Classical Statistical Mechanics

in the Canonical Ensemble

 The Equipartition Theorem is
Valid in Classical Stat. Mech. ONLY!!!
Classical Statistical Mechanics
1. The Equipartition Theorem
2. The Classical Ideal Gas
a. Kinetic Theory
b. Maxwell-Boltzmann
Distribution
 The Equipartition Theorem is
Valid in Classical Stat. Mech. ONLY!!!
“Each degree of freedom in a system of
particles contributes (½)kBT to the
thermal average energy of the system.”
Note: 1. This theorem is valid only if each term
in the classical energy is proportional to a momentum
(p) squared or to a coordinate (q) squared.
2. The degrees of freedom are associated with
translation, rotation & vibration of the system’s
molecules.
• In the Classical Cannonical
Ensemble, it is straighforward to
show that
The average energy of a
particle per independent
degree of freedom  (½)kBT.
We just finished an outline of the proof
 The Boltzmann Distribution
Canonical Probability Function P(E):
• Defined so that P(E) dE  probability to find a
particular molecule between E & E + dE is:
e E kT
P(E ) 
kT
Z
Define: Energy Distribution Function
 Number Density  nV(E):
• Defined  nV(E) dE  Number of molecules per
unit volume with energy between E & E + dE
E kT
nV (E )  n0 e
Examples: Equipartition of Energy
in Classical Statistical Mechanics
Free Particle E  KE  mv2 2
(One dimension):
 mv 2 2 kT
e
P (v ) 
Z
kT
1 1
KE  m vx  kT
2

2 2
Equipartition Theorem Examples

LC Circuit:

1 d Harmonic Oscillator:
Equipartition Theorem Examples

Free Particle in 3 Dimensions:

Rotating Rigid Body:

1d Simple Harmonic Oscillator
1 1
KE  m vx  kT
2

2 2

1
PE  kT
2

E  E  KE  PE  kT
 Classical Ideal Monatomic Gas
For this system, it’s easy to show
that The Temperature is related to
the average kinetic energy. For one
molecule moving with velocity v in
3 dimensions this takes the form:
1 3
KE  m v  kT
2

2 2
Also, for each degree of freedom, it can be shown that
1 1 1 1
m v x  m v y  m v z  kT
2 2 2

2 2 2 2
 Classical Statistical Mechanics:
Canonical Ensemble Averages
Probability Function: e E kT
P(E ) 
kT
Z
• P(E) dE  probability to find a
particular molecule between E & E + dE
 
Normalization:  P(E )dE   P(v)dv  1
0 0
 E kT
e
P(E ) 
kT
Z


 EP(E )dE
E E  0
Average Energy: 

 P(E )dE
0

Average Velocity:  vP(v)dv

v v  0


 P(v)dv
0
 Classical Kinetic Theory Results
• We just saw that, from the Equipartition
Theorem, the kinetic energy of each particle in an
ideal gas is related to the gas temperature as:
<E> = (½)mv2 = (3/2)kBT (1)
v is the thermal average velocity.
• Canonical Ensemble Probability Function:
e E kT
P(E ) 
kT
Z
• In this form, P(E) is known as the
Maxwell-Boltzmann Energy
Distribution
 e E kT
P(E ) 
kT
Z
• Using <E> = (½)mv2 = (3/2)kBT along with
P(E), the Probability Distribution of
Energy E can be converted into a
Probability Distribution of Velocity P(v)
This has the form:
P(v) = C exp[- (½)m(v)2/(kT)]
• In this form, P(v) is known as the
Maxwell-Boltzmann Velocity
Distribution
 Kinetic Molecular Model for Ideal Gases
Assumptions
1. The gas consists of large number of individual
point particles (zero size).
2. Particles are in constant random motion &
collisions.
3. No forces are exerted between molecules.
Equipartition Theorem: 
Gas Kinetic Energy is Proportional to the
Temperature in Kelvin.
3
KE   R  T
2
 Maxwell-Boltzmann Velocity Distribution
• The Canonical Ensemble gives a distribution
of molecules in terms of Speed/Velocity or
Energy.
• The 1-Dimensional Velocity Distribution
in the x-direction (ux) has the form:
1
dN  mu x / k T
2

 A e 2  du x
N
Maxwell-Boltzmann dN 1
 mu x 2 / k T
Velocity Distribution N  A  e 2  du x

Low T High T
 3D Maxwell-Boltzmann Velocity
Distribution a  (½)[m/(kBT)]
 dN  a  au x 2  dN  a  au z 2
   e  du x    e  du z
 N 1D u x   N 1D u z 

 dN  a au y 2
   e  du y
 N 1D u y 

In Cartesian Coordinates:
3/ 2
 dN  a  a[u x 2  u y 2  u z 2 ]
    e  du x  du y  du z
 N  3D   
 Maxwell-Boltzmann Speed
Distribution
• Change to spherical coordinates in Velocity
Space. Reshape the box into a sphere in
velocity space of the same volume with radius u .
V = (4/3) u3 with u2 = ux2 + uy2 + uz2
dV = dux duy duz = 4  u2 du
 dN / N  4  au 2
    a u e
3/ 2 2
 du  3D 
3D Maxwell-Boltzmann Speed Distribution

Low T

High T
 Maxwell-Boltzmann Speed
Distribution
 dN / N  4  au 2
    a u e
3/ 2 2
 du  3 D u 
Convert the speed-distribution into an energy-
distribution:  = (½)mu2, d = mu du
3/ 2 
 dN / N  2  1  
      1/ 2
e kT
 d  3D    kT 
 Some Velocity Values from
the M-B Distribution
• urms = root mean square (rms) velocity
• uavg = average speed
• ump = most probable velocity

 dN 

( x ) average  x   
n n
 N x
Comparison of Velocity Values

Ratios in Terms of
urms uavg ump
kT 8 kT kT
3  2
m  m m

1.73 1.60 1.41

Maxwell-Boltzmann Velocity Distribution
f  v   T 3/ 2 exp  mv 2 / 2kT 
f  vi   T 3/ 2 exp  mvi2 / 2kT 
Maxwell-Boltzmann Speed Distribution
3/ 2
 m 
f  v   4 
 2 kT



v 2 exp mv 2 / 2kT 
Maxwell-Boltzmann Speed Distribution
3/ 2
 m 
f  v   4   v 2 exp  mv 2 / 2kT  ; N (v )  N  f (v )
 2 kT 

1/ 2 1/ 2 1/ 2
 2kT   8kT   3kT 
vm     v    vrms    ;
 m    m   m 
The Probability Density Function
•Random motions of the molecules
can be characterized by a probability
distribution function.
•Since the velocity directions are
uniformly distributed, we can reduce
the problem to a speed distribution
Function f(v)dv which is isotropic.
 The Probability Density Function
•Let f(v)dv  fractional number of
molecules in the speed rangefrom
v to v + dv.
•A probability distribution
function has to satisfy the
Condition: 
 f  v  dv  1
0
 The Probability Density Function
• We can use the distribution function to
compute the average behavior of the
molecules: 
 f  v  dv  1
0

 
v   vf  v  dv v   v f  v  dv
2 2
0 0

vrms  v 2