Correlated calculations model potential issues

The behavior of the SCF solutions is not the only issue of interest in the energetics of model potentials. Because Bk is finite, the core spinors are not moved an infinite distance from the valence space, but a finite distance. Any representation of the core spinors remains in the molecular basis set, and can contaminate a correlated calculation, if they are not removed (Klobukowski 1990). The result can be an overestimation of correlation effects. Diagonalizing B in the virtual spinor space should provide a means of recognizing and removing core-like spinors. 

However, before proceeding with the description of simulation data, we would like to comment the theoretical background. Similarly to the previous example, in order to obtain the pair correlation function of matrix spheres we solve the common Ornstein-Zernike equation complemented by the PY closure. Next, we would like to consider the adsorption of a hard sphere fluid in a microporous environment provided by a disordered matrix of permeable species. The fluid to be adsorbed is considered at density pj = pj-Of. The equilibrium between an adsorbed fluid and its bulk counterpart (i.e., in the absence of the matrix) occurs at constant chemical potential. However, in the theoretical procedure we need to choose the value for the fluid density first, and calculate the chemical potential afterwards. The ROZ equations, (22) and (23), are applied to decribe the fluid-matrix and fluid-fluid correlations. These correlations are considered by using the PY closure, such that the ROZ equations take the Madden-Glandt form as in the previous example. The structural properties in terms of the pair correlation functions (the fluid-matrix function is of special interest for models with permeabihty) cannot represent the only issue to investigate. Moreover, to perform comparisons of the structure under different conditions we need to calculate the adsorption isotherms pf jSpf). The chemical potential of a... 

---