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The Journal of Physical Chemistry A 2022, 126 Photochemical Synthesis and Spectroscopy of Covalent PAH Dimers. Journal of Chemical Information and Modeling 2022, 62 Updated Calibrated Model for the Prediction of Molecular Frontier Orbital Energies and Its Application to Boron Subphthalocyanines. Holst, Pascal Friederich, Alán Aspuru-Guzik, Timothy P. Platinum(II)-Substituted Phenylacetylide Complexes Supported by Acyclic Diaminocarbene Ligands. This article is cited by 568 publications. A linear correlation between the calculated HOMO eigenvalue and the experimental −IP and calculated HOMO−LUMO gap and experimental lowest excitation energy enables us to derive a simple correction formula. We find that TD−DFT with all functionals accurately predicts the HOMO−LUMO gaps. On the other hand, the LUMO eigenvalues of the hybrid functionals fail to predict the EA to the extent that they include HF exchange, although increasing HF exchange improves the correspondence between the HOMO eigenvalue and −IP so that the HOMO−LUMO gaps are inaccurately predicted by hybrid DFT functionals. Although the GGA functionals inaccurately predict both the HOMO and LUMO eigenvalues, they predict the HOMO−LUMO gap relatively accurately (∼0.73 eV). The LUMOs of all functionals fail to accurately predict the EAs. We find that the HOMO eigenvalues predicted by KMLYP, BH&HLYP, B3LYP, PW91, PBE, and BLYP predict the −IPs with average absolute errors of 0.73, 1.48, 3.10, 4.27, 4.33, and 4.41 eV, respectively. The 11 DFT functionals include the local spin density approximation (LSDA), five generalized gradient approximation (GGA) functionals, three hybrid GGA functionals, one hybrid functional, and one hybrid meta GGA functional. We also report how accurately the HOMO−LUMO gaps of these methods predict the lowest excitation energies using both time-independent and time-dependent DFT (TD−DFT). We report how closely the Kohn−Sham highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) eigenvalues of 11 density functional theory (DFT) functionals, respectively, correspond to the negative ionization potentials (−IPs) and electron affinities (EAs) of a test set of molecules.