We present a conceptual model and calculational procedure for the study of the electronic structure of metallic compounds. The model consists of spherical atoms compressed into finite volumes appropriate to the solid. The model involves no adjustable or experimentally derived parameters. All contributions to the total energy (other than the Madelung energy) are obtained from independent compressed-atom calculations. Interatomic interactions enter the calculations through the electronic configuration (the distribution of the valence charge among s, p, d, etc., states) and boundary conditions which give the atomic valence levels a finite width. These environmental constraints, which specify the state of the compressed atoms, are obtained from energy-band calculations. For the latter we introduce a new method, which we call the augmented-spherical-wave (ASW) method to stress its conceptual similarity to Slater's augmented-plane-wave (APW) method. The ASW method is a direct descendant of the linear-muffin-tin-orbitals technique introduced by Andersen; when applied to pure metals, it yields results which closely approximate those of the much more elaborate Korringa-Kohn-Rostoker calculations of Moruzzi, Williams, and Janak. The combined ASW compressed-atom procedure is tested on (i) the empty lattice, (ii) the pure metals Na, Al, Cu, and Mo, and (iii) the ordered stoichiometric compounds NaCl, NiAl, and CuZn. Finally, we demonstrate the utility of the procedure by using it to study the anomalous tendency of Ni and Pd (as compared to their Periodic Table neighbors Co, Cu, Rh, and Ag) to form hydride phases. We have calculated the total energies of the six pure metals and their monohydrides. The total energy differences exhibit the anomaly and an analysis of quantities internal to the calculation reveals its origin. © 1979 The American Physical Society.