Species with negative electron affinity and standard DFT methods. Finding the valence anions

MARCELO PUIATTI; D. MARIANO A. VERA; ADRIANA B. PIERINI

PHYSICAL CHEMISTRY CHEMICAL PHYSICS

Royal Society of Chemistry 2007

Lugar: London; Año: 2008 vol. 2008 p. 1394 - 1394

1463-9076

ecently, 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 present an alternative simple and chemically intuitive approach for stabilizing the valence anion in a polar solvent and calculating thermodynamically correct EA values (i.e. beyond the Koopman´s theorem approximation)