title: Species with negative electron affinity and standard DFT methods. Finding the valence anions.
abstract: Recently, we have shown that traditional bound-electron DFT models are reliable enough to reproduce negative electron affinities (EA) within a few meV, as long as the valence anion state is found, but they seem to fail in predicting the lowest EA when the ground anion state obtained is non-valence, which holds the extra electron in a diffuse orbital around the molecule; here we propose an alternative approach for finding the valence anion state, based on the stabilization exerted by a polar solvent; the methodology yields correct EA values (i.e. beyond the Koopman's theorem approximation) by gradually decreasing the dielectric constant of the medium.
authors.affiliation: INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina.
authors.forename: Marcelo
authors.initials: M
authors.lastname: Puiatti
authors.forename: D Mariano A
authors.initials: DM
authors.lastname: Vera
authors.forename: Adriana B
authors.initials: AB
authors.lastname: Pierini
mesh_terms: D000838:Anions / Q000737:chemistry; D003198:Computer Simulation; D004583:Electrons; D008956:Models, Chemical; D008958:Models, Molecular; D011789:Quantum Theory
chemical_list: D000838:Anions