From point of view of weighted density procedure, it is guessed that a Percus-Yevick （PY） compressibility excess free energy density, appearing in the Kierlik Rosinberg type fundamental measure functional （KR-FMF）...From point of view of weighted density procedure, it is guessed that a Percus-Yevick （PY） compressibility excess free energy density, appearing in the Kierlik Rosinberg type fundamental measure functional （KR-FMF） and expressed in terms of scaled particle variables, can be substituted by a corresponding expression dictated by a more accurate Mansoori Carnahan-Starling Leland （MCSL） equation of state, while retaining the original weighting functions; it is numerically indicated that the resultant undesirable non-self-consistency between the PY type weighting function and MCSL type excess free energy density had no bad effect on the performance of the resultant augmented KR-ffMF which, on the one hand, preserves the exact low-density limit of the original KR-FMF and holds a high degree of pressure self-consistency, on the other hand, improves significantly, as expected, the predictions of density profile of hard sphere fluid at single hard wall contact location and its vicinity, and of the bulk hard sphere second order direct correlation function （DCF）, obtained from functional differentiation. The FMF is made applicable to inhomogeneous non-hard sphere fluids by supplementing a functional perturbation expansion approximation truncated at the lowest order with summation of higher order terms beyond the lowest term calculated by the FMF for an effective hard sphere fluid; the resultant extended FMF only needs second order DCF and pressure of the fluid considered at coexistence state as inputs, consequently is applicable whether the considered temperature is above critical point or below critical point. The extended MCSL-augmented KR-FMF is found to be endowed with an excellent performance for predictions of density profile and surface tension by comparing the present predictions of these two quantities with available computer simulation data for inhomogeneous hard core attractive Yukawa fluid and Lennard-3ones fluid.展开更多
基金Supported by the National Natural Science Foundation of China under Grant No.20973202
文摘From point of view of weighted density procedure, it is guessed that a Percus-Yevick （PY） compressibility excess free energy density, appearing in the Kierlik Rosinberg type fundamental measure functional （KR-FMF） and expressed in terms of scaled particle variables, can be substituted by a corresponding expression dictated by a more accurate Mansoori Carnahan-Starling Leland （MCSL） equation of state, while retaining the original weighting functions; it is numerically indicated that the resultant undesirable non-self-consistency between the PY type weighting function and MCSL type excess free energy density had no bad effect on the performance of the resultant augmented KR-ffMF which, on the one hand, preserves the exact low-density limit of the original KR-FMF and holds a high degree of pressure self-consistency, on the other hand, improves significantly, as expected, the predictions of density profile of hard sphere fluid at single hard wall contact location and its vicinity, and of the bulk hard sphere second order direct correlation function （DCF）, obtained from functional differentiation. The FMF is made applicable to inhomogeneous non-hard sphere fluids by supplementing a functional perturbation expansion approximation truncated at the lowest order with summation of higher order terms beyond the lowest term calculated by the FMF for an effective hard sphere fluid; the resultant extended FMF only needs second order DCF and pressure of the fluid considered at coexistence state as inputs, consequently is applicable whether the considered temperature is above critical point or below critical point. The extended MCSL-augmented KR-FMF is found to be endowed with an excellent performance for predictions of density profile and surface tension by comparing the present predictions of these two quantities with available computer simulation data for inhomogeneous hard core attractive Yukawa fluid and Lennard-3ones fluid.
