Direct excess entropy calculation for a Lennard-Jones fluid by the integral equation method.

The present work is devoted to the calculation of excess entropy by means of correlation functions, in the framework of integral equation theory. The tangent linear method is set up to get exact thermodynamic derivatives of the pair-correlation function, essential for the calculation of the physical quantities, as well as to carry out an optimization process for the achievement of thermodynamic consistency. The two-body entropy of the Lennard-Jones fluid is in very good agreement with the available molecular dynamics results, attesting the high degree of accuracy of the integral equation scheme. It is shown that an accurate prediction of the excess entropy and the resulting residual multiparticle entropy relies on the correct evaluation of the excess chemical potential, especially at high density. Two independent routes to calculate the latter are compared, and the consequences are discussed.