Abstract
The interaction site cluster series is derived for the Helmholtz free energy of a molecular mixture in which molecules can interconvert by chemical reactions. This series expresses the free energy as a functional of the single-molecule (intramolecular) distribution functions. Variations of this functional are studied. It is shown that when the total numbers of atoms in the mixture are fixed, the free energy functional is a minimum with respect to variations of the intramolecular distribution functions. Further, this variational principle is shown to be equivalent to the cluster series formulas derived earlier [J. Chem. Phys. 65, 2925 (1976)] for chemical equilibrium constants and intramolecular distribution functions of nonrigid molecules in condensed phases.
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