This paper develops a classification scheme for non-crystalline dielectrics that separates them into three groups with different amorphous morphologies, and identifies a linear scaling relationship between average bond ionicity and oxygen atom coordination. The classification scheme is applied to transition metal silicate and aluminate alloys and provides a structural model for molecular orbital, MO, calculations that are based on the coordination and symmetry of transition metal atoms and the orbital energies of their oxygen neighbors. The MO calculations show that conduction band offset energies with respect to Si scale inversely with the energy difference between transition metal atomic n+1 s- and n d-states providing an important insight into the choice of alternative gate dielectrics for advanced Si devices.