title: Communication: Avoiding unbound anions in density functional calculations.
abstract: Converged approximate density functional calculations usually do not bind anions due to large self-interaction error. But Hartree-Fock (HF) calculations have no such problem, producing negative HOMO energies. Thus, electron affinities can be calculated from density functional total energy differences using approximations such as PBE and B3LYP, evaluated on HF densities (for both anion and neutral). This recently proposed scheme is shown to work very well for molecules, better than the common practice of restricting the basis set except for cases such as CN, where the HF density is too inaccurate due to spin contamination.
authors.affiliation: Department of Chemistry and Institute of Nano-Bio Molecular Assemblies, Yonsei University, Seoul, South Korea.
authors.forename: Min-Cheol
authors.initials: MC
authors.lastname: Kim
authors.forename: Eunji
authors.initials: E
authors.lastname: Sim
authors.forename: Kieron
authors.initials: K
authors.lastname: Burke
mesh_terms: D000838:Anions / Q000737:chemistry*; D004583:Electrons; D011789:Quantum Theory
chemical_list: D000838:Anions