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A theory of the valence band splittings at k=0 in zinc-blende and wurtzite structures is proposed, in which the wurtzite levels are treated as perturbations of those in zinc blende. Starting from one-electron Hamiltonians for the two structures, the two-parameter formulas originally derived by Hopfield are obtained, with a minimum of approximations, along with explicit expressions for the parameters in terms of Hamiltonian matrix elements. The two-parameter formulas are compared with experimental data and agreement is found to be good. A simple tight-binding (linear combination of atomic orbitals), 3p valence band, point-ion lattice model is used to calculate an effective charge for ZnS from the known valence band splittings in the wurtzite and zinc-blende dimorphs; a value of 2. 3e is obtained.
Stephen L. Adler (Sun,) studied this question.
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