Adequacy of the virial equation of state and cluster expansion.
Phys Rev E Stat Nonlin Soft Matter Phys
; 87(4): 042111, 2013 Apr.
Article
em En
| MEDLINE
| ID: mdl-23679377
The limits for the accuracy of the virial expansion and the problem of its divergence have been investigated using the exact cluster expansion of the configuration integral. In the subcritical temperature regimes the virial equation of state is applicable up to the singularity point of the isothermal compressibility, i.e., to the possible beginning of the condensation process. At supercritical temperatures this equation should be applicable within the region where the cluster expansion is adequate. The problem of the virial series divergence has been found to be irrelevant to the actual behavior of the cluster expansion. Considering the Lennard-Jones fluid as well as the system of hard spheres, the inadequate behavior of the cluster expansion has been discovered in the high density regime. The major reason for this inadequacy should be the basic simplification of the cluster expansion: the integration of irreducible diagrams over the infinite limits.
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Phys Rev E Stat Nonlin Soft Matter Phys
Ano de publicação:
2013
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Article