New first-principles calculations of valence-band offsets at ZnTe/InAs, CuBr/Ge, CuBr/AlAs, and ZnSe/CuBr interfaces are reported. These are used, together with earlier theoretical values for other systems, to investigate the range of validity of the transitivity rule. For a wide class of systems this rule is found to hold with good precision, but a few compounds (e.g. CuBr) cause pronounced nontransitivity. For three common-anion systems, GaAs/AlAs, AlP/GaP, and AlSb/GaSb, they examine the dependence of the offset on growth direction. The differences between the (110) and (001) discontinuities for these systems are small, less than 0.07 eV.
 

Physical Review B, 38 12687-90, 1988.