Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 15, Issue 12, Pages 2979-2989Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200802134
Keywords
ab initio calculations; bond theory; charge-shift bonding; electron pairing; valence bonds
Categories
Funding
- Natural Science Foundation of China [20873106, 20533020]
- The National Basic Research Program of China [2004CB719902]
- ISF [16/06]
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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 arc 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 file 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.
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