By J.P. Suchet
Crystal Chemistry and Semiconduction in Transition steel Binary Compounds.
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Additional info for Crystal Chemistry and Semiconduction in Transition Metal Binary Compounds
4). The theory assumes that one obtains as many MOs as there are combined AOs, and that the energy range of the MOs is always wider than that of the AOs used. 2]. Here we again find the division shown by the electrostatic theory. Like it, the MO theory allows the energies of the d orbitals to be classified in relation to one another but not in relation to the energies of other orbitals. (c) (d) Fig. 3. 3. shows the different a MOs in the commonest case of octahedral arrangement, assuming the intervention of the s, px, p r p z , d x -2y 2 , and d z 2 AOs 2 3 of the metal.
If, for example, one has N i cations of formula 3 d and O 2 6 anions of formula 2 s p , and if a nickel vacancy introduces a local deficit of two electrons, these will therefore be taken from two neighboring cations, 3+ 7 which change to the state N i with formula 3 d (Fig. 14). If there are 12 neighboring cations (as in the Bl structure), they are all 2+ 3 + equally likely to supply an electron. A given configuration (10Ni , 2 N i ) therefore has no stability and can be replaced immediately by another, differing from the first one by the transfer of an electron between two neighbor2+ 3+ ing cations, which immediately exchange their symbols N i and N i and 8 7 their formulas 3 d and 3 d .
They leave behind them, in the valence band, a hole which behaves like a positive particle (Fig. 6). 13) Energy E Conduction energy band Electrons Forbidden energy band E, Holes Valency energy band Fig. 6. Intrinsic conductibility in the band model. The presence of EF in a permitted energy band would mean that the band is partially filled even at absolute zero, in other words that a metal is involved. When a crystal is not perfect, defects or impurities cause local disturbances in the Bloch waves and create discrete levels in the forbidden energy band, capable of giving the conduction band or accepting from the valence band a limited number of electrons.