1.

6 Classical Statistical Mechanics

http://personal.rhul.ac.uk/UHAP/027/PH4211/

b.cowan@rhul.ac.uk

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Classical Statistical Mechanics
• Classical Mechanics is best formulated in terms of position (q) and momenta (p)
coordinates (inc. generalized coordinates).


• So we would say a state is specified when we know all the position and
momenta coordinates.


• The p − q space is called phase space. 


• So in classical mechanics a state is a point in phase space.


• Difficulty in counting such states since p and q vary continuously; there would
be an infinite number of states in any region of phase space.


• In Statistical Mechanics it is expedient to erect a grid in phase space with cells

Δqx Δqy Δqz Δpx Δpy Δpz.


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 • In classical statistical mechanics
a state corresponds to a cell in
phase space.


• I.e. a system is in a given (micro)

state if it is in a specified cell in
phase space.



A state in phase space.






• What should be the size of the

cells?


• Dimension of p × q is action (like

in Planck’s constant h).


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• We argue that the precise size of the cells should not be important. 


• But we note that Quantum Mechanics (Uncertainly principle) tells us we cannot

discern a state to finer than a Δp Δq cell smaller than Planck’s constant.




Our Philosophy
• We shall write the size of a Δp Δq cell as h. At this stage its size will be un-
determined. Later, by comparing results with those calculated by quantum
statistical mechanics, we will identify this h as Planck’s constant.


Connection between classical/quantum statistical mechanics

• The general rule is that sums over states in the quantum case correspond to
integrals over phase space in the classical case. 



1
∫
→ 3 d3p d3q

∑ h
single particle states
Note the appearance of the h factors ensures dimensionality.
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1.6.2 Boltzmann and Gibbs Phase Spaces
.

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1.6.3 The Fundamental Postulate in the Classical Case

The classical version of the Fundamental Postulate states that for an

isolated system all available regions of phase space on the constant
energy hypersurface are equally likely.

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1.6.4 The classical partition function

The classical analogue of the quantum partition function is given by

1
Z = 3N ∫ e−H ( pi ,qi ) kT d 3N p d 3N q
h

The function H ( pi ,qi ) is the energy of the system expressed as a

function of the position and momentum coordinates {qi } and {pi } . This
is the Hamiltonian.

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1.6.5 The equipartition theorem
Energy of ith degree of freedom
1
Ei = ∫ Ei e ( 1 i N 1 i N ) d 3N q d 3N p
− E q ...q ...q , p ... p ... p kT

− − no pi − −
↓ ↓
− E ( q1 ...qi ...qN , p1 ..... pN ) kT
∫ i dpi ∫ e
− Ei
E e kT
d 3 N q d 3 N −1 p
Ei =
∫ e − Ei kT
dpi ∫ [same integral as above - no pi ]

∫ i
− Ei kT
E e dpi
Ei =
∫
− Ei kT
e dpi
Use the beta trick: β = 1/kT….

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gives
− β Ei ∂ − β Ei
Ei e =− e
∂β
so that
1
Ei = − − β E
∂
∫
− β Ei
e d pi =
∂
ln ( ∫ d pi
e − β Ei
)
∫ e d pi ∂β
i ∂β

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1.6.6 Consequences of equipartition

• Each “quadratic” degree of freedom gives internal energy kT/2 .

• Lattice vibrations (p and q contributions): CV = 3R per mol.

3
• Gas of particles (only p contribution): CV = R per mol.
2

Equipartition breaks down when quantum effects become important – at

low temperatures.

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1.6.7 Liouville’s theorem

Entropy – classical analogue of

S = −k ∑ Pj ln Pj = −k ln P
j

is
S = −k ∫ ρ ln ρ d n p d n q = −k ln ρ
where ρ ( pi ,qi ,t) = density of points in phase space.

Evolution of S (or ρ) with time? Should be consistent with Second Law.

But… Liouville’s theorem →

dρ
=0
dt
- S appears to remain constant !!!!!!!!!

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1.6.8 Boltzmann’s H theorem

1 2

Evolution of a region of phase space

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1.6.8 Boltzmann’s H theorem

1 2

Evolution of a region of phase space

evolves to which
appears as

Apparent reduction in density in phase space

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Chapter 2
Practical Calculations with Ideal
Systems

2.2 Identical Particles

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2.2.1 Indistinguishability

If we had an assembly of N identical but distinguishable particles the

resultant partition function would be the product of the (same) partition
functions of a single particle, z

Z = zN .

