If a system is composed of weakly interacting particles we can use perturbative methods to compute the partition function of such systems.
For example, consider a fluid composed of particles in a region of volume , interacting through a generic two-body potential that depends only on the relative distance between the particles:
Its Hamiltonian will be:
and its partition function:
is the thermal wavelength and
is the configurational sum:
Of course for ideal gases
, and the dependence on the temperature is included only in
; if we consider also the interaction terms we must insert a correction
in the configurational contribution to the partition function
which (depending on the possible presence of attractive terms in the interaction potential
) can in general be also a function of the temperature
; furthermore the correction depends strongly on the gas density: if it is low the particles will not "perceive" the presence of the other ones and the ideal gas approximation is a good one, while for high densities the particles will be closer to each other and corrections to
Let us note that inserting the correction
the free energy of the system will be:
Virial and cluster expansion[edit | edit source]
The virial expansion is a systematic approach that can be used to incorporate the corrections due to the interactions between the particles, and as we will shortly see it can be obtained from a much general method, the cluster expansion.
The virial expansion consists in expanding the thermodynamic quantities of a system in powers of the density ; for example, the virial expansion for the pressure of a gas is:
are called virial coefficients
, and in general they can depend on the temperature. The virial expansion is very useful because the coefficients
can be experimentally measured (for example, in the case of the pressure they can be determined by properly fitting the isotherms of a system), and as we will see they can be related to microscopic properties of the interparticle interaction.
Let us see for example the virial expansion of the Van der Waals equation. From Van der Waals equation we have:
which can be rewritten as:
where of course
is the density of the system. Therefore, expanding the first term in a Taylor series:
We can thus immediately identify the first virial coefficient:
vanishes is in general called Boyle temperature
; in this case
Now, let us see how the cluster expansion works and how we can obtain the virial expansion from it. Of course, we start from the general configurational partition function:
The idea is to find a "small quantity" in terms of which we can expand
; this quantity is the so called Mayer function
In fact, when the gas is ideal
, and if the particles interact weakly
is small, and so is
. In particular, this expansion will work well for low densities (namely
is large and so
) or high temperatures (namely
): in both cases, in fact,
Using the short notations
by definition, in the end we will have:
where the missing terms contain the product of two or more Mayer functions. Therefore, the configurational contribution to the partition function will be:
where in the last step we have extracted the contributions of the integrals with
. Now, the remaining integral can be easily computed with the definition of the new variable
where in the last step we have defined
the first virial coefficient. Of course, we should have set
equal to a generic coefficient, but in the end we should have found exactly that this coefficient is
: we have done this for the sake of simplicity.
From this we see precisely how the virial coefficient, which as we have already stated can be experimentally measured, is related to the microscopic properties of the interaction between the particles, represented by the Mayer function
It can also be shown that all the virial coefficients can be expressed in terms of integrals of products of Mayer functions; for example the second virial coefficient is:
Higher order coefficients involve the computation of increasingly difficult integrals, which can however be visualized in terms of graphs.
What we have seen now is how the cluster expansion works in general. Let us now apply it in order to find the virial expansion for real gases.
From what we have found, the configurational partition function of the system becomes:
The remaining sum is equal to
: in fact, for any of the
and, considering that
, the complete partition function of the system will be:
We recognise in this expression that
is the correction
to the ideal gas partition function that we have mentioned earlier; therefore, the free energy of the system will be:
and its pressure:
Now, neglecting the terms involving
, and expanding in terms of
, which is small)
This expansion contains only low-order terms in the density
, so strictly speaking it is valid only for low densities. However, we can use a "trick" in order to extend its range; in fact, remembering that the McLaurin expansion of
, from the last equation we can write:
and now re-expand
, so that we can express all the virial coefficients in terms of the first one:
So in the end:
Computation of virial coefficients for some interaction potentials[edit | edit source]
Let us now see this method in action by explicitly computing some coefficients for particular interaction potentials.
As a first trial, we use a hard sphere potential similar to the one we have seen for the derivation of the Van der Waals equation:
(the difference with what we have seen in Van der Waals equation
is that now the potential is purely repulsive, and has no attractive component).
In this case:
Therefore, from the definition of
and shifting to spherical coordinates:
In this case
does not depend on the temperature, and in the end we have:
We now use a slight refinement of the previous potential:
This can be seen as a hard sphere potential where the spheres have an attractive shell of thickness
We thus have:
is the first virial coefficient of the hard sphere potential we have previously seen. Now, if the temperature is sufficiently high, namely
, we can approximate
, so that:
For the sake of simplicity, defining:
we will have, in the end:
so in this case
actually depends on the temperature.
This potential is a quite realistic representation of the interatomic interactions. It is defined as:
which contains a long-range attractive term (the one proportional to
, which can be justified in terms of electric dipole fluctuations) and a short-range repulsive one (proportional to
, which comes from the overlap of the electron orbitals).
With this interaction potential, the first virial coefficient is:
which is not analytically computable. However, it can be simplified defining the variables
Now, we can expand the exponential and integrate term by term; this gives an expression of
as a power series of
is the Euler gamma function and
is a constant.
Note that the attractive part of the Lennard-Jones potential has introduced in
a dependence on the temperature.
- ↑ We can always insert a multiplicative correction. We could have also written it as an additive correction, but the core of the subject doesn't change.
- ↑ Referring to what we have stated previously, if we set with a generic constant, then we should have found:
and proceeding like we have done now, in the end:
and so we see that indeed .