1.

Consider a gas at a temperature of 2500 K whose atoms can occupy only two energy
levels separated by 1.50 eV. Determine the ratio of the number of atoms in the higher
energy level to the number in the lower energy level. (1 eV=1.60 × 10-19 J).

2. At what temperature would one in a thousand of the atoms in a gas of atomic hydrogen
be in the n=2 energy level? (Beiser Problem 1)

3. The first excited sate in sodium is 2.093 eV above the ground state. Find the ratio
between the numbers of atoms in each state in sodium vapor at 1200 K. (Beiser Problem

4. The moment of inertia of the H2 molecule is 4.64×10-48 kg·m2. (a) Find the relative
populations of the J=0, 1, 2, 3, and 4 rotational states at 300 K. (b) can the populations of
the J=2 and J=3 states ever be equal? If so, at what temperature does this occur? (Beiser
Problem 5)
5. At what temperature will the average molecular kinetic energy in gaseous hydrogen
equal the binding energy of a hydrogen atom? (Beiser Problem 9)

6. Verify that the average value of 1/v for an ideal-gas molecule is . (Beiser Problem 13)
 Rayleigh-Jeans Formula
“OK, this quantum statistics stuff has some pretty math in it, but what good is it?”

We’ll find we need to use Fermi-Dirac statistics to “explain” properties of metals and
semiconductors.

Bose-Einstein statistics “explains” blackbody radiation.

What is a black body?

A blackbody is the best possible absorber / emitter of radiation.

The spectrum of blackbody radiation depends only on the temperature of the blackbody.

This is nice because you don't need to worry about the details of the composition of the
blackbody.

A box with a hole in it makes a good laboratory approximation to a blackbody emitter.

 Spectra of Black body radiation

Plotted to the right are a couple of spectra for blackbodies at different temperatures.
John William Strutt (Lord Rayleigh) tried to calculate this
classically.

To calculate the spectrum of radiation from a blackbody,

consider a box with a hole in it.

Radiation can get in the hole. It then reflects back and forth inside the cavity.

a spherical cavity turns out to be

the best device for
experimentally realizing
blackbody radiation
This problem may be discussed in several different contexts. If the radiation interferes
destructively, it will never get out. We only see radiation (waves) getting out that were able
to set up standing waves inside the cavity.

Our job is thus to determine what kinds of standing waves can exist in the cavity, and what
their energies are.
Consider a black body at temperature T.

The black body is a cubic cavity of length L.

We treat it classically then condition for standing wave formation will be

2 Lx
jx   1,2,3,....  no of half wavelengt hs in x direction

2 Ly
jy   1,2,3,....  no of half wavelengt hs in y direction

2 Lz
jz   1,2,3,....  no of half wavelengt hs in z direction


For standing wave in any arbitrary direction, it must be true that

2
 
2 2 2
 2 L  2 L  2 L   
2 L
j x2  j y2  j z2   z       z    
y

            (a)
j  0,1,2,... x

j y  0,1,2,...
j z  0,1,2,...
Let’s count the number of standing waves g(λ) dλ whose wavelengths lie between λ+ dλ

For this we have to count the number of permitted states jx, jy, jz values that yield the
wave lengths lie between λ+ dλ

Consider a j-space whose coordinate axes are jx, jy, and jz such that,

j jx2  j y2  jz2

The total number of wave lengths between λ and λ+d λ will be same as the number of
Points in j-space whose distance from origin lie between j and j+dj

The volume of spherical shell of radius j and j+dj=4πj2dj

 But we are intrested only in the octant of the shell having non-negative values of jx, jy, jz.
Also for each standing wave counted, there are two perpendicular direction of polarization.

Total number of standing waves in the cavity is

1 2
No. of standing waves g ( j )dj  (2) 4j dj  j 2 dj (b)
8

But we want number of standing waves in the cavity as a function of frequency ν instead of j.
Using equation (a), we can have
2L 2 L 2L (c)
j   dj  d
 c c

Using equation (c), equation (b) can be rewritten as

 2 L  2 L 8L3 2
2

No. of standing waves g ( )d     d  3  d

 c  c c
(d)
The volume of the cavity is L3.
Number of standing waves per unit volume will be
82 d
Density of standing wave in cavity G( )d  3 g  d 
1
L c3
(e)
Note that the density of standing wave in the cavity is
(1) proportional to ν2.
(2) Independent of shape and size of cavity.
(3) Higher the frequency, shorter is the wavelength and greater is
the number of standing waves are possible.
To get the energy density (energy per unit volume), simply multiply g(f) by the energy of an
oscillator of frequency f (we assume the waves originate in oscillators in the cavity walls).

Remember, kT/2 goes with each degree of freedom, and an oscillator has two degrees of
freedom, so multiply by kT.

