Micro Canonical Ensemble − Some Case Studies

K.M. UDAYANANDAN,1,* R.K. SATHISH,1 P. SETHUMADHAVAN2

1. Department of Physics, Nehru Arts and Science College, Kerala, 671328, India
2. Department of Physics, S.N.G. College, Chelannur, Kerala 673616, India
E.mail: udayanandan_km@rediffmail.com

While teaching statistical mechanics, calculations of the thermodynamics

of physical problems using Micro Canonical Ensemble (MCE) are
seldom done except in the case of nonrelativistic free particles. Most of
the authors of popular text books1,2 directly pass over to Canonical
Ensemble (CE) without discussing the merits or demerits of micro
canonical ensemble. Hence to equip students with MCE we present
thermodynamics of six physical problems. It is also shown that the
existing methods provide only high temperature results for MCE in the
case of systems with quantum energies.

1 Introduction
Micro Canonical Ensemble (MCE) is a
collection of systems with constant energy,
constant number of particles and constant
volume. In statistical mechanics we aim at
obtaining the thermodynamic properties like
energy(E), pressure(P), entropy(S) , specific
heat(Cv), susceptibility(χ) etc for a system. For
this in MCE we calculate the number of
available states Ω for the particles to occupy in
the system. From Ω using Boltzmann relation:
S = klnΩ
entropy S is calculated and from S all other
thermodynamic quantities are obtained. Here k
is the Boltzmann’s constant. But calculation for
actual physical problems is quite difficult. T.L.
Hill in his book3 [p. 29] says that only for
simple systems Ω can be calculated. Kerson
Huang2 says “there seems little hope that we
can straight forwardly carry out the recipe of
the microcanonical ensemble for any system
but the ideal gas”. In this article we calculate Ω

Physics Education • July − September 2009 205

for three classical cases and three cases with momentum space. Particles have a 3N
quantum energy. dimensional momentum space and 3N
dimensional spatial space to occupy. In the
momentum space the particles will be
2 Classical Systems occupying on a sphere of radius R. Since
For classical systems we calculate Ω for entropy is related to the logarithm of this
particles with energy number of states it can be shown that logarithm
of the number of states contained in a volume
p2 with radius R (Σ) and surface area (Ω)are
i) , where p is the momentum and m is the
2m nearly equal.2 Hence for convenience we will
mass of the particle, choose the number of states within a volume of
ii) pc, where c is the velocity of light, radius R. Thus the total volume will be a
p2 1 2 product of the volume of spatial and
iii) + k ′q where k′ is the spring constant momentum space. A particle occupies a spatial
2m 2 volume V and hence N particles occupy volume
and q is the coordinate. For solving classical VN. Now we have to find the volume of the
problems we will imagine a combined p and q- particles in momentum space. Volume of a 3N-
space.1 dimensional sphere is given by1

3N
2.1 Nonrelativistic Free Particles
π 2
R3 N
V3 N ( R) =
The derivations present in this section in the 3N
case of a nonrelativistic free particles is not !
2
new in principle, but is present in a more
explicit, direct and complete manner which Total volume of the particles in momentum
makes it possible to find Ω for more complex and spatial space is
systems easily. The methods that we follow in
other cases are simply followed from the 3N
method given in this case. N π 2
R3 N
For classical non relativistic free particles V
3N
with same mass m, popularly known as !
2
Boltzmann gas, the Hamiltonian
Substituting the value of R, total volume
p2
3N
H= ∑ i occupied is
i =1 2m
3N 3N

where pi is the momentum of the ith particle in N π 2

(2mE ) 2
V
one direction. Rearranging 3N
!
2
3N 3N

∑p
i =1
2
i = 2m∑ ε i = 2mE = R 2
i =1
But the minimum volume required for
occupation of a micro state is h3.1 Hence the
number of states available is
Here we imagine a p-space (momentum space)
and R is the effective radius of N particles in
206 Physics Education • July − September 2009
 3N
2.3 Relativistic Massless Free Particle
⎛ V ⎞ (2π mE )
N
2

∑ = ⎜⎝ h3 ⎟⎠ 3N Here for massless relativistic free particles

! Hamiltonian
2
3N
⎡ 3
⎤
V ⎛ 4π mE ⎞ 2 ⎥ 3
H= ∑pc i
ln ∑ = N ln 3 ⎜
⎢
⎟ + N i =1
⎢ h ⎝ 3N ⎠ ⎥ 2
⎣ ⎦ εi = pic
Entropy S is given by the Boltzmann relation 3N
1 3N E
∑p
i =1
i = ∑
c i =1
εi = = R
c
S = klnΩ ≈ klnΣ
Here R is effective radius of N particles in
⎡ 3
⎤ momentum space. Total volume of the particles
V ⎛ 4π mE ⎞ 2
⎥ + 3 Nk
S = NK ln ⎢ 3 ⎜ in momentum and spatial space is
⎢ h ⎝ 3 N ⎟⎠ ⎥ 2
⎣ ⎦
3N
3N
Rearranging ⎛E⎞ 2
π 2
⎜ ⎟
⎛ 2S ⎞ VN ⎝c⎠
2
3h N ⎜ −1⎟
3N
E= 2
e ⎝ 3 Nk ⎠
!
2
4π mV 3

