Wave Functions in a Periodic Potential

A new method for approximating the solutions of the problem of the motion of an electron in a periodic potential, as a crystal lattice, is suggested. The potential is supposed to be spherically symmetrical within spheres surrounding the atoms, constant outside. The wave function is expanded in spherical harmonics and radial solutions of the wave equation within the spheres, and in plane waves outside the spheres, joining continuously at the surface. A single unperturbed function consists of a single plane wave outside the spheres, together with the necessary spherical functions within the spheres. The matrix components of energy are set up between these unperturbed functions, and the secular equation set up. This equation involves the energy explicitly, and also implicitly through the ratio of the slope of the various radial functions to the functions themselves at the surfaces of the spheres, and must be solved numerically. It is hoped that the method will be useful for comparatively low energy excited electrons, for which the usual method of expansion in plane waves converges too slowly.