The entropy change that occurs upon mixing two fluids has remained an intriguing topic since the dawn of statistical mechanics. In this work, we generalize the grand-isobaric ensemble to mixtures and develop a Monte Carlo algorithm for the rapid determination of entropy in these systems. A key advantage of adiabatic ensembles is the direct connection they provide with entropy. Here, we show how the entropy of a binary mixture A–B can be readily obtained in the adiabatic grand-isobaric (μA, μB, P, R) ensemble, in which μA and μB denote the chemical potential of components A and B, respectively, P is the pressure, and R is the heat (Ray) function, that corresponds to the total energy of the system. This, in turn, allows for the evaluation of the entropy of mixing and the Gibbs free energy of mixing. We also demonstrate that our approach performs very well both on systems modeled with simple potentials and with complex many-body force fields. Finally, this approach provides a direct route to the determination of the thermodynamic properties of mixing and allows for the efficient detection of departures from ideal behavior in mixtures.
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