From I law of thermodynamics(TD) The number of states is

TdS = dE + PdV − μdN 3N
3N
⎛E⎞
Hence N π 2
⎜ ⎟
⎛V ⎞ ⎝c⎠
∑=⎜ 3 ⎟
⎛∂ E ⎞ ⎝h ⎠ 3N
T =⎜ ⎟ !
⎝ ∂ S ⎠V , N 2

3 ⎡ 2 2⎤
3

E= ⎛ 2π ⎞ ⎥+ 3N
ln ∑ = N ln ⎢ 3 3 ⎜
NkT V E
2 ⎢ h c ⎝ 3 N ⎟⎠ ⎥ 2
Again using I law of TD ⎢⎣ ⎥⎦

⎛∂S ⎞ Entropy S is given by

T⎜ ⎟ =P
⎝ ∂ V ⎠E , N
⎡ 2 2⎤
3
⎛ 2π ⎞ ⎥ + 3 Nk
S = Nk ln ⎢ 3 3 ⎜
NkT V E
P= ⎢ h c ⎝ 3 N ⎟⎠ ⎥ 2
V
⎢⎣ ⎥⎦
The above two equations give the Equation of
State (EoS) for non relativistic ideal gas. Rearranging

Physics Education • July − September 2009 207

 1 Total volume of the particles in momentum
⎡ 2 2 ⎛ 2S ⎞ ⎤2
and spatial space is VpVq, where
⎢ 3h c N ⎜⎝ 3 Nk −1⎟⎠ ⎥
E= e
⎢ 2
⎥ 3N 3N
⎣ 2π V 3
⎦ π 2
(2mE1 ) 2
Vp =
E=3NkT 3N
!
2
NkT
P= and
V
3N
The above equations give the EoS for any 3N
⎛ 2 E2 ⎞ 2
massless relativistic ideal gas π 2
⎜ mω 2 ⎟
Vq = ⎝ ⎠
3N
2.4 Nonrelativistic Harmonic Oscillator !
2
Harmonic oscillator is one of the simplest of The number of states is
systems with both kinetic and potential energy.
3N
It has been extensively studied both classically 3N 3N
⎛ 4π 2 ⎞ 2
as well as quantum mechanically. It has served ( E1 ) 2
( E2 ) ⎜ 2 ⎟
2

⎝ω ⎠
N
as the first approximate solution to many new ⎛ 1 ⎞
∑=⎜ 3 ⎟
physics problems and played a very important ⎝h ⎠ 3N 3N
! !
role in the development of nonrelativistic 2 2
quantum mechanics, Plancks radiation law,1
theory of specific heat,1 etc. and many other ⎡ 3
⎤
⎢ 1 ⎛ 16π 2
E E ⎞ 2
⎥ + 3N
areas. Hence it is always of great academic ln ∑ = N ln 3 ⎜ 1 2

value to investigate the thermodynamics of a ⎢ h ⎝ 9ω 2 N 2 ⎟⎠ ⎥

⎣⎢ ⎥⎦
harmonic oscillator.
For non relativistic harmonic oscillator, Entropy S is given by
Hamiltonian
⎡ 3
⎤
3N
⎛ p 2
1 ⎞ ⎢ 1 ⎛ 16π 2 E1 E2 ⎞ 2 ⎥
S = Nk ln 3 ⎜ + 3 Nk
H= ∑ ⎜ 2m + 2 mω qi 2 2
i ⎟ ⎢ h ⎝ 9ω 2 N 2 ⎟⎠ ⎥
i =1 ⎝ ⎠ ⎢⎣ ⎥⎦

Here pi and qi form separate space, the first one S = S1 + S2

is p-space and the second one is q-space. Let ⎡ 3
⎤
the total kinetic energy be E1 and the total 1 ⎛ 4π mE ⎞ 2
⎥ + 3 Nk
S = Nk ln ⎢ 3 ⎜ 1
potential energy be E2 and the effective radius ⎢ h ⎝ 3 N ⎟⎠ ⎥ 2
in the momentum space be R1 and that in the ⎣ ⎦
spatial space be R2
⎡ 3
⎤
⎛ 4 π E ⎞ 2
⎥ + 3 Nk
+ Nk ln ⎢⎜ 2
⎢⎝ 3 Nmω 2 ⎟⎠ ⎥
3N 3N

