The potential energy surfaces associated with the triplet electronic state of the Ir(ppZ)(3) and Ir(PPY)(3) cyclometalated complexes, respectively, are calculated using density functional theory [where ppz = 1-phenylpyrazolyl-NC2', ppy = 2-phenylpyridyl]. Both surfaces present a metal-to-ligand charger-transfer energy minimum and a ligand-field energy minimum, connected by a chemical path involving only the rotation of one pyrazolyl or pyridyl group. Unlike lr(PPY)(3), the lowest energy minimum of lr(ppZ)(3) is the ligand-field state.