Time-dependent density functional theory (TD-DFT) is applied to the UV-vis absorption and circular dichroism (CD) spectra of a series of transition metals (M = Ru, Zn, Fe) complexed with an enantiopure hemicage ligand, (-)-(5R,5 ' R,5 '' R,7R,7 ' R,7 '' R,8S,8 ' S,8 '' S)-8,8 ',8 ''-[(2,4,6-trimethyl-1,3,5-benzenetriyl)tris(methylene)]tris[5,6,7,8-tet rahydro-6,6-dimethyl-3-(2-pyridinyl)-5,7-methanoisoquinoline (1). The electronic spectra of the Ru and Fe complexes contain two regions, one featuring low-energy (MLCT)-M-1 transitions and the other higher energy U transitions; the Zn analog possesses only the (LC)-L-1 transitions due to its filled 3d shell. TD-DFT is able to identify correctly these transitions in the spectra, as well as to reproduce experimental spectra accurately, with regard to both the transition energies and the relative intensities of the different transitions. Additionally, it is possible to use TD-DFT to assign the absolute configuration at the metal center with high confidence by matching the experimental and calculated spectra.