Scribd
Upload
46 views11 pages

The Canonical Ensemble: ZCT207/2 - 2 Statistical Mechanics

The document discusses the canonical ensemble in statistical mechanics. It describes a system S in contact with a heat reservoir R at temperature T, where S can exchange energy with R without changing T. The probability of S being in a state |n> is given by the Boltzmann distribution, which depends on the state energy En and partition function Z. The partition function contains thermal information about the system and determines averages like the internal energy and entropy based on temperature T.

Uploaded by

Nur Munirah
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
46 views11 pages

The Canonical Ensemble: ZCT207/2 - 2 Statistical Mechanics

The document discusses the canonical ensemble in statistical mechanics. It describes a system S in contact with a heat reservoir R at temperature T, where S can exchange energy with R without changing T. The probability of S being in a state |n> is given by the Boltzmann distribution, which depends on the state energy En and partition function Z. The partition function contains thermal information about the system and determines averages like the internal energy and entropy based on temperature T.

Uploaded by

Nur Munirah
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
You are on page 1/ 11

The Canonical Ensemble

To model this, we will consider a system let's call it S


in contact with a second system which is a large heat
reservoir let's call it R.
This reservoir is taken to be at some equilibrium
temperature T. The term "reservoir" means that the
energy of S is negligible compared with that of R.
In particular, S can happily absorb or donate energy
from or to the reservoir without changing the ambient
temperature T.
How are the energy levels of S populated in such a
situation? We label the states of S as |n , each of
which has energy En.
The number of microstates of the combined systems S
and R is given by the sum over all states of S,
ZCT207/2 - 2

Statistical Mechanics


But we know that SR/Etotal = 1/T , so we have

We now apply the fundamental assumption of


statistical mechanics that all accessible energy
states are equally likely.
This means that each of the (Etotal) states above is
equally likely the number of these states for which
the system sits in |n is

ZCT207/2 - 2

Statistical Mechanics

So the probability that the system sits in state |n is


just the ratio of this number of states to the total
number of states,

This is the Boltzmann distribution, also known as the


canonical ensemble.
The Partition Function
The inverse factor of the temperature is universally
denoted,
The normalization factor that sits in the denominator
of the probability is written,
ZCT207/2 - 2

Statistical Mechanics

In this notation, the probability for the system to be


found in state |n is

Z, is defined as a function of the (inverse) temperature


and is called the partition function.
Suppose that we have two systems which don't
interact with each other. The energy of the combined
system is then just the sum of the individual energies.
The partition function for the combined system is

ZCT207/2 - 2

Statistical Mechanics

Energy and Fluctuations


Let's see what information is contained in the
partition function. We'll start by thinking about the
energy.
In the microcanonical ensemble, the energy was
fixed. In the canonical ensemble, that is no longer
true. However, we can compute the average energy,

But this can be expressed in terms of the partition


function by

ZCT207/2 - 2

Statistical Mechanics

We can also look at the spread of energies about the


mean in other words, about fluctuations in the
probability distribution.

In the canonical ensemble, where the energy is not


fixed, the corresponding definition is

Then, since =1/kBT, the spread of energies can be


expressed in terms of the heat capacity as

ZCT207/2 - 2

Statistical Mechanics

Entropy
Recall that in the microcanonical ensemble, the entropy
counts the (log of the) number of states with fixed
energy. We would like to define an analogous quantity in
the canonical ensemble where we have a probability
distribution over states with different energies.
Suppose that we don't have just one copy of our system
S, but instead a large number, W, of identical copies.
Each system lives in a particular state |n . If W is large
enough, the number of systems that sit in state |n
must be simply p(n)W.
To determine the entropy we can treat the whole
collection of W systems as sitting in the microcanonical
ensemble to which we can apply the familiar Boltzmann
definition of entropy.
ZCT207/2 - 2

Statistical Mechanics

We must only figure out how many ways there are of


putting p(n)W systems into state |n for each |n
which is

And the entropy is therefore


This is the entropy for all W copies of the system. But
we also know that entropy is additive. So the entropy
for a single copy of the system, with probability
distribution p(n) over the states is
This is the Gibbs formula.

ZCT207/2 - 2

Statistical Mechanics

In the canonical ensemble, the probability distribution


is entirely determined by the choice of temperature T.
This means that the entropy is naturally a function of T.
Indeed, substituting the Boltzmann distribution p(n) =

e-En/Z into the Gibbs formula, we find that the entropy


in the canonical ensemble is given by

This can be expressed in terms of the partition function


by

ZCT207/2 - 2

Statistical Mechanics

Free Energy
The most important quantity in the canonical ensemble
is called the free energy,
F = E TS
It is sometimes referred to as the Helmholtz free
energy.
If we look at the first law of thermodynamics which
reads dE = TdS pdV and if we look at small variations
in F, we get
This form of the variation is telling us that we should
think of the free energy as a function of temperature
and volume: F = F(T,V ).
From the free energy, the entropy is given by

ZCT207/2 - 2

Statistical Mechanics

Similarly, the pressure is given by

The free energy is the most important quantity at fixed


temperature. It is also the quantity that is most
directly related to the partition function Z:
F = kBT log Z
_______________________________________________________

ZCT207/2 - 2

Statistical Mechanics

You might also like