CHM 112M: Lecture 1

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Arnab Ghosh
August 12, 2023

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1 Introduction
Quantum theory gives the first satisfactory answer to the black-body problem
which was a major unsolved problem in theoretical science at the turn of the

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last century.1

2 Black-body radiation and Quantum Theory:

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• A body that absorbs and emit radiation at all frequencies is called a black-
body. A closest practical realization of a perfect black-body is a cavity-
like container with a tiny hole on it. Once radiation enters the container,
it faces difficulty in escaping and undergoes multiple reflections on the
walls. This makes the radiation to reach equilibrium with the black-body
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temperature.

• The radiation that escapes through the hole, known as black-body radia-
tion, exhibits a spectral distribution Eλ which is specific to the black-body
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temperature T . Here Eλ is the energy density within the range λ to

λ + dλ. The quantitative understanding of Eλ in relation to λ was lacking
between 1860-1900 until Max Planck provided a satisfactory explanation
for the black-body problem in 1900.
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2.1 Observations between 1860-1900:

Gustav Kirchhoff was the person who conceived the idea of black body ∼ 1860.
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• Kirchhoff ’ Law (1860): At a given T and λ

emissive power(Wλ ) energy emitted per unit area per unit time
=
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absorptivity(Aλ ) fraction of the incident radiation that gets absorbed

is independent of the substance.

1 Note: This is Brief Overview of Class Topics (For Internal Use): Not a Lecture Substitute.

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 • In 1865 John Tyndall conducted some measurements on the radiation
emitted from hot Pt-wires and noted that the total emission from a Pt-
wire at 1473K is 11.7 times that at 798K.
• Stefan-Boltzmann Law (1879 & 1884) : From Tyndall’s experiment,

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Josef Stefan first pointed out (1879) the correct relationship between the
radiance (R) of a black-body (i.e., the energy emitted per unit area per
unit second) and its absolute temperature. Identifying (1473/798)4 ∼
11.7, he proposed a purely an empirical law
Z ∞
R= Wλ dλ ∝ T 4 . (1)

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In 1884, Ludwig Boltzmann provided the theoretical proof of this law

where the constant of proportionality σ is known as Stefan-Boltzmann
constant, having value 5.67 × 10−8 Jm−2 s−1 K−4 .

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• Wien’s distribution and displacement law: In 1896, Wilhelm Wien
derived the radiation law for spectral energy distribution as
c1 −c2 /λT
Eλ dλ = e dλ, (2)
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with c1 and c2 are constants. The distribution law was experimentally
verified in 1897 for the short wavelength visible region but did not fit at
all the long wavelength experimental results that were available in 1899!
Wien also observed that an increase in temperature shifts the black-body
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radiation spectrum towards shorter wavelengths, following the relationship

λmax T = constant (Expt: 0.0029mK), (3)

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where λmax represents the wavelength at which the black-body radiation

reaches maximum intensity.
• Rayleigh-Jeans Law: In 1900, Lord Rayleigh and James Jeans pro-
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posed a theoretical derivation of the black-body problem based on the

assumption that a black-body contains standing waves of radiation:
8πkB T
Eλ dλ = dλ, kB = 1.38 × 10−23 JK−1 . (4)
λ4
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The law predicted the long wavelength behaviour fairly well, but failed at
short wavelength, leading to the so-called “ultraviolet catastrophe”, i.e.,
an absurd situation since Eλ increased monotonically with decreasing in λ,
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implying an infinite energy content within the black-body cavity [Fig. 1].

2.2 Planck’s Radiation Law:

Planck assumed the radiating body as a collection of many resonators resonating
at all frequencies. At frequency νi , if there are Ni resonators with average energy

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Figure 1: Spectral distribution at 1449K, 1259K according to Planck’s and RJ
(Adapted from PKG’s book).
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i i
Ui , then the total energy of N resonators is UN = Ni Ui . While, classically, UN
i
can take take any values, Planck made a revolutionary assumption that UN is
composed of Pi discrete packets of energy, each of value i , so that Ni Ui = Pi i .
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Dropping the subscript for a specific ν, one can compute the number of ways
W in which P energy elements could be distributed among N resonators, with
no constraint on the number of energy elements that each resonator can have.
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Then according to Boltzmann’s 1877 derivation of the statistical entropy of a

system of N resonators is given by
SN = kB ln W, where, W = F (N, P ) (5)
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Substituting, P = U N/, we can write average entropy S of each resonator

   
SN U U
S= = kB f , ⇒ S=f . (6)
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At equilibrium,
 
dqrev dU dS 1
dS = = , = . (7)
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T T dU T
From the Wien’s displacement law, we obtain 1/T = λ/constant = c/(ν ×
constant). Combining this with Eq. (7), we write
 
λ c dU U
dS = dU = × , ⇒ S=g . (8)
constant constant ν ν

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 Striking similarity between Eqs. (6) and (8), led Planck to assert that  and ν
are related linearly as

 = hν, (9)

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with proportionality constant h, which now known as Planck’s constant. This
was the origin of quantum theory and Eq. (9) implies that there is a definite
energy associated with radiation of frequency ν, and the energy of the resonator
with frequency ν can only be in quanta of hν. The above equation should not to
be confused as the derivation of  = hν, but as an existence of a linear relation-
ship between  and ν. h is a fundamental constant of nature, has dimension of
action and its value is 6.626 × 10−34 Js. Its meaning is yet not fully understood,

