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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. 24, 9101, 2018), evidences the differences between the physicist's concept of interaction and the chemist's concept of bond. We argue that for the former all types of interactions are treated on the same footing, while for the latter only the covalent short-ranged ones have been actually used to build intuition about chemical graphs and chemical bonds. This has lead to overlook the bonding role of long-range Coulombic terms in molecular Chemistry. Simultaneously, blind consideration of electrostatic terms in chemical bonding parlance may lead to confusion. The relation among all these concepts is examined here, and some notes of caution on how to merge them are put forward.

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