A reexamination of virial coefficients of the Lennard-Jones fluid

Kippi M. Dyer, John S. Perkyns, Bernard Pettitt

Research output: Contribution to journalArticle

14 Scopus citations

Abstract

The fourth-order virial coefficients have been calculated exactly to five decimal places for pure fluids of the Lennard-Jones potential at many points in the phase diagram. The calculations were performed through direct evaluation of the integrals, or diagrams, which make up the density expansion of the radial distribution function: included were the standard fast Fourier transform method of evaluating the simply connected diagrams and the evaluation of the bridge diagram for the fourth order in density by expansion in Legendre polynomials. The polynomial-order dependence of the bridge diagram calculation and the range dependence of the simply connected diagrams of the fourth order are found to have more significance than was thought from previous studies, especially in the low-temperature range. This result was confirmed by direct evaluation of the diagrams which construct the virial coefficients, as given by Rowlinson, Barker, and coworkers. This calculation confirmed that numerical convergence has not been achieved at the precision levels previously reported in the literature. These differences, though minor at higher temperatures, can be seen to be more significant at the lower temperature ranges.

Original languageEnglish (US)
Pages (from-to)244-251
Number of pages8
JournalTheoretical Chemistry Accounts
Volume105
Issue number3
DOIs
StatePublished - Jan 2001
Externally publishedYes

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Keywords

  • Bridge diagrams
  • Numerical convergence
  • Phase diagrams

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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