Kohn–Sham Density in a Slater Orbital Basis Set

Abstract

Finite, atom-centered Slater basis sets are used to determine approximate Kohn−Sham molecular orbitals. This is achieved by minimizing the kinetic energy plus the sum-squared difference between the Kohn−Sham density and the full configuration interaction density. As a result of the finite basis, a weight factor is introduced to balance the two minimization components. Results herein show that this can be done systematically, without sensitive dependence on the choice of scaling factor. In addition, the algorithm is applied to the LiH diatomic for fractional electron counts, where stretching the bond introduces significant reorganization of the electron density. The analysis will show the correct KS orbital structure and reveal the effects of correlation and electron locality on the KS solutions.