On Electrostatics, Covalency, and Chemical Dashes: Physical Interactions versus Chemical Bonds

The increasing availability of real‐space interaction energies between quantum atoms or fragments that provide a chemically intuitive decomposition of intrinsic bond energies into electrostatic and covalent terms [see, for instance, Chem. Eur. J. 2018, 24, 9101] provides evidence for differences between the physicist's concept of interaction and the chemist's concept of a bond. Herein, it is argued that, for the former, all types of interactions are treated equally, whereas, for the latter, only the covalent short‐range interactions have actually been used to build intuition about chemical graphs and chemical bonds. This has led to the bonding role of long‐range Coulombic terms in molecular chemistry being overlooked. Simultaneously, blind consideration of electrostatic terms in chemical bonding parlance may lead to confusion. The relationship between these concepts is examined herein, and some notes of caution on how to merge them are proposed. Uniting chemists and physicists: The increasing availability of real‐space interaction energies between quantum atoms or fragments that provide a chemically intuitive decomposition of intrinsic bond energies into electrostatic and covalent terms result in differences between the physicist's concept of interaction and the chemist's concept of a bond. For the former, all types of interactions are treated equally, whereas, for the latter, only covalent short‐range interactions are used in chemical graphs and chemical bonds (see figure).