Superalkalis with Hydrogen as Central Electronegative Atom and their Possible Applications: Ab Initio and DFT Study

Superalkalis are unusual species having ionization energies lower than that of the alkali metals. These species with various applications are of great importance in chemistry due to their low ionization energies and strong reducing property. A typical superalkali contains a central electronegative core decorated with excess metal ligands. In the quest for novel superalkalis, we have designed the superalkalis HLi2, HLiNa and HNa2 using hydrogen as central electronegative atom for the first time employing high level ab initio (CCSD(T), MP2) and density functional theory (ωB97X‐D) methods. The superalkalis exhibit very low ionization energies, even lower than that of cesium. Stability of these species is verified from binding energy and dissociation energy values. The superalkalis are capable of reducing SO2, NO, CO2, CO and N2 molecules by forming stable ionic complexes and therefore can be used as catalysts for the reduction or activation of systems possessing very low electron affinities. The superalkalis form stable supersalts with tailored properties when interact with a superhalogen. They also show remarkably high non‐linear optical responses, hence could have industrial applications. It is hoped that this work will enrich the superalkali family and spur further theoretical and experimental research in this direction. Superalkalis having hydrogen as central electronegative core are designed. They exhibit very low ionization energies even lower than that of cesium. The superalkalis are capable of reducing molecules having very low electron affinities. They can act as the building blocks of supersalts and also show remarkable non‐linear optical property.