Species with negative electron affinity and standard DFT methods. Finding the valence anions.
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.
Puiatti
Marcelo
M
INFIQC, Departamento de Química Orgánica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000 Córdoba, Argentina.
Vera
D Mariano A
DM
Pierini
Adriana B
AB
D000838:Anions / Q000737:chemistry; D003198:Computer Simulation; D004583:Electrons; D008956:Models, Chemical; D008958:Models, Molecular; D011789:Quantum Theory
D000838:Anions