Topology of Electron Charge Density for Chemical Bonds from Valence Bond Theory: A Probe of Bonding Types

Abstract

Abstract Covalent, ionic, or something new? A new interpretation of the topology of the electron density at the bond critical point is proposed to characterize covalent, ionic, and charge‐shift bonding from the density point of view (see figure). The topological properties of the density representation confirm the reality of charge‐shift bonds, in which the covalent contribution is weak or repulsive, and most of the bonding is due to the covalent–ionic resonance energy. magnified image To characterize the nature of bonding we derive the topological properties of the electron charge density of a variety of bonds based on ab initio valence bond methods. The electron density and its associated Laplacian are partitioned into covalent, ionic, and resonance components in the valence bond spirit. The analysis provides a density‐based signature of bonding types and reveals, along with the classical covalent and ionic bonds, the existence of two‐electron bonds in which most of the bonding arises from the covalent–ionic resonance energy, so‐called charge‐shift bonds. As expected, the covalent component of the Laplacian at the bond critical point is found to be largely negative for classical covalent bonds. In contrast, for charge‐shift bonds, the covalent part of the Laplacian is small or positive, in agreement with the weakly attractive or repulsive character of the covalent interaction in these bonds. On the other hand, the resonance component of the Laplacian is always negative or nearly zero, and it increases in absolute value with the charge‐shift character of the bond, in agreement with the decrease of kinetic energy associated with covalent–ionic mixing. A new interpretation of the topology of the total density at the bond critical point is proposed to characterize covalent, ionic, and charge‐shift bonding from the density point of view.