 Solution

Write $\mathbf{r}={\sum }_i{s}_i{\mathbf{a}}_i$. The electron density is periodic with period one in each $s_i$, so its three-dimensional Fourier series has integer harmonics:If $\Omega$ is a primitive unit cell of volume ${\Omega }_c$, Fourier orthogonality givesConversely, translation by ${\mathbf{a}}_i$ multiplies a general plane wave by $e^{i\mathbf{q}\cdot {\mathbf{a}}_i}$. Periodicity permits only $\mathbf{q}\cdot {\mathbf{a}}_i\in 2\pi \mathbb{Z}$, precisely the reciprocal lattice vectors. For a physical bounded periodic electron density, the expansion exists in the usual square-integrable sense.