Abstract
We have performed an unbiased structure search for a series of neutral and anionic FeL(4) (L = BO(2), CN, NO(2), NO(3), OH, CH(3), NH(2), BH(4) and Li(2)H(3)) clusters using the CALYPSO (Crystal structure Analysis by Particle Swarm Optimization) structure search method. To probe the superhalogen properties of neutral and anionic FeL(4) clusters, we used density-functional theory with the B3LYP functional to examine three factors, including distribution of extra electron, pattern of bonding and the nature of the ligands. Theoretical results show that Fe(BO(2))(4), Fe(NO(3))(4) and Fe(NO(2))(4) can be classified as magnetic superhalogen due to that their electron affinities even exceed those of the constituent ligands. The magnetic moment of Fe atom is almost entirly maintained when it is decorated with various ligands except for neutral and anionic (Li(2)H(3))(4). Moreover, the current work is also extended to the salt moieties formed by hyperhalogen/superhalogen anion and Na(+) ion. It is found that these salts against dissociation into Na + FeL(4) are thermodynamic stable except for Na[Fe(OH)(4)]. These results provides a wealth of electronic structure information about FeL(4) magnetic superhalogens and offer insights into the synthesis mechanisms.