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Derivation
They introduced what is now known as the Mayer funcThe rst step in obtaining a closed expression for virial tion:
coecients is a cluster expansion[1] of the grand canonical
partition function
[
]
u(|r1 r2 |)
f
(1,
2)
=
exp
kB T
=
n Qn = e(pV )/(kB T )
n
and wrote the cluster expansion in terms of these funcHere p is the pressure, V is the volume of the vessel con- tions. Here u(|r1 r2 |) is the interaction potential betaining the particles, kB is Boltzmanns constant, T is the tween particle 1 and 2 (which are assumed to be identical
absolute temperature, = exp[/(kB T )] is the fugacity, particles).
with the chemical potential. The quantity Qn is the
canonical partition function of a subsystem of n particles:
Here H(1, 2, . . . , n) is the Hamiltonian (energy operator) of a subsystem of n particles. The Hamiltonian is a
sum of the kinetic energies of the particles and the total n
-particle potential energy (interaction energy). The latter
includes pair interactions and possibly 3-body and higherbody interactions. The grand partition function can be
expanded in a sum of contributions from one-body, twobody, etc. clusters. The virial expansion is obtained from
this expansion by observing that ln equals pV /(kB T )
. In this manner one derives
Bi+1 =
i
i
i+1
i = The sum of all connected, irreducible graphs with one white and i blac
The rule for turning these graphs into integrals is as follows:
)
1 Q2
2
B2 = V
2 Q1
[
(
) 1 ( 6Q
)]
3
2 2Q2 2Q2
B3 = V
1
1
Q21 Q21
3 Q31
(
These are quantum-statistical expressions containing kinetic energies. Note that the one-particle partition function Q1 contains only a kinetic energy term. In the classical limit = 0 the kinetic energy operators commute
1
5 FURTHER READING
3. With each bond linking two vertices associate the
Mayer f-function corresponding to the interparticle
potential
4. Integrate over all coordinates assigned to the black
vertices
5. Multiply the end result with the symmetry number
of the graph, dened as the inverse of the number of
permutations of the black labelled vertices that leave
the graph topologically invariant.
B2 = 2
)
eu(|r1 |)/(kB T ) 1 r2 dr1 ,
See also
Boyle temperature - temperature at which the second virial coecient B2 vanishes
Excess virial coecient
Compressibility factor
References
Further reading
Dymond, J. H.; Smith, E. B. (1980). The Virial
Coecients of Pure Gases and Mixtures: a Critical Compilation. Oxford: Clarendon. ISBN
0198553617.
Hansen, J. P.; McDonald, I. R. (1986). The Theory of Simple Liquids (2nd ed.). London: Academic
Press. ISBN 012323851X.
http://scitation.aip.org/content/aip/journal/jcp/50/
10/10.1063/1.1670902
http://scitation.aip.org/content/aip/journal/jcp/50/
11/10.1063/1.1670994
Reid, C. R., Prausnitz, J. M., Poling B. E., Properties
of gases and liquids, IV edition, Mc Graw-Hill, 1987
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