Theoretical, empirical and experimental electron affinities of SF ₆: solving the density functional enigma

We postulate that the adiabatic electron affinity of SF ₆ is 2.40(10) eV, obtained from the photodetachment onset, 3.2(1) eV and a rearrangement energy of 0.8(1) eV. This eliminates the perceived "SF ₆ density functional enigma". All of the experimental electron affinities are evaluated and 14 significantly different values selected to construct empirical anionic Morse potentials. These values are (in eV): 2.40(10), 2.20(10), 2.00(10), 1.80(10), 1.60(10), 1.20(10), 1.07(7), 0.93(10), 0.80(10), 0.63(10), 0.43(10), 0.30(10), 0.10(10), and 0.0(2). Comparisons are made to theoretical calculations and relative bond orders. The calculated electron affinities of SF ₆ are: density functional, 1.6-3.0 eV; ab initio, -1.0-2.2 eV; semiempirical, 0.1-2.2eV, and for SF ₅ is 0.3-3.8 eV. Curves calculated using semiempirical, density functional and ab initio procedures are similar to the anionic Morse potentials. This work attempts to correct for differences in the EA calculated for this species.