Degrees of freedom,

Equipartition of Energy and

Black Body Radiation

Prof. B.N. Jagatap

Department of Physics
IIT Bombay
Recapitulate

Classical Physics

Physics before 20th century, i.e., physics before the

birth of Quantum Mechanics

 Mechanics
 Electrodynamics
 Thermodynamics
Mechanics

Newton’s first law:

Law of inertia

Newton’s second law: F  ma

Introduces force ( F ) as responsible for the
change in linear momentum ( p  m v ) F  d p / dt

Newton’s second law: F21   F12

Law of action and reaction

m1m2 
Newton’s law of gravitation: F  G 2 r
r
Electrodynamics Maxwell’s Equations

Gauss’s law (Electric field)   E   / 0

Gauss’s law (Magnetic field) B  0

Faraday’s law   E   B / t

Ampere’s law   B   0 0  E / t

1  2
E
Wave equation  E 2 2
2

c t
1
Light is an electromagnetic wave with velocity c 
 0 0
Thermodynamics
Zeroth Law: This is the game
Two systems in thermal equilibrium with a third system are in
thermal equilibrium with each other.

First Law: You cannot win

You cannot get something out of nothing, because matter and
energy are conserved. E=Q+W

Second Law: You cannot break even

Any transfer of energy will result in some wastage (disorder)
unless temperature of absolute zero is achieved.
Stotal = Ssurrounding +Ssystem
Third Law: You cannot get out of the game
Absolute zero is unattainable.
 Law of Equipartition of Energy
Degrees of freedom (DF): The minimum number of
independent variables required for complete description
of the state of a physical system.

Monoatomic molecule:

3 translational DF
Diatomic rigid molecule

(a) Translational motion (b) Rotational motion along

(of centre of mass) along two axes  to the line
three  axes joining the two atoms.

Total degrees of freedom: 3 translational, 2 rotational

 Diatomic weakly bonded molecule

(a) Translational (b) Rotational motion (c) Vibrational

motion (of centre along two axes  to motion along
of mass) along the line joining the two the line joining
three  axes atoms. the two atoms.

Total DF: 3 translational, 2 rotational, 1 vibrational

Generalization: N-atom Molecule

Linear Molecules
Translational DF : 3
Rotational DF : 2
Vibarional DF : 3N-5

Non Linear Molecules

Translational DF : 3
Rotational DF : 3
Vibarional DF : 3N-6
Summary:

Translation* Rotation Vibration Total DF

Monatomic 3 0 0 3

Diatomic 3 2 1 6

Linear 3 2 3N-5 3N
polyatomic
(N>2)

Nonlinear 3 3 3N-6 3N
polyatomic
(N>2)
* Centre of Mass
Law of Equipartition of Energy

At finite temperature (T), the energy is distributed as:

1
kT For each Translational and Rotational DF
2

kT For each vibrational DF

(kT/2 each for KE and PE)

k is the Boltzmann constant  1.38 10 23 J .K 1

Supporting Material Boltzmann distribution
E
f ( E )  Ae

1-D translational motion (x-direction) kT

KE  mv 2x / 2 E  mv 2x / 2
f v  f ( v)dv
Average Energy
v v  dv

 Ef ( E )dv 
m
  mv 2x

 
e

v e dv x
2  1/ 2

dx   
2 kT
x 2
2 
x x

E  
  
 f ( E ) dv e
  mv 2x 

2 kT
dv x
 1/ 2
 e
x

dx 
- 
x 2 x 2

  m / 2kT 2 3 / 2
1


 kT
2
 E
Supporting Material f ( E )  Ae

kT

1-D oscillator
1 2 1 2
E  KE  PE  mv x  x
2 2
 = force constant
Average Energy
 mv 2x x 2   mv 2x / 2 kT x 2 / 2 kT
Ef ( E )dv x dx dx dv x  2  2 e
  
e
E   
 f ( E )dv x dx  dx  dv x e
 
e
 mv 2x / 2 kT x 2 / 2 kT

-  

  mv 2x / 2 kT x 2 / 2 kT  x 2   mv 2x / 2 kT x 2 / 2 kT
dx dv x  2
 
 mv 2x
e e   e e
   2 

e dx  e
 
x / 2 kT  mv 2x / 2 kT
dv x
2

 
  dx  dv mv   
 

x
2
x /2 e  mv 2x / 2 kT
e x 2 / 2 kT
 x / 2 e 2  mv 2x / 2 kT
e x 2 / 2 kT

E   

e dx  e
 
x / 2 kT  mv 2x / 2 kT
dv x
2

 

 mv  dv x  e  (x dx  e
   
2
/2 e  mv 2x / 2 kT x / 2 kT
dx 2
/ 2) e x / 2 kT  mv 2x / 2 kT
dv x
2 2

E   
  

e dx  e e dx  e
   
x / 2 kT  mv 2x / 2 kT
dv x x / 2 kT  mv 2x / 2 kT
dv x
2 2

   

 mv   (x
 
2
/2 e  mv 2x / 2 kT
dv x 2
/ 2) e x 2 / 2 kT
dx
1 1
x

E  
   kT  kT
e e
 
2 2
 mv 2x / 2 kT
dv x x 2 / 2 kT
dx

 kT
 
 Thinking of Physicists towards the end of 19th century

“The more important fundamental laws and the facts

of physical science have all been discovered and they
are so firmly established that the possibility of their
ever being supplanted in consequence of the new
discoveries is exceedingly remote…. Our future
discoveries must be looked for in sixth place of
decimal”

