Abstract
A thermodynamic consistency principle is established for the closure relations in integral equations that can yield accurate correlation functions as well as accurate thermodynamic properties, A brief lour d'horizon is given for existing consistency approaches. In addition to the common pressure consistency and the pressure energy consistency, we introduce a third requirement based on the Gibbs-Duhem relation. We found that Gibbs Duhem relation, mediated through the chemical potential, is instrumental in procuring accurate behavior of the bridge function and cavity Junction in the overlapping region (0 <r < σ). We test the Lennard Jones fluid over wide ranges ofT * andp * (T * as low as 0.72 andp * up to 11,90(, For more than IS state points we obtain excellent agreement in internal energy, pressure, and chemical potential. Comparison with Monte Carlo data on the bridge Junction and the radial distribution function also shows that the present approach is highly accurate.
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Lomba, E., Lee, L.L. Consistency conditions for the integral equations of liquid structures. Int J Thermophys 17, 663–672 (1996). https://doi.org/10.1007/BF01441512
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DOI: https://doi.org/10.1007/BF01441512