The nearly-free electron model treats a weak periodic potential as a perturbation of plane waves. Near a Bragg plane, states with wavevectors and are nearly degenerate and must be mixed together. Their two-state Hamiltonian isAt the unperturbed crossing, the band gap is . The corresponding standing waves place different charge densities near the ions and between them, giving different potential energies. Far from a crossing, ordinary perturbation theory is adequate; near it, the degenerate two-wave calculation is essential. In three dimensions, gaps at individual zone boundaries do not guarantee a global insulating gap because bands from different directions can overlap.
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