Applications of the Optimized Effective Potential Method of Density Functional Theory to Atomic and Molecular Systems

TL;DR

This paper applies the optimized effective potential method combined with semi-analytical approximations to perform self-consistent density-functional calculations for molecules and ions, showing improved accuracy over traditional Kohn-Sham methods.

Contribution

It introduces a fully self-consistent exchange-only DFT approach using the OEP method with Krieger, Li, and Iafrate approximation, demonstrating enhanced performance.

Findings

Results closely match Hartree-Fock calculations.

Improved accuracy over conventional Kohn-Sham calculations.

Effective for atomic ions with correlation contributions.

Abstract

Using the optimized effective potential method in conjunction with the semi-analytical approximation due to Krieger, Li and Iafrate, we have performed fully self-consistent exact exchange-only density-functional calculations for diatomic molecules with a fully numerical basis-set-free molecular code. The results are very similar to the ones obtained with the Hartree Fock approach. Furthermore we present results for ground states of positive atomic ions including correlation contributions in the approximation of Colle and Salvetti. It is found that the scheme performs significantly better than conventional Kohn-Sham calculations.