Lecture 36 (Schroeder, chapter 7.4).

One of the great conceptual advances of 20th-

century physics, the quantum theory, begun in
1900 when Max Planck introduced his explanation
of blackbody radiation.

“In short, the essential change in our outlook

brought about by the quantum theory is due to the
discovery [by Planck] that the unit h is finite and
not infinitesimal.” A. D’Abro, The Rise of the
New Physics.
 Photons
The problem we want to address is the electromagnetic radiation confined
in the box with the walls in thermal equilibrium with the radiation (a
“blackbody cavity”). The electromagnetic field has an infinite number of T
modes (standing waves) in the cavity. Any radiation field is a
superposition of plane waves of different frequencies. The characteristic
feature of the radiation is that a mode may be excited only in units of
the quantum of energy hf (similar to a harmonic oscillators) : ε = (n + 1 / 2 )h f
i i

This fact leads to the concept of photons as quanta of the electromagnetic field.
The state of the el.-mag. field is specified by the number n for each of the modes, or, in
other words, by enumerating the number of photons with each frequency.
According to the quantum theory of radiation, photons are massless bosons of spin
1 (in units ħ). They move with the velocity of light
E ph f h
E ph = h f E ph = cp ph p ph = =h = k
c c 2π
The linearity of Maxwell equations implies that the photons do
not interact with each other. (Non-linear optical phenomena
are observed when a large-intensity radiation interacts with 1
nBE =
matter). Presence of a small amount of matter is essential for ε −µ
establishing equilibrium in the photon gas. We’ll treat a system
exp −1
k BT
of photons as an ideal photon gas, and, in particular, we’ll
apply the BE statistics to this system:
 Chemical Potential of Photons
What is the chemical potential in the BE distribution for 1
nBE =
photons? ε −µ
exp −1
In general, the occupancy n cannot be negative – this k BT
imposes some restrictions on µ. In particular, for bosons, µ ≤ 0
(ε varies from 0 to ∞).
→ =0

For fermions, the chemical potential may be either positive or

µ −ε
negative. For the systems with Boltzmann statistics, µ < 0, since nB = exp << 1
k BT
∂E
Another way to look at it: µ ≡ Normally, when you add a particle to a system,
∂N S ,V
the entropy is not fixed. If you want to keep S fixed, you typically have to remove
some energy from the system as you add the particle. So µ for an ideal gas is
negative.
The mechanism of establishing equilibrium in a photon gas is absorption and
emission of photons by matter. Thus, the number of photons, N, is not a constant, in
contrast to a conventional gas. N can be found from the equilibrium condition: ∂ F
∂F =0
On the other hand, = µ ph ∂N T ,V
∂N T ,V

Thus, in equilibrium, the chemical potential for a photon gas is zero: µ ph = 0

 Blackbody Radiation
For µ = 0, the BE distribution reduces to the Planck distribution:
1 1 Planck distribution provides the
n ph = =
ε hf average number of photons in a
exp −1 exp −1 single mode of frequency f.
k BT k BT
hf
ε = n hf =
The average energy in the mode: hf
exp −1
k BT
In the classical (high temperature) limit: ε = k BT
In order to calculate the average number of photons per small energy interval dε, the
average energy of photons per small energy interval dε, etc., as well as the total
average number of photons in a photon gas and its total energy, we need to know the
density of states for photons as a function of photon energy.

When we considered the density of states, we got g (ε )dε ∝ v 2 dv ∝ p 2 dp

The result for g(ε) as a function of ε depends on the relationship between the energy ε
and the momentum p: e.g., for non-relativistic electrons (ε ∝ p2), we obtained g(ε) ∝ √ ε .

The density of states for photons (ultra-relativistic limit, ε = cp): ε 2 dε

g (ε )dε = 8π
(per unit volume) (hc )3
 Spectrum of Blackbody Radiation
The number of photons per unit volume (concentration) with energies in the range ε to ε+dε:
1 ε2
N (ε )dε = n (ε )× g (ε )× dε = 8π dε
exp(βε i ) − 1 (hc ) 3

The energy of a photon gas per unit volume (the energy density) within the range ε to ε+dε:
ε ε2
u (ε )dε = ε × g (ε )× dε = 8π dε
exp(βε i ) − 1 (hc )3
The spectrum of blackbody radiation:

