附带学习资料 ：Opt_Mats_Bands_and_Bonds.doc

BANDS AND BONDS Lionel C. Kimerling CHEMICAL BONDS IN SOLIDS The chemical bond arises from a redistribution of electronic charge when atoms are brought in close proximity. The bond in a solid results from the superposition of charge densities of all atoms in the system. In an atom all electrons reside in their ground states at equilibrium. Only a few low lying excited states are typically accessed. The chemical bond in the solid consists of excited electronic configurations which are created to satisfy the constraints of a minimum energy, semi-infinite solid. These constraints create not only a variation on atomic energy level structure, but a compromise between the limiting classifications of bonding. These limiting classifications and their compromises are discussed in this section. Ionic Solids Ionic solids are compounds which are composed of atoms with large electronegativity differences. They typically involve the strongly electronegative group VI and VII elements together with an electropositive counterpart. In the limit of complete charge transfer (closed shells), the structure and properties are those expected from array of electrostatically interacting charges. Structure can be predicted from Paulings radius ratio approach and electrical insulating behavior is derived from the strongly bound valence electrons (Eg 3 eV). The internal energy of the system can be calculated simply and accurately by superimposing the measured compressibility relation on the electrostatic interactions of a point charge array as shown in Figure 1.5. U r * F attractive F repulsive dr A N Ae2 2 / R Be2 / Z Rn (1.3) 1 1 NAe2 Z R n 2 . / 0 Z Z N U(attractive) e 1 2 (1.4) R ij where R is the interatomic distance, Z is the ionic charge, A is the Madelung constant, N is Avogadvos number, B is the repulsive potential coefficient and n is the Born exponent. _________________________________ Example 1.6 List the first three terms of the Madelung (attractive) poten