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Superalkali character of alkali-monocyclic (pseudo)oxocarbon clusters.

A series of polynuclear superalkali cations C3X3Li3(+), C3(NCN)3Li3(+), C3X(NCN)2Li3(+), C3[C(CN)2]3Li3(+), C3(NCN)[C(CN)2]2Li3(+), C3X[C(CN)2]2Li3(+) (X = O, S, Se) and their corresponding neutral species were investigated by using the density functional theory. Except for C3Se3Li3, the ionization potentials for the studied neutral species are in the range of 2.52-3.75 eV, which are lower than the ionization potential of Cs atom (3.89 eV). For C3Se3Li3, although it has larger IP value of 4.51 eV than 3.89 eV of Cs, it is still less than IP = 5.39 eV of Li atom. Hence, they can be classified as superalkalies. In addition, the calculated results also indicated that besides the hyperlithiated configuration and segregated configuration, the excess electron may fully delocalize over various atoms (both center and ligands) in superalkalies. The present investigation gives hints to scientists that the search to a superatom can be extended by using more complicated cyclic (pseudo)oxocarbons as the central core of polynuclear superalkalies.