The functional form of ∆ε changes for the third row of the periodic table [Eq. ( )]. Results for K-edge transition energies of heavier elements are presented in Table , including molecules containing third-row elements Si, P, S, and Cl, along with a few organometallic complexes containing a 3d transition metal, 101-104 as shown in Fig. . (The latter are taken from a much larger database of geometries for organometallic complexes. 105 ) For the main-group molecules, results can be compared to experiment but for the 3d metal-containing systems we compare to K-edge excitation energies for the isolated metal atoms. 100 This is sufficient to estimate the overall shift that is required in a TD-DFT or DFT/CIS calculation. Relativistic Douglas-Kroll-Hess corrections are listed in Table and they are quite large for the 3d elements. These corrections have been added to the computed excitation energies in Table , as a post-processing step.