The spectral energy density is thus

82 kT
u ( )d   G ( )d  kTG( )d  3
d
c

This is called the Rayleigh-Jeans formula because British mathematician and astronomer
James Jeans corrected a small mathematical error in Rayleigh’s work.
The formula leads to the "ultraviolet
catastrophe." It predicts increasing energy
density with increasing ν. It doesn't match theory
experiment at all. It doesn't even come
close. Something is seriously wrong.

experiment

Rayleigh produced a lifetime of brilliant work. He won the Nobel prize in 1904 for
discovering the inert gas argon. However, as Beiser points out, Rayleigh’s most
important contribution to physics may have been this disastrous theory of
blackbody radiation. Rayleigh died never really accepting the quantum theory of
light.

“An important scientific innovation rarely makes its way by gradually winning over and
converting its opponents…What does happen is that its opponents gradually die out”—Max
Planck.
 Planck Radiation Law
In the last section we derived the Rayleigh-Jeans formula for the spectral energy density for
blackbody radiation. We found that it failed miserably.

What's wrong with the Rayleigh-Jeans formula?

Rayleigh divided up the energy into kT/2 for each degree of freedom. This is fine for a
continuous energy distribution.

We now know that it doesn't work for harmonic oscillators, where energy is quantized in
units of hν. Therefore, our energy density was wrong.

Our density of standing wave modes,

8L3 2
No. of standing waves g ( )d  3  d
c

as calculated above is OK.

Planck assumed that the oscillations in the cavity walls are limited to
 n  nh ; n  1, 2, 3, . . .
Then he used Maxwell Boltzmann distribution to find the number of
oscillation with energy εn at temperature T   
 n 
 kT 
In such cases average energy per oscillator is e
h
  h
e kT
1
Plank’s radiation formula

8h  d 3
u ( )d   G( )d  3 h / kT
c e 1
 To get the correct energy density of photons in the cavity, we multiply our density of modes
by the energy of each mode and the probability as a function of T that a mode is occupied.

u ( )d  (energy of mode)  (density of mode)

 (probabili ty that mode is " occupied" )
u ( )d  hG ( ) f BE ( )d
8h  3
u ( )d  3 h kT d
c e 1
The above equation is called the Planck radiation formula, and it works very well.

It tells us that every body of condensed matter radiates, regardless of its temperature.

An object need not be so hot that it glows conspicuously in the visible region in order to
radiate.

The radiation from an object at room temperature is mainly in the far infrared part of the
spectrum to which eye is not sensitive.
 Wien's displacement law
You can calculate the wavelength at the peak of the energy density by expressing u as a
function of wavelength and taking the derivative.

8h  3
u ( )d  3 h kT d
c e 1
Use c = f  to write u = u() and set 0 = du
/d to find  for maximum. The result is
Wien's displacement law:

hc
 4.965
kTmax
λ max T = 2.898×10-3 m K .
 at which u is maximum!
not maximum  in spectrum!
Wien's displacement law tells which way the peak in the
blackbody spectrum shifts as the temperature changes.
You can write a formula for u(f) as we did, or for u(). The plots look similar:

But the Rayleigh-Jeans formula blows up as f   and as

  0 (can be visually confusing!).

Also, the peak in the spectrum shifts towards higher f as T increases, but to lower .

In these plots, B corresponds to our u and  corresponds to our f.

 The Stefan-Boltzmann Law

The total energy density inside the cavity is found by integrating the energy density over all
frequencies.

 8h f3
utotal =  0 c3 ehf / kT -1
df = a T 4 .
a constant
The result is proportional to T 4.

The Stefan-Boltzmann law says R=eσT4, where R is the radiated energy per second
per unit area, and e is the emissivity of the radiating surface, and σ is a constant (see Beiser
for the value of σ).
 What is phonon?
• Consider the regular lattice of atoms in a uniform solid material.
• There should be energy associated with the vibrations of these
atoms.
• But they are tied together with bonds, so they can't vibrate
independently.
• The vibrations take the form of collective modes which propagate
through the material.
• Such propagating lattice vibrations can be considered to be sound
waves.
• And their propagation speed is the speed of sound in the material.
 Phonon

• The vibrational energies of molecules are quantized and

treated as quantum harmonic oscillators.
• Quantum harmonic oscillators have equally spaced energy
levels with separation ΔE = h.
• So the oscillators can accept or lose energy only in discrete
units of energy h.
• The evidence on the behaviour of vibrational energy in
periodic solids is that the collective vibrational modes can
accept energy only in discrete amounts, and these quanta of
energy have been labelled "phonons".
• Like the photons of electromagnetic energy, they obey Bose-
Einstein statistics.
PHONONS PHOTONS
• Quanta of lattice vibrations • Quanta of electromagnetic
• Energies of phonons are radiation
quantized • Energies of photons are
quantized as well

h s hc
E phonon  E photon 
 
~a0=10-10m
~10-6m

h
p phonon  p photon 
h
 
 Global Warming?

It is a fact that human activity has put enormous amounts of “extra” CO 2 into the
atmosphere since the beginning of the industrial revolution.

It is also a fact that CO2 is a greenhouse gas.

There exists extensive data which suggests the

earth is warming. Much of the data is subject to
interpretation. (i.e., one might say “yes, warming,”
or one might say “coincidence, not proof.”