Neutral and anionic superhalogen hydroxides

Abstract

The properties of superhalogen M ( OH ) k + 1 - anions and their M(OH) k +1 neutral parents (where M = Li, Na, K, Be, Mg, Ca, B, Al, Ga) were investigated at the ab initio CCSD(T)/6–311++G(3df,3pd)//MP2/6–311++G(d,p) level of theory. All the M ( OH ) k + 1 - anions and some of their M(OH) k +1 neutral parents ( k is the maximal formal valence of M) were found to be thermodynamically stable against the fragmentations (OH, OH −, O 2 or H 2O loss). The vertical electron detachment energies (VDE) of the M ( OH ) k + 1 - anions were calculated with the OVGF method and using the 6-311++G(3df,3pd) basis sets. The VDE values calculated for the anions studied exceed 4 eV in all cases, whereas the largest values of the electron binding energies were found for the Al ( OH ) 4 - (6.07 eV) and Ga ( OH ) 4 - anions (6.21 eV). Finally, formation of most of the species considered was predicted to be spontaneous due to the lack of kinetic barriers for these processes and their thermodynamic favorability.