The rigorous application of multiple‐scattering theory to contiguous nonoverlapping truncated atomic spheres leads to a molecular‐orbital secular determinant which is identical to that solved in the overlapping‐sphere SCF‐Xα scattered‐wave method, except for the subtraction of on‐diagonal and off‐diagonal terms associated with multiple scattering in the overlap regions. The possible importance and approximate evaluation of these terms as corrections to the overlapping‐sphere method are discussed.