Superhalogens Among 3-Metal Compounds: F, F, F, and F ( = Sc-Zn).

The ground states of the neutral and anionic tetrafluoride and hexafluoride series of 3-metal atoms from Sc to Zn were assigned by using a double-check approach in which the pure and hybrid density functional methods were interchangeably used. It was confirmed that all these neutral fluorides are superhalogens except for TiF. The electron affinities of the hexafluorides were shown to be consistently higher than those of the tetrafluorides in accordance with the superhalogen conception of the extra electron delocalization over a larger number of the electronegative ligands. In the search for mononuclear fluorides possessing higher electron affinities, we considered the (F) and (F) series where = Sc-Zn. We found that the optimized geometrical structures in both series may be described as F- (F), = 3 and 6, of which the geometry of the F core mimics that of the corresponding hexafluoride anion and the F dimers are kept in a bound state by polarizing forces. In these cases, the electron affinity is decreased by tenths of eV with respect to the electron affinity of the core hexafluorides due to a confinement of the extra electron by the F environment.