Michelson (1899)
But there were problems looking for satisfactory
answers………

 Black body radiation

 Specific heats of gases and solids

 Line spectra of atomic gases

 Photoelectric effect
 Cathode rays and X Rays

 Compton effect
 Blackbody Radiation
Any heated object radiates energy
 The hotter the body, the higher the frequency of radiation
 The frequency () of radiation is independent of the object
being heated. It depends only on the temperature (T)

Power emitted per

unit area per unit
frequency interval

Wavelength (nm)
Kirchhoff’s Theorem (1859)

e( )  J ( , T ) A( )

e() : Emissivity; Power emitted per unit area per unit

frequency by a heated object

A() : Fraction of incident power absorbed per unit area

per unit frequency

J(,T) : A universal function, same for all back bodies

Blackbody is a body for which A()=1,

It absorbs all the power incident on it, e( )  J ( , T )
Stefan’s Law (1879)
Total power (etotal) per unit area emitted at all frequencies by
a blackbody

etotal   e( )d  T


4  = Stefan-Boltzmann constant
= 5.6710-8 Wm-2K-4
0

Wien’s displacement Law (1893)

The wavelength of maximum
power emission shifts towards
shorter wavelength when T is
increased.

maxT = 2.89810-3 mK

Energy density of a blackbody

J ( , T ) Power emitted by a blackbody per unit

area per unit frequency

u ( , T ) Energy density of a blackbody, i.e., energy

per unit volume per unit frequency

c
J ( , T )  u ( , T )
4
 c
Supporting Material: How to show J ( , T )  u ( , T )
4

x  ct x
t 
c
V  A x
A

Energy  Power per unit area  t  A  2

Energy  2  Power per unit area  (x / c)  A

2
u J Additional factor 2?
c
 Supporting Material
Power emitted by
cu ( ) cos  surface A will spread
A out in the entire
hemisphere defined by
 0    /2 and 0  
 cu ( ) 2

Radiation emitted per unit area = u ( , T ) cdt

Power radiated per unit area
normal to the surface = u ( , T ) c cos 
Power radiated per unit d
area in solid angle d = cu ( , T )d cos 
4
cu ( , T )
 d  sin  cos d
d  sin dd
2  /2
J ( ) 
4
c
J ( , T )d  u ( , T )d
0 0

4
Energy density of a black body : u(,T)
(Energy per unit volume per unit frequency)

Black body radiation curve

u(,T) vs  u(,T) vs 

How to explain this behaviour?

 Wien’s Exponential Law

u ( , T )  A e
A guess work!
3   / T

A and  are constants

Does not agree for longer wavelengths (> 6m (6000 nm)) !
 Blackbody Cavity
Light entering the small
opening strikes the walls and
gets reflected in the cavity.

At each reflection, a portion

of the light is absorbed by the
cavity walls. After many
reflections, all of the incident
energy is absorbed.

Consider properties of waves in a box and work out an

expression for the radiation spectrum at temperature T.
 Waves in a box

Amplitude of wave in r-direction

A(r )  A0 sin(2 /  )r  A0 sin kr

 = wavelength, k = wave vector

Radiation in empty volume = L3

in thermal equilibrium with
L the container at temperature T

L L Can be viewed as the

superposition of standing
waves.
 Waves in a box
L A(r )  A0 sin(2 /  )r  A0 sin kr

L L Waves in x-direction
Waves which can fitted in the box must satisfy

nx x / 2  L nx are positive integers.

A( x)  A0 sin k x x k x  nx / L

For y- and z-directions:

A( y )  A0 sin k y y k y  n y / L

A( z )  A0 sin k z z k z  nz / L
 No. of standing waves in a box?

L frequency

L    d
L

8
 3 d
2
No. of modes per unit volume in
frequency interval  and d
c
Supporting Material

Modes of oscillation in 3-D

A( x, y, z )  A0 sin( k x x) sin( k y y ) sin( k z z )

k x  nx / L k y  n y / L k z  nz / L

Define,
2 2
k 2  k x2  k y2  k z2  (nx2  n y2  nz2 )  n2
L2 L2
2
2  n
k   
 c c L
 Counting Number of modes in frequency interval  and d
 2
 2
ny
k  kx  k y  kz 
2 2 2 2 2 2 2
(nx  n y  nz ) 
2
n
L 2
L
2

Volume of a spherical shell of

radius n and thickness dn  4n 2 dn
dn
1
No. of modes = N (n)dn  4n 2 dn
8
n

n
(factor 1/8 since nx, ny, nz all need be +ve integer) nx
n

k  n / L n  Lk /  dn  Ldk / 
k  2 / c
1  Lk  Ldk 1 3 2
2

N (n)dn      L k dk dk  2d / c
2    2 2

1  2   2 
2
V  L3
 V    d
2  c   c 
2

4 2
No. of modes per unit volume in  and +d  3 d
c
Now account for the Polarization of Electromagnetic Wave

Electric (E) and Magnetic (B)

fields of an electromagnetic wave
are  to each other and to the
direction of propagation (C).
There is an independent mode of
propagation in which E and B are
rotated through 90o w.r.t. C.

Any polarization of the wave can be expressed as the sum of

these two independent modes of propagation. Therefore
multiplying previous expression by 2,

8 2
 3 d
No. of modes per unit volume in
frequency interval  and d
c
Energy density of a blackbody = u ( , T )
= No. of modes per unit volume per unit frequency
X Average energy per mode


Ee  E / kT
dE
Invoke equipartition theorem: E  0
 kT



Average energy of a harmonic oscillator e  E / kT

dE
in thermal equilibrium = kT 0

8
Rayleigh-Jeans Law

u ( , T )  3 kT
2

c
Rayleigh-Jeans Law

Valid for h << kT

For high frequencies u(,T) diverges: Ultraviolet Catastrophe