DFT with effective potential expressed as a mapping of the external potential: Applications to closed‐shell molecules

Abstract

ABSTRACT:In density functional theory (DFT), the Kohn-Sham (KS) potential V KS is expressed in terms of the ground-state density. As a consequence, V KS does not always have the symmetry of the external potential V. The symmetry requirements are used to derive a noninteracting potential, V eK , as a direct mapping of the external potential V. This mapping gives the following V eK for molecules and solids:where Z i are the nuclear charges at positions R i . An explicit form of the kernel K is given. Applications are made to small molecules (H 2 , LiH, BH, and H 2 O) in order to test its accuracy. The energies calculated were found to deviate very little from those of Hartree-Fock, as the relative deviation of the two energies, ⌬E/E, was found to be of the order of 10 Ϫ4. This accuracy is much higher than that of standard DFT in its local exchange potential approximation. This method is appropriate for large molecules, as it is much faster than HF and standard DFT, because the potential is known from the start.

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