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Divergence of activity expansions: Is it actually a problem?
Ushcats, M V; Bulavin, L A; Sysoev, V M; Ushcats, S Yu.
Afiliação
  • Ushcats MV; Admiral Makarov National University of Shipbuilding, 9 Geroyev Stalingrada Avenue, Mykolayiv 54025, Ukraine.
  • Bulavin LA; Taras Shevchenko University of Kiev, 2 Academic Glushkov Avenue, Kiev 03680, Ukraine.
  • Sysoev VM; Taras Shevchenko University of Kiev, 2 Academic Glushkov Avenue, Kiev 03680, Ukraine.
  • Ushcats SY; Taras Shevchenko University of Kiev, 2 Academic Glushkov Avenue, Kiev 03680, Ukraine.
Phys Rev E ; 96(6-1): 062115, 2017 Dec.
Article em En | MEDLINE | ID: mdl-29347358
For realistic interaction models, which include both molecular attraction and repulsion (e.g., Lennard-Jones, modified Lennard-Jones, Morse, and square-well potentials), the asymptotic behavior of the virial expansions for pressure and density in powers of activity has been studied taking power terms of high orders into account on the basis of the known finite-order irreducible integrals as well as the recent approximations of infinite irreducible series. Even in the divergence region (at subcritical temperatures), this behavior stays thermodynamically adequate (in contrast to the behavior of the virial equation of state with the same set of irreducible integrals) and corresponds to the beginning of the first-order phase transition: the divergence yields the jump (discontinuity) in density at constant pressure and chemical potential. In general, it provides a statistical explanation of the condensation phenomenon, but for liquid or solid states, the physically proper description (which can turn the infinite discontinuity into a finite jump of density) still needs further study of high-order cluster integrals and, especially, their real dependence on the system volume (density).

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Phys Rev E Ano de publicação: 2017 Tipo de documento: Article

Texto completo: 1 Coleções: 01-internacional Base de dados: MEDLINE Idioma: En Revista: Phys Rev E Ano de publicação: 2017 Tipo de documento: Article