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Partition function (statistical mechanics)

In physics, a partition function describes the statistical properties of a system in thermodynamic equilibrium. Partition
functions are functions of the thermodynamic state variables, such as the temperature and volume. Most of the aggregate
thermodynamic variables of the system, such as the total energy, free energy, entropy, and pressure, can be expressed in
terms of the partition function or its derivatives. The partition function is dimensionless, it is pure number.

Each partition function is constructed to represent a particular statistical ensemble (which, in turn, corresponds to a
particular free energy). The most common statistical ensembles have named partition functions. The canonical
partition function applies to a canonical ensemble, in which the system is allowed to exchange heat with the
environment at fixed temperature, volume, and number of particles. The grand canonical partition function applies
to a grand canonical ensemble, in which the system can exchange both heat and particles with the environment, at fixed
temperature, volume, and chemical potential. Other types of partition functions can be defined for different
circumstances; see partition function (mathematics) for generalizations. The partition function has many physical
meanings, as discussed in Meaning and significance.

Contents
Canonical partition function
Definition
Connection to probability theory
Calculating the thermodynamic total energy
Relation to thermodynamic variables
Partition functions of subsystems
Meaning and significance
Grand canonical partition function
See also
References

Canonical partition function

Definition
Initially, let us assume that a thermodynamically large system is in thermal contact with the environment, with a
temperature T, and both the volume of the system and the number of constituent particles are fixed. A collection of this
kind of systems comprises an ensemble called a canonical ensemble. The appropriate mathematical expression for the
canonical partition function depends on the degrees of freedom of the system, whether the context is classical mechanics
or quantum mechanics, and whether the spectrum of states is discrete or continuous.

Classical discrete system

For a canonical ensemble that is classical and discrete, the canonical partition function is defined as

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where

is the index for the microstates of the system,

is the thermodynamic beta, defined as ,
is the total energy of the system in the respective microstate.

The exponential factor exp(−βEi) is known as the Boltzmann factor.

Derivation of canonical partition function (classical, discrete)

There are multiple approaches to deriving the partition function. The following derivation
follows the powerful and general information-theoretic Jaynesian maximum entropy
approach.

According to the second law of thermodynamics, a system assumes a configuration of

maximum entropy at thermodynamic equilibrium. We seek a probability distribution of states
that maximizes the discrete Gibbs entropy

subject to two physical constraints:

1. The probabilities of all states add to unity:

2. In the canonical ensemble, the average energy is fixed:

Using the method of Lagrange multipliers, we write the Lagrangian (or Lagrange function)
as

Differentiating and extremizing with respect to leads to

Isolating for yields

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To obtain , one substitutes the probability into the first constraint:

where is defined as the canonical ensemble partition function:

Rewriting in terms of gives

Rewriting in terms of gives

To obtain , we differentiate with respect to the average energy and apply the fact that

Thus the canonical partition function becomes

where is the thermodynamic beta. Finally, the probability distribution and

entropy are respectively

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Classical continuous system

In classical mechanics, the position and momentum variables of a particle can vary continuously, so the set of microstates
is actually uncountable. In classical statistical mechanics, it is rather inaccurate to express the partition function as a sum
of discrete terms. In this case we must describe the partition function using an integral rather than a sum. For a canonical
ensemble that is classical and continuous, the canonical partition function is defined as

where

is the Planck constant,

is the thermodynamic beta, defined as ,
is the Hamiltonian of the system,
is the canonical position,
is the canonical momentum.

To make it into a dimensionless quantity, we must divide it by h, which is some quantity with units of action (usually taken
to be Planck's constant).

Classical continuous system (multiple identical particles)

For a gas of N identical classical particles, the partition function is

where

pi indicate particle momenta,

xi indicate particle positions,
d3 is a shorthand notation serving as a reminder that the pi and xi are vectors in three-
dimensional space,
H is the classical Hamiltonian.

The reason for the factorial factor N! is discussed below. The extra constant factor introduced in the denominator was
introduced because, unlike the discrete form, the continuous form shown above is not dimensionless. As stated in the
previous section, to make it into a dimensionless quantity, we must divide it by h3N (where h is usually taken to be Planck's
constant).

