Home – Home – Jornals – Journal of Structural Chemistry 2009 number 3

It was proven that after averaging over the canonical Gibbs ensemble, the mean perturbation energy was singled out of the classical partition function before the expansion in a series of perturbation theory. Therefore, the term that formally coincides with first order perturbation theory in a decomposition of the Helmholtz free energy bears no relationship to perturbation theory. Then the proper series of the thermodynamic perturbation theory always starts with a second order infinitesimal. Therefore, the well-known condition of applicability of the thermodynamic perturbation theory, "…the requirement that the perturbation energy per particle be small compared with Т…" (L. D. Landau and E. M. Livshits, Statistical Physics, Vol. V, Pt. I), can be substantially weakened. The most important factor for applicability of thermodynamic perturbation theory is the value of many-particle correlations in an unperturbed system, but not the smallness of the perturbation potential.