BX₄⁻ and AlX₄⁻ Superhalogen Anions (X = F, Cl, Br): An ab Initio Study

Abstract

The vertical electron detachment energies (VDEs) of 30 MX 4 (-) (M = B, Al; X = F, Cl, Br) anions were calculated at the OVGF level with the 6-311+G(3df) basis sets. The largest vertical electron binding energy was found for the AlF 4 (-) system (9.789 eV). The strong VDE dependence on the symmetry of the species, ligand type, ligand-central atom distance, and bonding/nonbonding/antibonding character of the highest occupied molecular orbital was observed and discussed.

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

“…5,[10][11][12][13][14][15][16][17][18][19][20][21][22][23][24][25][26] Along with the deepening of the related researches, it has been a Author to whom correspondence should be addressed. Electronic mail: rayinyin@nwu.edu.…”

“…Electronic mail: rayinyin@nwu.edu. indicated that the VDEs of superhalogens could be improved both by strengthening the electronegativity of the ligand 12,16,20,23,[27][28][29][30][31] and by increasing the number of ligands. 10,11,29,30,[32][33][34] 8,42,43 have been utilized to design new superhalogens recently.…”

“…The direct calculation is based on the OVGF method which has become popular in theoretical prediction of the VDE values of superhalogen systems. 10,11,19,20,22,24,26,34,48,49,52,53,[56][57][58] Although OVGF has been successfully utilized in many mononuclear superhalogens, 11,16,19,26,28,29,36,59,60 its capability for superhalogens of polynuclear structure is not a matter free of debate. Large deviation of OVGF results has been reported for binuclear superhalogen anions [Mg 2 (CN) 5 ] −1 when compared with high-level CCSD(T) calculations.…”

Theoretical Search for an Iron‐Based Magnetic Superhalogen with Halogen or Interhalogen as Ligand

“…[15,20] Along with the growing interest in the design and synthesis of new superhalogens, these studies have been extended to systems composed of transition-metal atoms [28,[30][31][32][33] or even hydrogen [34] at the center surrounded with halogen or oxygen [35][36][37] as ligand atoms. Furthermore, superhalogens that contain more than one metal atom, such as Na x Cl x+1 (x = 1-4), [38] Ta 3 F 16 -, [19] and Mg 2 F 5 , [39] have also been found.…”

“…Such interhalogens are good halogenating agents, but there is almost no data on mixed species. Only Skurski's group [20,21] has investigated Na-, B-, and Al-based complexes that contain mixed halogen atoms as ligand. This lack of data has motivated us to take a closer look at the various iron-based clusters that contain chlorine, bromine, and interhalogen compounds to explore new magnetic superhalogens.…”