Integral equation theories for fluid with very short-range screened Coulomb plus power series interactions

Monte Carlo NVT simulations have been performed to obtain the thermodynamic and structural properties of fluids with a potential consisting in a hard-core and screened Coulomb plus power series (HC-SPS) interactions for three sets of the potential parameters. These 'exact' data are used to check the accuracy of two integral equation theories and a local excess chemical potential formula for very short-ranged potentials. The theories considered are the reference hypernetted-chain (RHNC) approximation and the local self-consistent OZ approximation (LSCOZA). The main conclusions of our study are described below. (i) The RHNC always underestimates the first peak of the radial distribution, which directly leads to an underestimation of the pressure and an overestimation of excess internal energy. In general, as the potential range becomes shorter ranged and the temperature decreases, the performance of the RHNC worsens and even becomes qualitatively incorrect. (ii) Local pressure self-consistency is of crucial importance to ensure that the hard sphere bridge function with an effective hard sphere diameter yields very accurate results for the pressure and excess internal energy even for very short-range potentials and at temperatures very close to the critical temperature. (iii) The accuracy of the excess chemical potential, obtained by thermodynamic integration of the excess internal energy, is also remarkable even for very short-ranged potentials and superior to that of a local excess chemical potential formula previously proposed [S. Zhou, Theor. Chem. Acc. 117, 555(2007)].

Automated summary

Monte Carlo NVT simulations were conducted to investigate the properties of fluids with HC-SPS interactions. The accuracy of two integral equation theories and a local chemical potential formula for short-ranged potentials was assessed. The study found that the RHNC approximation underestimates the radial distribution peak and that local pressure self-consistency is crucial for accurate results.