We present the early results of our ongoing effort to identify and characterize new TE materials. Using the linear muffin‐tin orbital method, we have studied the shape of the eigenenergy surfaces of the conduction electrons in Si and other TE materials. We describe a multi‐valley multi‐band computational approach in which we perform the Fermi‐integrations directly over the 3D eigenenergy surfaces. Furthermore, by performing these integrations against a delta‐function in carrier energy, &egr;, we are able to characterize the geometric non‐scattering structural aspects of the material in terms of a ‘‘partial conductivity’’ function, &sgr;(&egr;). From this standpoint, it is possible to quantitatively compare the TE properties of different materials within the same structural family, and to gain some insight into the TE structure/function relationship. ©1995 American Institute of Physics.