Maximum entropy formulation of the Kirkwood superposition approximation

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Abstract

The Kirkwood superposition approximation for systems at equilibrium in the thermodynamic limit was derived using a variational formulation. The entropy of the triplet correlation function was defined and it was shown that the Kirkwood closure brings the entropy to its maximal value. It was shown that this approach leads to a different interpretation for the Kirkwood closure relation, usually explained by probabilistic considerations of dependence and interdependence of particles. A variational approach was used to find closure relations for high order correlation functions.

Original languageEnglish (US)
Pages (from-to)3657-3666
Number of pages10
JournalJournal of Chemical Physics
Volume121
Issue number8
DOIs
StatePublished - Aug 22 2004

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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