Ab initio supercell calculations employing the periodic Hartree-Fock formalism are presented of the (0001) alpha-Cr2O3 surface with a partially or totally AI-substituted external layer. In the simulations a fraction of the Cr atoms at the surface of the chromia slab are replaced by AI atoms, and the AI surface coverage is varied between zero (pure chromia) and 100% (Al-terminated chromia). The surface Al atoms are found to relax inwards considerably, with the magnitude of the relaxation decreasing with increasing AI surface coverage. The calculations also reveal that the surface energy of the slab decreases with increasing Al coverage. Finally, the electronic properties at the surface of the AI-substituted (0001) alpha-Cr2O3 slabs are investigated Here the calculations show that the substitution of Cr by Al gives rise to an increase in the covalency of the Al-O bonds compared to slabs of pure alumina. In contrast, the influence of the surface AI atoms on the electrostatic potential in the (0001) plane of metal ions is relatively small. These findings support the utilisation of alpha-chromia substrates for the templated growth of alpha-alumina, which is consistent with recent experiments. (C) 2009 Elsevier B.V. All rights reserved.