Quantitatively, the solid-state band gap (Eg) as measured by UPS-IPES can be related to the electrochemical HOMO-LUMO gap (Eox-red) with a normalization factor that accounts for different screening mechanisms (polarization) acting in the solid state and in solution. As shown in Table , good agreement between the two energies is found for a normalization factor of 1.15. A leastsquares fit procedure revealed the presence of three low-energy states (see Gaussian curves beneath the spectra in Figure ) that could be rationalized with the help of DFT results. a The calculations were carried out with a scalar-relativistic ZORA (Zeroth Order Regular Approximation to the Dirac equation) Hamiltonian, all-electron ZORA STO-TZ2P basis sets, fine integration grids and tight criteria for SCF and geometry optimization cycles, and C2 point group symmetry, all as implemented in the ADF program system. 74 a Note that a more positive electron affinity corresponds to a lower-energy LUMO. In the isolated molecules, the lowest-energy IPES feature (LUMO) can be assigned with a high degree of confidence from DFT calculations. Thus, the scalar-relativistic OLYP 75,76 -D3 77,78 /ZORA-STO-TZ2P method (which has been extensively tested by one of us 79,80,81,82,83 ) yields gas-phase electron affinities 84,85,86 that closely track the energies of the lowest-energy IPES feature (Table ). For Cu[TPC], the LUMO corresponds to an antibonding combination of the corrole p-HOMO and the formally empty Cu 3dx2-y2 orbital, a consequence of the ligand noninnocence-driven saddled geometry of copper corroles (Figure ). In the case of Ag[TPC], the saddling is much more muted so the corrole p-HOMO does not interact as much with the Ag 4dx2-y2 orbital and the LUMO corresponds to essentially the latter orbital (Figure ; note the significantly smaller amplitudes at the corrole meso positions relative to Cu[TPC]). A very different scenario holds for Au[TPC]: relativistic effects 87,88 raise the energy of the Au 5dx2-y2 to such a degree that it corresponds to the LUMO + 2, while the LUMO corresponds to a pure corrole-based p-orbital (Figure ). In summary, an IPES study of coinage metal triphenylcorroles has uncovered major differences in the energetics of the unoccupied states for the three metals.