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All of the particle statistics have been derived on the assumption that the particles to
be distributed over energy levels do not interact. If they were to interact, we cannot be
certain that each microstate would have the same probability, which is the fundamental
assumption made in the derivation of the distribution functions. For
*interacting particles*,

we can obtain distribution functions by considering an
*ensemble*

of identical copies of the system and letting them all evolve and equilibrate separately. Alternatively, we can conceive of the one system being sliced up into many individual cells which can evolve separately. Depending on the kind of walls between the copies or cells of the system, three different types of ensemble are distinguished:

- canonical ensemble: $N, V, T$ identical - closed system
- microcanonical ensemble: $N, V, U$ identical - system in adiabatic enclosure
- great canonical ensemble: $\mu, V, T$ identical - open system

These are used under different sets of conditions, but the most generally used ensemble is
the canonical ensemble, which is characterised by
*diathermal boundaries*

between the contributing systems, keeping them in thermal contact.

The fundamental idea of ensemble statistics is that
**time average equals ensemble average**.

We can therefore apply the same statistics to average a single snapshot of many identical
systems as we would for multiple snapshots of a single system at different times. Since
the particles cannot cross the boundaries separating the cells of the ensemble, interaction
between the particles can be ruled out in this fashion.

The statistical weight of a distribution of an ensemble is calculated in the same way as a
particle distribution function:
$$\mathscr{\Omega}=\prod_i{\frac{\mathscr{N}!}{\mathscr{N}_i!}}\qquad,$$
where the
number of instances, $\mathscr{N}$

and the
total energy of ensemble, $\mathscr{E}$

substitute for the corresponding quantities in the Boltzmann distribution. We can find the
most probable ensemble configuration

and the
*ensemble partition function*

$$\mathscr{Z}=\sum_i\exp{\left(-\frac{\mathscr{E}_i}{k_BT}\right)}$$
in an exactly analoguous way.

Partition functions are the interface between quantum mechanics and thermodynamics. Different
quantum mechanical models have been developed for different aspects of the behaviour of atoms
and molecules such as translation, vibration, rotation, electronic excitation and magnetic
interaction. Each model produces a series of energy levels and a partition function. Below
are the rules for combining them.
Energies are additive:

$$E=\sum_i{E_i}\qquad,$$
while
partition functions are multiplicative:

$$Z=\sum_i\exp{\left(-\frac{E_i}{k_BT}\right)}=\prod_i z_i\qquad.$$
For
*distinguishable particles*

the system partition function is the product of the partition functions of the individual processes:
$$Z=z^N\qquad.$$
For
*indistinguishable particles*,

we have to take into account that swapping two particles doesn't constitute a new microstate, so
the system partition function reduces to
$$Z=\frac{z^N}{N!}\qquad.$$

That concludes the second-year thermodynamics course. There will be more on the quantum-mechanical
models supporting partition functions in the second-year
quantum mechanics course

(notes linked from a past edition of the module).
Phase transitions and energy levels in atoms and molecules feature again in the third-year
condensed matter

and
atomic and molecular physics

modules.