Quantum mechanical discrete system

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For a canonical ensemble that is quantum mechanical and discrete, the canonical partition function is defined as the trace
of the Boltzmann factor:

where

is the thermodynamic beta, defined as ,

is the Hamiltonian operator.

The dimension of is the number of energy eigenstates of the system.

Quantum mechanical continuous system

For a canonical ensemble that is quantum mechanical and continuous, the canonical partition function is defined as

where

is the Planck constant,

is the thermodynamic beta, defined as ,
is the Hamiltonian operator,
is the canonical position,
is the canonical momentum.

In systems with multiple quantum states s sharing the same energy Es, it is said that the energy levels of the system are
degenerate. In the case of degenerate energy levels, we can write the partition function in terms of the contribution from
energy levels (indexed by j) as follows:

where gj is the degeneracy factor, or number of quantum states s that have the same energy level defined by Ej = Es.

The above treatment applies to quantum statistical mechanics, where a physical system inside a finite-sized box will
typically have a discrete set of energy eigenstates, which we can use as the states s above. In quantum mechanics, the
partition function can be more formally written as a trace over the state space (which is independent of the choice of
basis):

where Ĥ is the quantum Hamiltonian operator. The exponential of an operator can be defined using the exponential
power series.

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The classical form of Z is recovered when the trace is expressed in terms of coherent states[1] and when quantum-
mechanical uncertainties in the position and momentum of a particle are regarded as negligible. Formally, using bra–ket
notation, one inserts under the trace for each degree of freedom the identity:

where |x, p⟩ is a normalised Gaussian wavepacket centered at position x and momentum p. Thus

A coherent state is an approximate eigenstate of both operators and , hence also of the Hamiltonian Ĥ, with errors of
the size of the uncertainties. If Δx and Δp can be regarded as zero, the action of Ĥ reduces to multiplication by the classical
Hamiltonian, and Z reduces to the classical configuration integral.

Connection to probability theory

For simplicity, we will use the discrete form of the partition function in this section. Our results will apply equally well to
the continuous form.

Consider a system S embedded into a heat bath B. Let the total energy of both systems be E. Let pi denote the probability
that the microstate that system S is in has energy Ei. According to the fundamental postulate of statistical mechanics
(which states that all attainable microstates of a system are equally probable), the probability pi will be proportional to the
number of microstates of the total closed system (S, B) in which S is in microstate i with energy Ei. Equivalently, pi will be
proportional to the number of microstates of the heat bath B with energy E − Ei:

Assuming that the heat bath's internal energy is much larger than the energy of S (E ≫ Ei), we can Taylor-expand to
first order in Ei and use the thermodynamic relation , where here , are the entropy and temperature
of the bath respectively:

Thus

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Since the total probability to find the system in some microstate (the sum of all pi) must be equal to 1, we can define the
partition function as the normalization constant:

Calculating the thermodynamic total energy

In order to demonstrate the usefulness of the partition function, let us calculate the thermodynamic value of the total
energy. This is simply the expected value, or ensemble average for the energy, which is the sum of the microstate energies
weighted by their probabilities:

or, equivalently,

Incidentally, one should note that if the microstate energies depend on a parameter λ in the manner

then the expected value of A is

This provides us with a method for calculating the expected values of many microscopic quantities. We add the quantity
artificially to the microstate energies (or, in the language of quantum mechanics, to the Hamiltonian), calculate the new
partition function and expected value, and then set λ to zero in the final expression. This is analogous to the source field
method used in the path integral formulation of quantum field theory.

Relation to thermodynamic variables

In this section, we will state the relationships between the partition function and the various thermodynamic parameters
of the system. These results can be derived using the method of the previous section and the various thermodynamic
relations.

As we have already seen, the thermodynamic energy is

The variance in the energy (or "energy fluctuation") is

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The heat capacity is

The entropy is

where A is the Helmholtz free energy defined as A = U − TS, where U = ⟨E⟩ is the total energy and S is the entropy, so that

Partition functions of subsystems

Suppose a system is subdivided into N sub-systems with negligible interaction energy, that is, we can assume the particles
are essentially non-interacting. If the partition functions of the sub-systems are ζ1, ζ2, ..., ζN, then the partition function of
the entire system is the product of the individual partition functions:

If the sub-systems have the same physical properties, then their partition functions are equal, ζ1 = ζ2 = ... = ζ, in which case

However, there is a well-known exception to this rule. If the sub-systems are actually identical particles, in the quantum
mechanical sense that they are impossible to distinguish even in principle, the total partition function must be divided by a
N! (N factorial):

This is to ensure that we do not "over-count" the number of microstates. While this may seem like a strange requirement,
it is actually necessary to preserve the existence of a thermodynamic limit for such systems. This is known as the Gibbs
paradox.

