Bond Valence Theory

This chapter shows that a unified concept of a chemical bond can be derived from a theoretical picture of the atom in which the Coulomb forces are described using the electric field rather than the electric potential. The localized chemical bond and its valence arises naturally from this picture, allowing the theorems of electrostatics to be used to describe the formation and properties of any chemical structure composed of localized bonds. There is no distinction made between ionic and covalent bonds. An empirical correlation links the theoretical bond valence to the experimental bond length. The resulting picture of chemical structure predicts where bonds will form, how long they will be, and in what direction they will point. It indicates the conditions for chemical stability, suggesting which reactions a compound might undergo either in solution or at a surface. Electronic anisotropies are handled in an ad hoc manner, in which the VSEPR theory of lone pairs is extended to cases where the lone pairs are inactive or only partially stereoactive. Steric constraints leading to compressed or stretched bonds are quantified by observing the difference between the real and theoretical structures. The potential of the bond valence theory is only beginning to be exploited.

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