 Solution

The nearly-free electron model treats a weak periodic potential as a perturbation of plane waves. Near a Bragg plane, states with wavevectors $\mathbf{k}$ and $\mathbf{k}-\mathbf{G}$ are nearly degenerate and must be mixed together. Their two-state Hamiltonian isAt the unperturbed crossing, the band gap is $2|V_{\mathbf{G}}|$. 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.