∑p
i =1
2
i = 2m∑ ε i = 2mE1 = R12
i =1
⎣ ⎦
2

3N
2 3N
2 E2 where
∑q
i =1
2
i =
mω 2
∑ ε ′ = mω
i =1
i 2
= R22

208 Physics Education • July − September 2009

 ⎡ 3
⎤ these systems specifically to compare the final
1 ⎛ 4π mE ⎞ 2
⎥ + 3 Nk
S1 = Nk ln ⎢ 3 ⎜ 1 results obtained for both classical and quantum
⎢ h ⎝ 3 N ⎟⎠ ⎥ 2 cases. Finally we will find that we obtain the
⎣ ⎦ same results as that of the classical cases,
which is in fact an inherent defect of this
⎡ 3
⎤
⎢ ⎛ 4π E2 ⎞ 2 ⎥ 3 Nk method. To be more exact we get the classical
S 2 = Nk ln ⎜ 2 ⎟
+
⎢⎝ 3 Nmω ⎠ ⎥ 2 results for quantum systems and hence a
⎣ ⎦ classification of the systems based on the spin
(a classification like Boson or Fermion) is not
The above equations show that entropy S is not
necessary. The exact thermodynamics can be
a function of volume in the case of harmonic
obtained by actually counting the number of
oscillator.
states or by deriving the exact formula for
Hence pressure
quantum systems. One such attempt has been
P=0 done in the case of quantum harmonic
oscillators4 and another in the case of
At constant V and N
paramagnetism.5 But to get exact Ω for
∂ S1 1 different systems like ferromagnets,
= diamagnets or collection of photons etc is very
∂ E1 T
difficult.
3
E1 = NkT
2 3.1 Nonrelativistic Free Particle (Non
relativistic Particles in a Box)
3
E2 = NkT
2 Energy quantization in atoms and molecules
plays an essential role in the physical sciences.
E = E1 + E2 = 3NkT A simple example of application of this, which
has great pedagogical value, is the study of a
3 Quantum Systems particle in a one-dimensional box, i.e., an
infinite one-dimensional square well.
We calculate for three quantum cases which Quantizing particle in a box is the way in
are the quantum equivalent energies of the which one is able to introduce the concepts of
above described classical cases. They are energy quantization. Beside quantum
n2 h2 mechanical interests it will be always
i) , where n=1, 2, 3,. . ., h is Planck’s interesting to find the statistical mechanics in a
8mL2
constant and L is the length of the box particle box. For non relativistic free particles
1 with same mass confined in a box, energy
hc 2
ii) (nx + n y2 + nz2 ) 2 , where nx, ny and nz = 1, eigen value is
2L
2, 3 . . .
ni2 h 2 ni2 h 2
⎛ 1⎞ εi = =
iii) ⎜ n + ⎟ hν , where n=0, 1, 2, 3, . . . and ν is 8mL2 2

⎝ 2⎠ 8mV 3
the frequency of the quantum oscillator.
where L is the length and V is the volume of
For solving quantum problems we will the box.
assume a continuum n-space.2 We had taken

Physics Education • July − September 2009 209

 2 2 box which is same for the non relativistic ideal
3N
8mV 3 3N
8mV 3 gas.
∑
i =1
ni2 =
h2
∑
i =1
εi =
h2
E = R2

3.2 Quantum Relativistic Massless Free

In this case we have n-space, hence the number Particle (Massless Relativistic Free
of states is directly obtained. Since only
Particles in a Box)
positive values of n are allowed the permissible
th
volume is only 18 of the total volume. Thus For relativistic free particles with same mass
confined in a box, the energy eigen values are
3N
⎛ 2
⎞ 2
1
⎜ 8mπ EV 3 ⎟ εi = (
hc 2
nix + niy2 + ni2z ) 2
⎜
N ⎜ h2 ⎟ 2L
⎟
⎛ 1⎞ ⎝ ⎠
∑=⎜ 3⎟
⎝2 ⎠ 3N 1 1
! 3N
2V 31 3N
2V 3
2
∑
i =1
(n + n + n ) =
2
ix
2
iy
2
iz
hc
2
∑
i =1
εi =
hc
E=R
Rearranging
3N 3N 3N
⎛V ⎞
N
( 2π mE ) 2 π 2 ⎛E⎞
⎜ ⎟
∑=⎜ 3 ⎟ ⎛V ⎞
N
⎝h ⎠ 3N ∑=⎜ 3 ⎟ ⎝c⎠
! 3N
2 ⎝h ⎠ !
2
⎡ 3
⎤
V ⎛ 4π mE ⎞ 2
⎥+ 3N
ln ∑ = N ln ⎢ 3 ⎜
⎢ h ⎝ 3 N ⎟⎠ ⎥ 2 ⎡ 2 2⎤
3
⎛ 2π ⎞ ⎥+ 3N
ln ∑ = N ln ⎢ 3 3 ⎜
⎣ ⎦ V E
⎢ h c ⎝ 3 N ⎟⎠ ⎥ 2
Entropy S is given by ⎢⎣ ⎥⎦

