In a recent paper, we investigated the electronic properties of a set of Ge–Al lattice‐matched interfaces. These interfaces were constructed by placing an ideal (001)Ge substrate next to a 45° rotated (001)Al film. In all cases the Ge–Al interatomic distance was kept fixed at someadhocvalue. Using a self‐consistent pseudopotential approach, we now extend these calculations to consider the case where the interlayer distance is fixed for the on top and interstitial model but the Ge–Al interatomic distance is allowed to vary. One striking result of our calculation is that the differences among diverse interface geometries lead only to small differences in electronic properties if the interlayer distance is kept fixed. Single atomic metal overlayer calculations by Chelikowsky, and Zhang and Schluter in different configurations show more pronounced differences. Our results indicate that inclusion of more than one metal layer tends to smear out these differences. We also calculate an optimal geometrical arrangement by minimizing the total energy of the system. We critically discuss the weakly interacting cluster model and the chemisorption model of metal–semiconductor interfaces and place our work in context. We also present a semiclassical calculation which relates the interface density of occupied states to surface quantized level spacing. It suggests a possible surface absorption experiment for determining this state density. Future ramifications of our idealized model and the role it can play in simulating interfacial chemical reactions are briefly stated.