Hückel orbital charge density ($n_i={\sum }_k{f}_k|c_{ik}{|}^2$)

In an orthonormal Hückel method basis, an occupied molecular orbital with occupancy $f_k$ contributes $f_k|c_{ik}{|}^2$ electrons to site $i$. Adding one electron to a fixed orbital changes the site population by $|c_i{|}^2$. A coefficient sign indicates orbital phase, not charge sign. A net atomic charge also needs a reference population and treatment of the electrons outside the model.