Triple-ζ basis functions with one polarization function from the def2 basis set family of the Ahlrichs group were used for all atoms of the first and second row of the periodic table (TZVP), while an additional polarization function was added for sulfur (TZVPP). In addition, augmented basis sets were used for formaldehyde, thioformaldehyde and nitromethane to account for low-lying Rydberg states. Since CP2K is not featuring an assigment of excited states regarding symmetry, the assignment of excited states was based on a comparison of CP2K results with analogous Turbomole computations .In general, it thus has to be highlighted that TDA and DFT/MRCI results were compared and corresponding errors were computed based on the symmetry assignment and not on the energetic ordering. Only for dithiin, nitrobenzene, nitromethane and o-benzyne, symmetry assignment was in full agreement with an ordering of excited states based on the excitation energy. For bithiophene, dithiosuccinimide and isoalloxaline, the energetic ordering of two states and for quinoxaline the ordering of three pairs of states differs from the reference assignment, increasing the listed error in the excitation energy. Resulting errors in the excitation energies amount up to 0.5 eV for both 1 1 B 2 and 2 1 A 2 of dithiosuccinimide and 1 1 A 2 and 2 1 A 2 for quinoxaline. Comparable deviations are discussed for full TDDFT not relying on the TDA in Ref. , suggesting the multireference character of these states to be significant. Further details on the assignment are given in the supplementary information.