  The electronic structure of the corundum-type transition-metal oxides V2O3
and Ti2O3 is studied by means of the augmented spherical wave method, based on
density-functional theory and the local density approximation. Comparing the
results for the vanadate and the titanate allows us to understand the peculiar
shape of the metal 3d a_{1g} density of states, which is present in both
compounds. The a_{1g} states are subject to pronounced bonding-antibonding
splitting due to metal-metal overlap along the c-axis of the corundum
structure. However, the corresponding partial density of states is strongly
asymmetric with considerably more weight on the high energy branch. We argue
that this asymmetry is due to an unexpected broadening of the bonding a_{1g}
states, which is caused by hybridization with the e_g^{pi} bands. In contrast,
the antibonding a_{1g} states display no such hybridization and form a sharp
peak. Our results shed new light on the role of the a_{1g} orbitals for the
metal-insulator transitions of V2O3. In particular, due to a_{1g} - e_g^{pi}
hybridization, an interpretation in terms of molecular orbital singlet states
on the metal-metal pairs along the c-axis is not an adequate description.