8π ε3
u (ε , T ) =
(hc )3 exp
ε
−1
k BT

u - the energy density per unit photon energy

This is the energy density for a photon gas in
equilibrium with a blackbody at temperature T.
dε
u as a function of the frequency: u (ε , T )dε = u ( f , T )df u ( f , T ) = u (ε , T ) = u (ε , T )× h
df
u( f ,T ) =
8π (hf )3 ×h
(hc )3 exp
hf
−1
k BT
 Wien’s Displacement Law
The maximum of u(f) shifts to higher frequencies with increasing
temperature. The position of maximum:

hf
3
Wien
du d k BT 3x 2 x 3e x
= const × = const × x − =0
df
d
hf
exp
hf
−1
e −1 e −1
x
( )
2

k BT k BT
h f max
f max
k T
≈ 2 .8 B (3 − x ) e x = 3 → x ≈ 2. 8
k BT
≈ 2 .8
h
Wien’s displacement law

- the “most likely” frequency of a photon in a

blackbody radiation with temperature T
u(f,T)

Numerous applications
(e.g., non-contact radiation thermometry)

f
 Stefan-Boltzmann Law of Radiation
The total number of photons per unit volume:
∞ ∞ 3∞ 3
N 8π f2 8π k BT x 2 dx kB
n≡ = ∫ n (ε )g (ε )dε = 3 ∫0 df = ∫0 e x − 1 = 8π T 3
× 2 .4
V 0 c hf c3 h hc
exp −1
k BT - increases as T 3

The total energy of photons per unit volume : U ε × g (ε )

∞
8π 5 (k BT )
4
u (T ) ≡ = ∫ dε =
(the energy density of a photon gas) V 0 exp(βε ) − 1 15(hc )
3

2π 5 k B
4
the Stefan-Boltzmann 4σ 4 the Stefan-
σ= constant u (T ) = T Boltzmann Law
15h 3c 2 c

The average energy per photon:

u (T ) 8π 5 (k BT ) (hc ) π4
4 3
ε = = = k B T ≈ 2. 7 k B T
15(hc ) 8π (k BT ) × 2.4 15 × 2.4
3 3
N

(slightly different than the “most” probable energy/frequency)

 Power Emitted by a Black Body

For the “uni-directional” motion, the flux of energy per unit area = c × u

energy density u

1m2
c × 1s
Integration over all angles provides a factor of ¼:
1
power emitted by unit area = c×u
4
(the hole size must be >> the wavelength)

Thus, the power emitted by a unit-area c c 4σ 4

surface at temperature T in all directions: power = u (T ) = × T =σ T4
4 4 c

The total power emitted

by a sphere of radius R:

total power emitted by a sphere = 4πR 2σ T 4

T
 GH Effect
Absorption: 2

(
Power in = α π RE σ (TSun )
2
) 4 RSun
Rorbit
the flux of the solar radiation energy
received by the Earth ~ 1370 W/m2
Power out = 4π RE σ TE
2 4
Emission:

2 1/ 4
α RSun
TE = TSun
4 Rorbit

Rorbit = 1.5·1011 m
Transmittance of the Earth atmosphere
RSun = 7·108 m

α = 1, –T Earth = 280K However, in reality α = 0.7, TEarth = 256K

To maintain a comfortable temperature on the Earth, we need the Greenhouse Effect.

 Thermodynamic Functions of Blackbody Radiation

∂u (T ) 16σ 3
The heat capacity of a photon gas at constant volume: cV ≡ = T
∂T V c

This equation holds for all T (it agrees with the Nernst theorem), and we can
integrate it to get the entropy of a photon gas:

c (T ′) 16σ 16σ 3
T T
S (T ) = ∫ V dT ′ = ∫ T ′ 2
d T ′ = T
0
T ′ c 0
3c

Now we can derive all thermodynamic functions of blackbody radiation:

4σ 4 16σ 4 4σ 4
the Helmholtz free energy: F = U − TS = T − T =− T
c 3c 3c

the Gibbs free energy: G = U − TS + PV = F + PV = 0 (= µN )

 Pressure of a Photon Gas
∂F 4σ 4 1 1
the pressure of a photon gas: P=− = T = u PV = U
radiation pressure ∂V T ,N 3c 3 3

For comparison, for a non-relativistic monatomic gas – PV = (2/3)U. The difference –

because the energy-momentum relationship for photons is ultra-relativistic, and the
number of photon depends on T.
In terms the average density of phonons:
1 1 1
PV = U = V × n × ε = V × n × 2.7k BT = 0.9 N k BT
3 3 3