Meaning and significance

It may not be obvious why the partition function, as we have defined it above, is an important quantity. First, let us
consider what goes into it. The partition function is a function of the temperature T and the microstate energies E1, E2, E3,
etc. The microstate energies are determined by other thermodynamic variables, such as the number of particles and the
volume, as well as microscopic quantities like the mass of the constituent particles. This dependence on microscopic

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variables is the central point of statistical mechanics. With a model of the microscopic constituents of a system, one can
calculate the microstate energies, and thus the partition function, which will then allow us to calculate all the other
thermodynamic properties of the system.

The partition function can be related to thermodynamic properties because it has a very important statistical meaning.
The probability Ps that the system occupies microstate s is

Thus, as shown above, the partition function plays the role of a normalizing constant (note that it does not depend on s),
ensuring that the probabilities sum up to one:

This is the reason for calling Z the "partition function": it encodes how the probabilities are partitioned among the
different microstates, based on their individual energies. The letter Z stands for the German word Zustandssumme, "sum
over states". The usefulness of the partition function stems from the fact that it can be used to relate macroscopic
thermodynamic quantities to the microscopic details of a system through the derivatives of its partition function.

Grand canonical partition function

We can define a grand canonical partition function for a grand canonical ensemble, which describes the statistics of
a constant-volume system that can exchange both heat and particles with a reservoir. The reservoir has a constant
temperature T, and a chemical potential μ.

The grand canonical partition function, denoted by , is the following sum over microstates

Here, each microstate is labelled by , and has total particle number and total energy . This partition function is
closely related to the Grand potential, , by the relation

This can be contrasted to the canonical partition function above, which is related instead to the Helmholtz free energy.

It is important to note that the number of microstates in the grand canonical ensemble may be much larger than in the
canonical ensemble, since here we consider not only variations in energy but also in particle number. Again, the utility of
the grand canonical partition function is that it is related to the probability that the system is in state :

An important application of the grand canonical ensemble is in deriving exactly the statistics of a non-interacting many-
body quantum gas (Fermi–Dirac statistics for fermions, Bose–Einstein statistics for bosons), however it is much more
generally applicable than that. The grand canonical ensemble may also be used to describe classical systems, or even
interacting quantum gases.
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The grand partition function is sometimes written (equivalently) in terms of alternate variables as[2]

where is known as the absolute activity (or fugacity) and is the canonical partition function.

See also
Partition function (mathematics)
Partition function (quantum field theory)
Virial theorem
Widom insertion method

References
1. Klauder, John R.; Skagerstam, Bo-Sture (1985). Coherent States: Applications in Physics and Mathematical Physics.
World Scientific. pp. 71–73. ISBN 978-9971-966-52-2.
2. Baxter, Rodney J. (1982). Exactly solved models in statistical mechanics. Academic Press Inc. ISBN 9780120831807.

Huang, Kerson, "Statistical Mechanics", John Wiley & Sons, New York, 1967.
A. Isihara, "Statistical Physics", Academic Press, New York, 1971.
Kelly, James J, (Lecture notes) (http://www.physics.umd.edu/courses/Phys603/kelly/Notes/IdealQuantumGases.pdf)
L. D. Landau and E. M. Lifshitz, "Statistical Physics, 3rd Edition Part 1", Butterworth-Heinemann, Oxford, 1996.
Vu-Quoc, L., Configuration integral (statistical mechanics) (http://clesm.mae.ufl.edu/wiki.pub/index.php/Configuration_
integral_%28statistical_mechanics%29), 2008. this wiki site is down; see this article in the web archive on 2012 April
28 (https://web.archive.org/web/20120428193950/http://clesm.mae.ufl.edu/wiki.pub/index.php/Configuration_integral
_%28statistical_mechanics%29).

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