Theoretical and experimental studies of bonding in the main group homonuclear diatomic molecules have been pursued for many years, and they possess serious challenges for scientists. Most of the early experimental work have been carried out by Herzberg.1,2 We take a relook at the bonding motifs of Period 2 homonuclear diatomic molecules (from Li2 to Ne2) using varieties of quantum chemical tools, commonly used for intermolecular bonding/interactions now. The methods employed include Atoms in Molecules (AIM), Non-covalent Index plot (NCI), Electrostatic potential (ESP), and Potential Acting on oneElectron in a Molecule (PAEM). The spectroscopic constants i.e., equilibrium bond distances (re), harmonic frequencies (x), bond dissociation energies (De) have all been evaluated using high-level ab initio methods and critically compared with the experimental results. Multi-reference calculations (CASSCF) on B2 and C2 have been carried out as they have a large number of low lying electronic states. Bonding within these homonuclear diatomic molecules show all the diversities that are encountered in inter/intra-molecular bonding in chemistry. Based on the AIM analysis, these 8 homonuclear diatomic molecules could be divided into three different groups, based on the correlation between binding energy and the electron density at the bond critical point. However, PAEM/ESP analysis allows us to analyse all eight of them as one group havinga good correlation between binding energy and the PAEM/ESP at the critical point between the two atoms. Our results highlight the arbitrariness in relying on some computational tools to characterize a bond as covalent (shared) or ionic/electrostatic (closed). In contrast, they also show the usefulness of the various methods in exploring similarities and differences in bonding. We propose that from Li2 to Ne2, all homonuclear diatomic molecules are bound by ‘chemical bonds’.
Volume 134, 2022
Continuous Article Publishing mode
Click here for Editorial Note on CAP Mode