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 language||English (US)|
|Number of pages||10|
|Journal||Journal of Chemical Physics|
|State||Published - Aug 22 2004|
All Science Journal Classification (ASJC) codes
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry