Metal-metal bonds with unusual oxidation states in early s-block elements: A computational perspective

Abstract

This review article features recent progress in the field of metal-metal bonding chemistry, with a focus on Li−Li, Be−Be, and Mg−Mg bonds via computational means. The use of advanced and sophisticated computational methods has allowed us to gain deeper insights into the nature of metal-metal and metal-ligand bonding which showed that the valence s and p orbitals of these metal atoms play a significant role. Computational methods such as density functional theory (DFT) and post-Hartree-Fock approaches have enabled researchers to explore the electronic structure and thermodynamic properties of metal-metal bonded systems. The computational tools such as natural bond orbital (NBO) analysis, energy decomposition analysis (EDA), and atoms-in-molecules (AIM) have been useful in predicting key electronic properties such as localized bond orbitals, interacting fragment orbitals, electron density-based descriptors, etc., which can be used to design new materials. This summarized study of metal-metal bonding will provide significant implications for the development of new materials with desirable properties for a wide range of applications.