Microcanonical Ensemble Unit 8

The microcanonical ensemble
Finding the probability distribution

We consider an isolated system in the sense that
the energy is a constant of motion.
N
E H ( p, q ) E
We are not able to derive from first principles

Two typical alternative approaches
Postulate of Equal a Priori Probability

Construct entropy expression from it and
show that the result is consistent
with thermodynamics
Use (information) entropy as starting

concept
Derive from maximum entropy
principle
Information entropy*
Introduced by Shannon. See textbook and E.T. Jaynes, Phys. Rev. 106, 620 (1957)
Idea: Find a constructive least biased criterion for setting up probability

distributions on the basis of only partial knowledge (missing information)
What do we mean by that?
Lets start with an old mathematical problem
Consider a quantity x with discrete random values
Assume we do not know the probabilities

We have some information however, namely
x1 , x2 , ..., xn
p1 , p2 , ..., pn
n
p
i 1
and we know the average of the function f(x) ( we will also consider cases
where we know more than one average)
f ( x ) pi f ( xi )
i 1
With this information, can we calculate an average of the function g(x) ?

To do so we need all the p1 ,
n
p
i 1
p2 , ..., pn but we have only the 2 equations
1 and f ( x ) pi f ( xi )
i 1
we are lacking (n-2) additional equations
What can we do with this underdetermined problem?

n
There may be more than one probability distribution creating f ( x ) pi f ( xi )

We want the one which requires no further assumptions
We do not want to prefer any pi if there is no reason to do so
i 1
Information theory tells us how to find this unbiased distribution

(we call the probabilities now rather than p)
Shannon defined information entropy, Si:
Si k n ln n
n
or
Si k dpdq ( p, q )ln ( p, q )
for continuous distribution
with normalization
n
dpdq ( p, q) 1
We make plausible that:

- Si is a measure of our ignorance of the microstate of the
system.
More quantitatively
- Si is a measure of the width of the distribution of the n.
Lets consider an extreme case:

An experiment with N potential outcomes (such as rolling dice)
However:
Outcome 1 has the probability 1=1
Si k n ln n 0
n
Outcome 2,3, ,N have
n=0
-Our ignorance regarding the outcome of the experiment is zero.
-We know precisely what will happen
- the probability distribution is sharp (a delta peak)
ets make the distribution broader:

1 1 1 1
Si k n ln n k ln ln 0 ... 0
utcome 1 has the probability 1=1/2
2 2 2 2
n
utcome 2 has the probability 2=1/2
1
1
utcome 3,4, ,N have
n=0
k ln 2 ln 2 k ln 2
2
2
ets consider the more general case:
utcome 1 has the probability 1=1/M
utcome 2 has the probability 2=1/M Si k n ln n
utcome M has the probability M=1/M

utcome M+1, ,N have
n=0
1
1
1
1
1
1
ln
ln
... ln
... 0
M M
M M M M
k ln M
k
So far our considerations suggest:

Ignorance/information entropy increases with increasing
width of the distribution
Which distribution brings information entropy to a maximum
For simplicity lets start with an experiment with 2 outcomes
Binary distribution with 1, 2 and 1+ 2=1
Si k 1ln 1 2ln 2
1 2 1
with
Si k 1ln1 1 1 ln 1 1
dSi
1
1
k ln 1 1 ln 1 1 1 1
k
ln
d i
1
1 1
1
0.7
0.6
maximum
1
1
1 1
0.4
Si
dSi
k ln 1 0
d i
1 1
0.5
1 1/ 2 2
uniform distribution
0.3
0.2
0.1
0.0
0.0
0.2
0.4
0.6
0.8
1.0
Lagrange multiplier technique

Once again
Si k 1ln 1 2ln 2
at maximum
with
1 2 1
constraint
F ( 1 , 2 , ) k 1ln1 2ln 2 1 2 1
F
k ln 1 1 0
1
F
k ln 2 1 0
2
F
1 2 1 0
From
http://en.wikipedia.org/wiki/File:LagrangeMultiplier
Finding an extremum of f(x,y) under the constrain
1 2
1 2 1
1 1/ 2 2
Lets use Lagrange multiplier technique to find distribution that maximizes

M
Si k n ln n
n 1
1
n
n 1
F ( 1 , 2 ,..., M , ) k n ln n
n 1
F
k ln j 1 0
j
with
n 1
Si
max
1 2 ... M e 1 / k
1 2 ... M
1
M
maximizes entropy
k ln M
In a microcanonical ensemble where each system has N particles, volume V

and fixed energy between E and E+ the entropy is at maximum in equilibrium.
Distribution function
- When identifying information entropy with thermodynamic entropy
const.
( p, q )
1
Z (E)
if E H ( p, q ) E
0 otherwise
Where Z(E) = # of microstate with energy in [E,E+ ]

called the partition function of the microcanonical ensemble
Information entropy and thermodynamic entropy

When identifying k=kB
S k B n ln n
n
has all the properties we expect from the thermodynamic entropy

