The advantage of accurate spectra is especially apparent in this case, as we obtain absolute excitation energies (without shifting) that differ by only a few eV from the experimental spectra, at energies of several thousand eV. As such, there is no need for large-scale shifting (by tens or even hundreds of eV) that is common in TD-DFT calculations for metal K-edges, as documented in Table for several 3d metal atoms. In the present case, TD-CAM-B3LYP/def2-TZVPD spectra at the Ti K-edge must be shifted by a further 76 eV in order to match experiment (Fig. ). For XANES at the Cl K-edge, the TD-CAM-B3LYP/def2-TZVPD spectra must be shifted by an additional 56 eV relative to CAM-B3LYP/CIS/def2-TZVPD, in order to coincide with experiment (Fig. ). In complex systems with multiple overlapping edges, the need for large shifts can render it difficult to understand the spectra, as for example in the case of titania where the Ti L 1 -edge overlaps with the oxygen K-edge.