Over 35 years ago, the low-lying bands in the absorption spectra of metal hexacarbonyls were assigned to ligandfield (LF) excitations. Recent time-dependent density functional theory (TDDFT) calculations on M(CO)(6) (M = Cr, Mo, W) are not in accord with this interpretation. Here we extend TDDFT calculations to the isoelectronic series V(CO)(6)(-), Cr(CO)(6), and Mn(CO)(6)(+). By analyzing the trends in the energies of the various electronic excitations, we are able to fully assign the spectra of the complexes. In particular, we demonstrate that the LF excitation (1)A(1g) -> T-1(1g) is observed at 4.12 eV in the Mn(CO)(6)(+) spectrum, but all LF features in the spectra Of V(CO)(6)(-) and Cr(CO)(6) are obscured by intense metal-to-ligand charge-transfer absorptions. Our results suggest that use of B3LYP as the exchange-correlation functional and inclusion of solvation effects through a continuum solvation model lead to the most accurate calculated transition energies.