Chemical Bonding in Solids

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Abstract
Solids are typically identified by their physical properties, which originate from the nature of the forces holding atoms or molecules together in the condensed phase. As a result, an understanding of chemical bonding in solids lies at the heart of solid state chemistry. The idealized cohesive forces lead to four main types of solids:ionic,covalent,metallic, andmolecular. The first three of these categories also describe their corresponding bonding limits, whereas molecular solids rely on van der Waals forces or anisotropic electrostatic interactions, such as dipole‐dipole or hydrogen bonding forces, to condense individual atoms or molecules into the solid state. However, very few solids exclusively exhibit one kind of cohesive force. Most of them engender multiple bonding modes.If solid‐state structures are viewed as molecules with quasi‐infinite numbers of atoms, then the same bonding concepts used in molecular chemistry should be appropriate for solid state chemistry. The atomic scale of solids, however, as compared to a single molecule, can bring about new collective features that lead to physical properties useful for technological applications. To reconcile these two extremes of atomic scale, quantum mechanics and the steady growth of computational capabilities have led to tremendous advances in how chemical bonding in solids, especially crystalline solids, can be analyzed and interpreted using localized and delocalized pictures of electronic structure. Yet, the experimental chemist relies significantly on simple valence electron counting rules to identify new synthetic targets, whereas the materials scientist and condensed matter physicist strive to relate the electronic structure of a solid to its measured properties. Both outlooks must be grounded in the computational results. With the goal of addressing these issues concerning chemical bonding in the solid state, this chapter is organized as follows: (1) a brief overview of fundamental characteristics and descriptions of chemical bonds in matter; (2) a summary of the types of solids and bonding motifs; (3) a description of how quantum mechanics is used to analyze chemical bonding in solids; (4) descriptions of important electron counting rules that are useful for experimentalists; and (5) selected examples of the synergies among chemical bonding, atomic structures, and properties.

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