Interaction of N, O and H Molecules with Superalkalis.

Superalkalis (SAs) are exotic clusters having lower ionization energy than alkali atoms, which makes them strong reducing agents. In the quest for the reduction of diatomic molecules (X) such as N, O, and H using Møller-Plesset perturbation theory (MP2), we have studied their interaction with typical superalkalis such as FLi, OLi, and NLi and calculated various parameters of the resulting SA-X complexes. We noticed that the SA-O complex and its isomers possess strong ionic interaction, which leads to the reduction of O to O anion. On the contrary, there are both ionic and covalent interactions in SA-N complexes such that the lowest energy isomers are covalently bonded with no charge transfer from SA. Further, the interaction between SA and H leads to weakly bound complexes, which results in the adsorption of H molecules. The nature of interaction is found to be closely related to the electron affinity of diatomic molecules. These findings might be useful in the study of the activation, reduction, and adsorption of small molecules, which can be further explored for their possible applications.