Entropy and Molecular Correlation Functions in Open Systems. I. Derivation

A method is presented for obtaining an expression for the entropy in terms of molecular correlation functions defined in the grand canonical ensemble. The procedure is for a system of a single molecular species whose dynamics are determined by classical equations of motion. The entropy is obtained as a sum of two different classes of functions each involving the correlations between n-tuples of molecules. One class contains logarithmic terms similar to those obtained for the closed system; the other class involves isothermal activity derivatives of potentials of mean force. The latter terms, which are moments of the correlations between disjoint sets of molecules, can make appreciable contributions to the entropy. The method leads to results similar to those obtained from a different procedure by Nettleton and Green. The expression for the entropy is obtained and properties of the results are discussed for a simple fluid system.