The LDA-1/2 Method Applied to Atoms and Molecules

The LDA-1/2 method evaluates ionization potentials as the energy of the highest occupied molecular orbitals (HOMOs) at half occupation. It has proven to be a viable approach for calculating band gaps of semiconductors. To address its accuracy for finite systems, we apply LDA-1/2 to the atoms and molecules of the GW100 test set. The obtained HOMO energies are validated against CCSD(T) data and the G₀ W₀ approach of many-body perturbation theory. The accuracy of LDA-1/2 and G₀ W₀ is found to be the same, where the latter is computationally much more involved. To get insight into the benefits and limitations of the LDA-1/2 method, we analyze the impact of each assumption made in deriving the methodology.