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Statistical Mechanics
in the
Canonical Ensemble
Outline of the
Formalism
and
Some Examples
(similar to parts of
Chs. 6 & 7
in Reif’s book)
The Canonical Ensemble:
Outline of the General Formalism
1 UkT r
Ur
pr e Z e kT
Z r
Z r
Z Ur
W
1 1
S k pi ln pi k ln k ln W
i i 1 W W
Entropy in The Canonical Ensemble
Ui
S k pi ln pi
Ui
Z e
1
pi e kT kT
i Z i
1 U
S piU i k ln Z pi k ln Z
T i i T
Helmholtz Free Energy
U
S k ln Z F U TS kT ln Z
T
• Ū Average value of the system
Internal Energy.
• (Ū - TS) Average value of the
Helmholtz Free Energy, F.
• The Partition Function Z is much more than a
mere normalizing factor. Z: Acts as a “Bridge”
linking microscopic physics (quantum states) to
the energy & so to all macroscopic properties of
a system.
Helmholtz Free Energy
F U TS kT ln Z
• F is a state function. Now, the calculation of some
thermodynamic properties of the system.
• Ignore the fact that Ū is an average & let U = Ū.
• Use the definitions for various thermodynamic variables.
For an infinitesimal, quasistatic reversible change:
F U TS dF dU TdS SdT
dF dQR PdV TdS SdT
dF TdS PdV TdS SdT PdV SdT
dF PdV SdT
F U TS kT ln Z
• Using the properties of partial derivatives gives:
F F T ln Z
P P k
V T V T V T
F F T ln Z
S S k
T V T V T V
• So, the energies of the microstates of the
system are linked to thermodynamic variables
such as pressure & entropy.
Various Measurable Parameters:
2nd Derivatives of the Helmholtz Free Energy F
• Elastic Moduli are the stress/strain or force/unit
area divided by the fractional deformation:
P F 2
K V V
V T V T
2
Q S F 2
CV T T 2
T V T V T V
Mean Internal Energy
• Ū Thermal Average of the system Internal
Energy. The actual internal energy fluctuates
because the system is interacting with the heat bath.
• How large are the fluctuations? Are they important?
(T ln Z )
U F TS kT ln Z kT
T V
T ln Z 2 ln Z
U kT ln Z kT ln Z kT
T V T
Fluctuations in Internal Energy
• A measure of the departure from the mean is the
standard deviation, as it is in any statistical theory.
( U ) U U U U
2
2 2 2
Ui
U U e i
kT
CV i
T V T
Ur
e r
kT
V
( U ) U U U U
2
2 2 2
Ui
U e
kT
i
1
CV
2
i
U U
2
T
U 2
r kT
e r
kT
V
2
( U ) U U kT CV
2 2 2
The Variance
The relative fluctuation (U/ Ū)
gives the most useful information.
U
2
kT CV
U U
• Ū & CV are extensive properties proportional to the size
of the system ~ N ( Number of particles in the system).
U 1
U N
• For Typical Macroscopic Systems with ~1023
particles, the fluctuations (U/ Ū) ~ 10-11
U 1
U N
• So, the fluctuations are tiny, which means that U & Ū
can be considered identical for all practical purposes.
• Based on this, it is clear that Macroscopic Systems
interacting with a heat bath effectively have their
energy determined by that interaction.
• Similar relationships can be found for other relative
fluctuations of properties of macroscopic systems.
Summary – Statistical Mechanics
• Microstate – The state of a system defined microscopically
– a complete description on the atomic scale.
• Macrostate – The state of a stystem of macroscopic size
specified by a few macroscopically observable quantities only.
• Statistical Weight (W or ) of a macrostate – is the
number of microstates compising the macrostate.
• Postulate of equal a priori probabilities – “for an
isolated system in a definite macrostate, the W microstates
comprising this macrostate occur with equal probability.
• Equilibrium Postulate – “For an isolated macroscopic
system, defined by U,V,N (which are fixed) and variable
parameters , equilibrium corresponds to those values of for
which the statistical weight W(U,V,N, ) attains its maximum.”