(for details see textbook)
We show here S is additive
S 1 2 S 1 S 2
S1
(1) n : probability distribution

for system 1
S2
(2) m : probability distribution

for system 2
Statistically independence of system 1 and 2

probability of finding system 1 in state n and system 2 in state m
S (1 2) k B n(1) m(2) ln n(1) m(2) k B n(1) m(2) ln n(1) ln m(2)

n,m
n,m
k B m(2) n(1) ln n(1) k B n(1) m(2) ln m(2)

m
k B n(1) ln n(1) k B m(2) ln m(2) S (1) S (2)

n
n m
(1)
(2)
Relation between entropy and the partition function Z (E)
S k B n ln n
n
1
1
1
k
lnZ
(
E
)
k B
ln
Z (E)
n Z (E)
n Z (E)
1
S k B lnZ ( E )
Derivation of Thermodynamics in the microcanonical Ensemble
Where is the temperature ?

In the microcanonical ensemble the energy, E, is fixed
E ( S ,V ) U ( S ,V )
with
dU TdS PdV
1 S
T U V
and
P S
T V U
Lets derive the ideal gas equation of state from the microcanonical ensemble
despite the fact that there are easier ways to do so
Major task: find Z(U) :=# states in energy shell [U,U+ ]
Z (U )
U+
1
3N
3N
d
p
d
q
3N
N !h U H ( p,q )U
another leftover from qm: phase space quantization, makes Z a dimensionless #
correct Boltzmann counting
Solves Gibbs paradox
requires qm origin of indistinguishability of atoms

We derive it when discussing the classical limit of qm gas
N
For a gas of N non-interacting particles we have H

i 1
1
Z (U )
N !h3 N
U
pi2
2m
i 1
N
V
d 3N p d 3N q
N ! h3 N
U
pi2
2 m U
i 1
pi2
2m
d 3 p1 d 3 p2 ...d 3 pN
pi2
i 1
3N dim. sphere
in momentum space
2 mU
VN
Z (U )
N !h3 N
U
d p1 d p2 ...d p N
pi2
2 m U
2 m (U )
2mU
V N C3 N
N !h3 N
2m(U )
3N / 2
2mU
3N / 2
V2 dim S2dim dr 2 rdr r 2
i 1
V3 N ( pU 2m(U )) V3 N ( pU 2mU )
Remember:
4
V3dim S3dim dr 4 r 2 dr r 3
3
...
V3 N dim S3 N dim dr r 3 N 1dr C3 N r 3 N
V U
3N / 2
U
1
S k B lnZ (U )

const
3N / 2
3
U
k B N ln V N ln U ln 1
2
U
ln const
3N / 2
In the thermodynamic limit of
N
V
U
lim a n 0
n
N
const
V
3
S k B N ln V N ln U
for 0 a 1
ln1=0
U
ln 1
3N / 2
http://en.wikipedia.org/wiki/Exponen
tiation
ln const
S k B N ln V N ln U ln const
2
with
1 S
T U V
P S
T V U
PV Nk BT
3
Nk BT
2

Microcanonical Ensemble Unit 8

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The microcanonical ensemble

Finding the probability distribution

We are not able to derive from first principles

Postulate of Equal a Priori Probability

Use (information) entropy as starting

Idea: Find a constructive least biased criterion for setting up probability

Assume we do not know the probabilities

where we know more than one average)

With this information, can we calculate an average of the function g(x) ?

p2 , ..., pn but we have only the 2 equations

we are lacking (n-2) additional equations

What can we do with this underdetermined problem?

There may be more than one probability distribution creating f ( x ) pi f ( xi )

Information theory tells us how to find this unbiased distribution

for continuous distribution

We make plausible that:

Lets consider an extreme case:

ets make the distribution broader:

utcome M has the probability M=1/M

So far our considerations suggest:

Lagrange multiplier technique

Finding an extremum of f(x,y) under the constrain

Lets use Lagrange multiplier technique to find distribution that maximizes

In a microcanonical ensemble where each system has N particles, volume V

Where Z(E) = # of microstate with energy in [E,E+ ]

Information entropy and thermodynamic entropy

has all the properties we expect from the thermodynamic entropy

We show here S is additive

(1) n : probability distribution

(2) m : probability distribution

Statistically independence of system 1 and 2

S (1 2) k B n(1) m(2) ln n(1) m(2) k B n(1) m(2) ln n(1) ln m(2)

k B m(2) n(1) ln n(1) k B n(1) m(2) ln m(2)

k B n(1) ln n(1) k B m(2) ln m(2) S (1) S (2)

Relation between entropy and the partition function Z (E)

Derivation of Thermodynamics in the microcanonical Ensemble

Where is the temperature ?

Major task: find Z(U) :=# states in energy shell [U,U+ ]

another leftover from qm: phase space quantization, makes Z a dimensionless #

correct Boltzmann counting

Solves Gibbs paradox

requires qm origin of indistinguishability of atoms

For a gas of N non-interacting particles we have H

V2 dim S2dim dr 2 rdr r 2

In the thermodynamic limit of

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