Interaction of N2, O2 and H2 Molecules with Superalkalis

• Published in: ChemistryOpen (Weinheim) Vol. 13; no. 7; pp. e202300253 - n/a
• Main Authors: Srivastava, Harshita, Kumar Srivastava, Ambrish, Misra, Neeraj
• Format: Journal Article
• Language: English
• Published: Weinheim John Wiley & Sons, Inc 01.07.2024; John Wiley and Sons Inc; Wiley-VCH
• Subjects: ab initio calculation; Adsorption; Charge transfer; Diatomic molecules; Electron affinity; Energy; Hydrogen; Ionic interactions; Isomers; Metals; Perturbation theory; Reducing agents; reduction; Superalkalis
• ISSN: 2191-1363; 2191-1363
• DOI: 10.1002/open.202300253

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 (X2) such as N2, O2, and H2 using Møller‐Plesset perturbation theory (MP2), we have studied their interaction with typical superalkalis such as FLi2, OLi3, and NLi4 and calculated various parameters of the resulting SA−X2 complexes. We noticed that the SA−O2 complex and its isomers possess strong ionic interaction, which leads to the reduction of O2 to O2− anion. On the contrary, there are both ionic and covalent interactions in SA−N2 complexes such that the lowest energy isomers are covalently bonded with no charge transfer from SA. Further, the interaction between SA and H2 leads to weakly bound complexes, which results in the adsorption of H2 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. N2 (blue), O2 (red) and H2 (grey) interact differently with superalkali clusters. Their interaction varies from strong covalent to weak van der Waals interaction leading to the possibility of reduction or adsorption of these small molecules.