Boltzmann Definition of Entropy
S (U ,V , N , ) k ln W (U ,V , N , )
Definition of Temperature
1 S (U ,V , N )
T U V ,N
Definition of Pressure
S (U ,V , N )
P T
V U , N
General Definition of Entropy
S k pi ln pi
i
Canonical Ensemble Distribution
• pi Probability that the system at temperature T
is in the state i with energy Ui: 1 U i
pi e kT
Z
• Partition Function Sum over All Microstates:
U i
Z e kT
• Mean Energy: ln Z
U kT 2
T
Z e kT
e kT
e kT
2 cosh 2 cosh x
i kT
B
x
kT
• We can now calculate the probability of spin up
versus spin down.
1 kTU
i
p
1
e x p
1
e x
pi e
Z 2 cosh x 2 cosh x
1 .0
0 .9
0 .8
0 .7
Probability
0 .6
Sp in alig ne d (U = - B)
0 .5 Sp in an tia lign ed (U = + B)
0 .4
0 .3
0 .2
0 .1
0 .0
0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 3 .0
X=B/kT
• We can now calculate the mean magnetic
moment of our individual dipole.
1 1
p e x p e x
cosh x cosh x
p p (e e )
x x
2 sinh x
2 cosh x 2 cosh x
tanh x
• So the mean energy of an individual dipole is:
U B tanh x
• We have the values necessary for the individual
dipole and because our dipoles do not interact all
other dipoles must behave similarly.
• A solid of N dipoles therefore has an energy:
U N U NB tanh x
• And a mean magnetic moment (or magnetization)
in the direction of the applied field of:
M N N tanh x
• Note that U = -MB
• The magnetization or the magnetic moment L
per unit volume: M N tanh x
L
V V
Nx N 2
L B
V VkT
1 .0 1 .0
0 .9
Magnetisation / N/V
0 .8 0 .8
0 .7
0 .6 0 .6
Probability
Spin Up
0 .5 Spin Down
0 .4 Magnetisation 0 .4
0 .3
0 .2 0 .2
0 .1
0 .0 0 .0
0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 3 .0
X=b/kT
Reif, Figure 6-3-1
“Saturation
Magnetization”
“Curie’s Law” of Paramagnetism
M0 χH, χ (N0μ2)/(kT)
χ “Curie Susceptibility”
Curie’s “Law”
• The susceptibility is the magnetization per
applied field intensity which for small
magnetizations is given by H = B/0.
L N 0 2
1
H VkT T
dQ U B
CH NB tanh
T H T H T kT
0.4
Magnetic Heat Capacity
CH / Nk
0.2
0.0
0 1 2 3 4 5
1/X = kT/ B
This is also called The Schottky Heat Capacity
B 2 B
2
C H Nk sech
kT kT
• In fact, this is a general result for the heat
capacity in any two level system.
0.4
Magnetic Heat Capacity
CH / Nk
0.2
0.0
0 1 2 3 4 5
1/X = kT/ B
Isolated Paramagnetic Solid
• Now consider a very similar problem to the one just
discussed. Now, constrain (fix) the total energy U of the
isolated system.
• N total dipoles, n spin-up aligned with the applied B
field:
• U is obviously a function of n.
U ( n) ( N n) B nB B( N 2n)
• A given energy U(n) corresponds to a given number of
n spin up atoms with statistical weight:-
N!
W ( n)
( N n)! n!
• So, the Entropy is given by:
N!
S ( n) k ln W ( n) k ln
( N n)! n!
T becomes negative! 0 .9
0 .8
Probability
0 .6
Sp in alig ne d (U = - B)
0 .5 Sp in an tia lign ed (U = + B)
0 .3
than T , because it is a
0 .2
0 .1
0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 3 .0
Energy / NB
0.0 0.0
-0.5 -0.5
-1.0 -1.0
-5 -4 -3 -2 -1 0 1 2 3 4 5 -20 -10 0 10 20
Temperature 1 / Temperature