Formation and properties of iron-based magnetic superhalogens: a theoretical study

In order to explore new magnetic superhalogens, we have systematically investigated the structures, electrophilic properties, stabilities, magnetic properties, and fragmentation channels of neutral and anionic Fe(m)F(n) (m = 1, 2; n = 1-7) clusters using density functional theory. Our results show that a maximum of six F atoms can be bound atomically to one Fe atom, and the Fe-Fe bonding is not preferred in Fe2F(n)(0/-) clusters. The computed electron affinities (EAs) indicate that FeF(n) with n ≥ 3 are superhalogens, while Fe2F(n) can be classified as superhalogens for n ≥ 5. To further understand their superhalogen characteristic, the natural population analysis charge distribution and the HOMOs of anionic clusters were also analyzed. When the extra negative charge and the content of HOMO are mainly located on F atoms, the clusters could be classified as superhalogens with EAs substantially surpass that of Cl. By calculating the binding energies per atom and the HOMO-LUMO gaps, FeF3, FeF4(-), Fe2F4, Fe2F5(-), and Fe2F7(-) clusters were found to have higher stabilities, corresponding to the Fe atoms that are attained at their favorite +2 and +3 oxidation states. Furthermore, we also predicted the most preferred fragmentation channel and product for all the ground state clusters. Even more striking is the fact that both neutral and anionic Fe(m)F(n) (m = 1, 2; n = 1-7) clusters carry large magnetic moments which mainly come from 3d orbital of iron atom.