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

Año: 2008 vol. 10 p. 1394 - 1399

1463-9076

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 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)