The key question is that of indistinguishability of the atoms or

molecules of a many-body system. When two identical molecules are
interchanged the system is still in the same microstate, so the
distinguishable particle result overcounts the states in this case.

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Now the number of ways of redistributing N particles when there are n1
particles in the first state, n2 particles in the second state etc. is

N!
n1 ! n2 ! n3 !......

so that for a given distribution {ni} the partition function for identical
indistinguishable particles is

n1 ! n2 ! n3 !...... N
Z= z .
N!

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2.2.2 Classical approximation

In the classical case we have then

1 N
Z= z .
N!
The Helmholtz free energy
F = −kT ln Z
is thus
F = − NkT ln z + kT ln N ! .

This is N times the Helmholtz free energy for a single particle plus an
extra term depending on T and N. So the second term can be ignored so
long as we differentiate with respect to something other than T or N.
Thus when differentiating with respect to volume to find the pressure,
the result is N times that for a single particle.

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2.3 Ideal Classical Gas
2.3.2 Classical approach
The classical partition function is given by the integral
1 −ε kT 3 3
z = 3 ∫e d pd q
h
where for the ideal gas ε = p 2
2m . Thus the q integrals are trivial,
giving a factor V, and we have
3
V ⎡ − p2 2 mkT ⎤
∞
z= 3 ⎢∫ e dp ⎥
h ⎣ −∞ ⎦ .
The integral is transformed to a pure number by changing variables:
p = x 2mkT so that
3
32⎡ ⎤
∞
V
z = 3 ( 2mkT ) ⎢ ∫ e dx ⎥
− x2

h ⎣ −∞ ⎦.

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As in the quantum calculation, the physics is all outside the integral and
the integral is just a pure number. The value of the integral is π so
that
32
⎛ 2π mkT ⎞
z =⎜ 2 ⎟ V
⎝ h ⎠
just as in the “quantum” calculation. This justifies the use of h in the
normalization factor for the classical state element of phase space.

Write
V h
z= 3, where Λ= .
Λ ( 2π mkT )
32

Here Λ is known as the thermal de Broglie wavelength. It has a very

important meaning.

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2.3.3 Thermodynamic properties
We start from the Helmholtz free energy:
⎡⎛ 2π mkT ⎞3 2 Ve ⎤
F = −kT ln Z = NkT ln ⎢⎜ 2 ⎟ ⎥
⎢⎣⎝ h ⎠ N ⎥⎦ ,
giving
∂ ln Z ∂ ln z NkT
p = kT = NkT =
∂V T , N ∂V T V .
This is the ideal gas equation, and from this we identify k as
Boltzmann’s constant.

The internal energy is

∂ ln Z d ln T 32
3
E = kT 2 = NkT 2 = NkT
∂T V ,N dT 2 .

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This is the result we obtained previously from equipartition. This gives
another important property of an ideal gas: the internal energy depends
only on temperature (not pressure or density). This is known as Joule’s
law. From the energy expression we obtain the thermal capacity
∂E 3
CV = = Nk
∂T V , N 2 .
This is a constant, independent of temperature, in violation of the Third
Law. This is because of the classical approximation – ignoring multiple
state occupancy etc. We also find the entropy and chemical potential:
⎡⎛ 2π mkT ⎞3 2 kTe5 2 ⎤
S = Nk ln ⎢⎜ 2 ⎟ ⎥,
⎢⎣⎝ h ⎠ p ⎥⎦
⎡⎛ 2π mkT ⎞3 2 kT ⎤
µ = −kT ln ⎢⎜ 2 ⎟ ⎥.
⎢⎣⎝ h ⎠ p ⎥⎦

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Sackur-Tetrode equation

⎡⎛ 2π mkT ⎞3 2 kTe5 2 ⎤
S = Nk ln ⎢⎜ 2 ⎟ ⎥
⎢⎣⎝ h ⎠ p ⎥⎦
⇒
5
S = Nk ln T − Nk ln p + Nks0
2

• Latter equation can be derived by thermodynamics alone.

• Constant s0 known as the Sakur-Tetrode constant

Naïve interpretation of this equation is wrong.

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2.3.4 The 1/N! term in the partition function

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