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but its presence indicates the quantum effects are important.
Let us now derive the spectral distribution law according to Planck’s quan-
tum theory. We can write

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energy density between ν to ν + dν = average energy of each resonator (U)
×no. of resonators per unit volume in the frequency range ν to ν + dν (dnν .
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The no. of resonators nν per unit volume with energy hν for electromagnetic
radiation is found to be

8πν 3
nν = Try! (10)
3c3
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Differentiating w.r.t ν, we get the no. of resonators dnν in frequency range ν to

ν + dν, as

8πν 2 dν
dnν = , (11)
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c3
whereas the average energy of each resonator can be calculated as

UN hν
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U= = hν/k T Try! (12)

N e B −1

Therefore, we obtain energy density in the range ν to ν + dν, as

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8πν 2
U dnν = U dν ≡ udν. (13)
c3
Substituting the value of U , we get the Planck’s radiation law
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8πν 2 hν
udν = 3 hν/k
dν (14)
c e BT − 1

which is valid in the entire range of EM spectrum.

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 In terms of wavelength, one can express using the relation ν = c/λ and
dν = −(c/λ2 )dλ as
8πhc 1
Eλ dλ = 5 hc/λk
dλ. (15)
λ e BT − 1

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For short wavelength (hc/λkB T  1), we recover Wien’s distribution law
8πhc −hc/λkB T
Eλ dλ = e dλ, (16)
λ5
and for long wavelength (hc/λkB T  1), approximating ehc/λkB T ≈ 1+(hc/λkB T ),
we obtain the Rayleigh-Jeans law and experimental results in IR region

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8πhc λkB T 8πkB T
Eλ dλ = dλ = dλ. (17)
λ5 hc λ4
Before the advent of Planck’s theory, there were several other phenomena that
could not be adequately explained. Here are few notable examples:

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2.3 Photoelectric effect:
It was observed that
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• Emission of electrons from metal surfaces occurs when subjected to radi-
ation of sufficiently high frequency.
• Electrons KE depends on the frequency (varies linearly) of the incident
light and not on the intensity of the light.
• There was virtually no time lag (∼ 10−9 s) between shining of light and
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emission of electrons.
— all the above observations were in conflict with classical theories.
Albert Einstein resolved the problem in 1905 using Planck’s concept that a
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light beam is made up of packets (quanta) of light energy which we called today
photons (due to G. N. Lewis) via relation E = nhν, where n is the # of photons
in the beam. For a single photon, the photoelectric effect is expressed as
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1
hν = φ + me ve2 (18)
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where φ is the work function — minimum energy required to remove an electron
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from a neutral metal surfaces.

Explanation: (i) Treating photons as particles, energy transfer between
a photon and an electron during collisions would be instantaneous. (ii) For
photons with energy above the threshold frequency (ν0 ), KE of the emitted
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electrons increase linearly with the energy of the incident photon, however the
# of collisions and # of emitted electrons depend on the intensity of the light
beam. (iii) Above the threshold frequency ν0 , with an increase in the intensity of
the light beam, the number of photons also increases. As a result, the probability
of collisions also increases, leading to a higher number of emitted electrons and
an increased value of the photo-current.

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 2.4 Compton effect:
In 1923, Arthur Compton, experimentally verified that there is indeed decrease
in photon energy due to collision with an electron and the loss in energy is equal
to the increase in KE of the electron. According to conservation of energy and

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momentum due to inelastic collisions, there will be an increase of wavelength of
the scattered photon which is given by
h ∆λ
λ0 = λ + (1 − cos θ) ⇒ = 1 − cos θ. (19)
m0 c λc
Note change in the wavelength ∆λ is independent of incident wavelength, and
λc = h/m0 c is the Compton wavelength, for electron, its value is 0.0024 nm.

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3 Theory of Atomic Structure

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In, 1910, Marsden and Geiger performed the renowned gold foil experiment.
They directed an intense beam of alpha particles, obtained from a Ra source, at
a gold foil. The alpha particles were detected by a rotatable ZnS screen which
scintillated upon interaction with the particles. The experimental findings re-
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vealed that while the majority of alpha particles passed through the foil without
deflection, a few scattered at large angles, and some even scattered by 180◦ . In,
1911, Ernest Rutherford proposed a theory of atomic structure to provide an
explanation for these experimental observations.

3.1 Rutherford’s Model

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To account for the large angle scattering by the α-particles, Rutherford pro-
posed almost entire mass of the atom is concentrated in a minute positively
charged nucleus having dimensions much smaller than that of atom and nega-
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tively charged electrons are revolving around it. Though the model explained
the observed large angle scattering, it was inconsistent with electrodynamic the-
ory, according to which an accelerated charge should emit radiation, thus loses
energy, and eventually falls into the nucleus. However, a continuous emission of
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radiation from atoms is not observed experimentally [Fig. 2]!

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Figure 2: Emission spectrum of hydrogen (Adapted from PKG’s book).

Reference:
1. Atomic Electronic Structure by P. K. Ghosh and P. K. Shukla. (PKG)