⎡ 3
⎤
⎢ V ⎛ 4π mE ⎞ 2 ⎥ 3 ⎡ 2 2⎤
3
S = Nk ln 3 ⎜ ⎟ + Nk ⎛ 2π ⎞ ⎥ + 3 Nk
S = Nk ln ⎢ 3 3 ⎜
V E
⎢ h ⎝ 3N ⎠ ⎥ 2
⎣ ⎦ ⎢ h c ⎝ 3 N ⎟⎠ ⎥ 2
⎢⎣ ⎥⎦
Rearranging
⎛ 2S ⎞ Rearranging
3h 2 N ⎜ −1⎟
E= 2
e⎝ 3 Nk ⎠

1
4π mV 3 ⎡ 2 2 ⎛ 2S ⎞ ⎤2
⎢ 3h c N ⎜⎝ 3 Nk −1⎟⎠ ⎥
3 E= e
E= NkT ⎢ 2
⎥
2 ⎣ 2π V 3
⎦

NkT E=3NkT
P=
V
The above two equations give the Equation of NkT
P=
State (EoS) for non relativistic particles in a V
210 Physics Education • July − September 2009
The final equations we obtained are same as ⎡ 3
⎤
that of relativistic ideal gas. ⎢ ⎛ π E 2
⎞ 2
⎥ + 3 Nk
S = Nk ln ⎜
⎢⎝ 6 Nh 2ν 2 ⎟⎠ ⎥ 2
⎢⎣ ⎥⎦
3.3 Harmonic Oscillator
The final equations are identical to the classical
Quantum harmonic oscillators can be classified harmonic oscillator.
into four groups. Oscillators with same
frequency which oscillate about a fixed
equilibrium position are called Einstein 4 Conclusions
oscillators. Oscillators with frequency varying In this short article we had explicitly shown
from 0 to infinity are called Planck oscillators.
that it is possible to use MCE to obtain the
Third type of oscillators with frequency
thermodynamics of different systems in
varying from 0 to a finite value is called De contrary to the common notion that only
bye oscillators. Oscillators whose center of thermodynamics of free particles can be solved
oscillation are not fixed, but can take any with MCE. We also show that MCE can be
where in a plane is the fourth oscillator and is taught more elaborately than the present
called Landau oscillators.6 We in this section manner, so that basic principles of statistical
develop the thermodynamics of Einstein mechanics and its relation with
oscillators neglecting zero point energy. These thermodynamics can be introduced with
type of oscillators has been used to explain
clarity. But the method suggested in Ref.[1]
specific heat of solids.1 Besides it serves as a and [2] only give high temperature results for
simple quantum system whose complete quantum energies. Thus the conventional
thermodynamics can be obtained very easily.
methods only provide high temperature
For an Einstein oscillator,4 the energy eigen equations for different physical systems. Hence
value is given by to get the complete thermodynamics we have
ei = nihν to go for Canonical Ensemble or Grand
Canonical Ensemble.
where ν is the frequency of the oscillator
3N 3N
εi E References
∑ n = ∑ hν
i =1
i
i =1
=
hν
=R
1. Kerson Huang, “Statistical Mechanics”, Wiley
3N Eastern Ltd, 4th edition (1991).
⎛ π E2 ⎞ 2 2. R.K. Pathria, “Statistical Mechanics”, Second
⎜ 2 2⎟ Edition, Butterworth/Heinmann (1999).
4h ν ⎠
∑=⎝ 3. Terrell L. Hill, “Statistical Thermodynamics”,
3N Dover Publications, New York (First South
! Asian edition, 2008).
2
4. American Journal of Physics, Arthur V
⎡ 3
⎤ Tobolsky, 799-802 (1964).
⎢ ⎛ π E 2
⎞ 2
⎥+ 3N 5. C. Kittel, “Introduction to Solid State Physics”,
ln ∑ = N ln ⎜
⎢⎝ 6 Nh 2ν 2 ⎟⎠ ⎥ 2 5th Edition, Wiley Eastern Ltd (1993).
⎢⎣ ⎥⎦ 6. K.M. Udayanandan and P. Sethumadhavan,
Physics Education, January-March, 2008.
Entropy S is given by

Physics Education • July − September 2009 211

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212 Physics Education • July − September 2009