 2
Combining, one finds r = (n /Z)a , where a = 4 /me is the Bohr radius
0 0 0
Also the energy E = p2/2m Ze2/40r = Ze2/80r

En = -mZ2e4/322022n2 = -RhcZ2/n2 where R is the Rydberg constant

Wave-particle duality

If light (radiation) can be viewed as a collection of particles, then can
the entities considered as particles be seen as waves?

Wave-particle duality

If light (radiation) can be viewed as a collection of particles, then can
the entities considered as particles be seen as waves?

de Broglie postulated the existence of matter waves associated with
particles, with a wave length given by = h/p

Confirmed by the electron-scattering experiments of Davisson and
Germer

Two-slit experiments
Experiment with Bullets:

Arrive in identical discrete lumps particles;
Distribution with both slits open = sum of the
distribution with slit 1 alone open and the distribution
with slit 2 alone open; (I12 = I1 + I2)
No interference observed
Experiment with water waves:

Intensity can be varied by changing amplitude of
source (Intensity proportional to square of
amplitude), no lumps;
Intensities dont add, the amplitudes do there
is interference waves (I12 I1+I2)

Experiment with electrons/photons etc.?
Arrive in identical lumps particles
But the distribution shows interference
wave behaviour
The system (electron or photon) has dual nature, but depending on

the experiment, particle-like or wave-like nature is observed.
Can one find if the electron/photon passed through slit 1 or slit 2? -
Yes. One can. But then, the interference pattern would be lost.

wave behaviour

wave behaviour
The system (electron or photon) has dual nature, but depending on

the experiment, particle-like or wave-like nature is observed.
Can one measure the wavelength of the electron/photon passed
through the slits? Yes. One can, from the interference pattern. But
then, the position would become uncertain.

wave behaviour
Interference pattern Wavelength Momentum; Position

uncertain
Fix the position (Electron emitted from Slit 1 or Slit 2?)

Interference pattern lost Wave properties undetermined;
Momentum Uncertain
It is thus impossible to simultaneously measure position and momentum of a

system with arbitrary accuracy. (Heisenberg's uncertainty principle)

Uncertainty principle
Mathematical formulations:
Position-momentum uncertainty
xp /2
(Here, x is the actual position not the x-coordinate)
In terms of individual coordinates one can write:

xpx /2; ypy /2; zpz /2;
Energy-time uncertainty
Et
Can be obtained for any conjugate position-momentum pair
What will be the expression for the product of uncertainties in the

simultaneous measurements of angular-position & angular-
momentum of fundamental particle?

Quantum Theory of Black Body Radiation

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CHEM F213 : Physical Chemistry-II

Failures of classical physics and origin of quantum

John Dalton Concept of atoms (1803)

BITSPilani, Pilani Campus

John Dalton Concept of atoms (1803)

Amedeo Avogadro Concept of molecules (1811)

BITSPilani, Pilani Campus

John Dalton Concept of atoms (1803)

Amedeo Avogadro Concept of molecules (1811)

Sir J. J. Thompson Concept of electron (1897)

BITSPilani, Pilani Campus

John Dalton Concept of atoms (1803)

Amedeo Avogadro Concept of molecules (1811)

Sir J. J. Thompson Concept of electron (1897)

Millikan Charge of elementary particles (1909)

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

In the light of the topics:

BITSPilani, Pilani Campus

In the light of the topics:

BITSPilani, Pilani Campus

In the light of the topics:

we will learn that

BITSPilani, Pilani Campus

In the light of the topics:

we will learn that

BITSPilani, Pilani Campus

In the light of the topics:

we will learn that

BITSPilani, Pilani Campus

William Herschel (1800) thermal radiation

Balfour Stewart (1858) compared the radiations from lamp-black with

Gustav Kirchoff (1859) independently discovered Stewarts finding

Lummer and Pringsheim (1899) plotted the dependence of intensity

Planck (1900) successfully explained the behavior of BBR using his

BITSPilani, Pilani Campus

Emittance M Total power emitted

BITSPilani, Pilani Campus

Emittance M Total power emitted

Weins displacement law:

BITSPilani, Pilani Campus

Why does the curve go through a maximum?

Attempts to explain BBR:

BITSPilani, Pilani Campus

Why does the curve go through a maximum?

Attempts to explain BBR:

Fairly well for

BITSPilani, Pilani Campus

Why does the curve go through a maximum?

Attempts to explain BBR:

BITSPilani, Pilani Campus

Why does the curve go through a maximum?

Attempts to explain BBR:

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

Reduces to Rayleigh and Jeans law at lower frequencies

BITSPilani, Pilani Campus

BITSPilani, Pilani Campus

Reduces to Rayleigh and Jeans law at lower frequencies

BITSPilani, Pilani Campus