Variational theory for lennard-jones chains

Richard O’Lenick, Yee Chiew

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

The Helmholtz energy and pressure for Lennard-Jones chains are derived using a variational first-order perturbation theory. The reference system, comprising freely jointed tangent hard-sphere chains is solved in the Percus-Yevick approximation. The optimal diameter of segments in the hard-sphere chain reference is determined by minimizing the free energy through the Gibbs-Bogoliubov inequality. Unlike previous perturbation theories for non-aggre-gated Lennard-Jones spheres, the resulting hard-sphere segment diameter depends on chain length in addition to density and temperature. The resulting theory exhibits excellent agreement with MC simulation, over a wide range of conditions, without adjustable parameters.

Original languageEnglish (US)
Pages (from-to)257-269
Number of pages13
JournalMolecular Physics
Volume85
Issue number2
DOIs
StatePublished - Jun 10 1995

Fingerprint

Pressure
Temperature
perturbation theory
reference systems
Chain length
tangents
Free energy
free energy
approximation
simulation
temperature
energy

All Science Journal Classification (ASJC) codes

  • Biophysics
  • Molecular Biology
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

O’Lenick, Richard ; Chiew, Yee. / Variational theory for lennard-jones chains. In: Molecular Physics. 1995 ; Vol. 85, No. 2. pp. 257-269.
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Variational theory for lennard-jones chains. / O’Lenick, Richard; Chiew, Yee.

In: Molecular Physics, Vol. 85, No. 2, 10.06.1995, p. 257-269.

Research output: Contribution to journalArticle

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