| Abstract
| - By combining the asymptotic correction scheme of Casida and Salahub for exchange-correlation potentialsand the phenomenological linear correlation between experimental ionization potentials and highest occupiedKohn−Sham (KS) orbital energies found by Zhan, Nichols, and Dixon, we propose a new, expedient, andself-contained asymptotic correction to exchange-correlation potentials in KS density functional theory (DFT)for use in time-dependent density functional theory (TDDFT) that does not require an ionization potential asan external parameter from a separate calculation. The asymptotically corrected (TD)DFT method isimplemented in the quantum chemistry program suite NWChem for both sequential and massively parallelexecution. The asymptotic correction scheme combined with the B3LYP functional [B3LYP(AC)] is shownto be well balanced for both valence- and Rydberg-type transitions, with average errors in excitation energiesof CO, N2, CH2O, and C2H4 being smaller than those of uncorrected BLYP and B3LYP TDDFT by factorsof 4 and 2, respectively, consistent with the improved orbital energies found for B3LYP(AC). We demonstratethe general applicability and accuracy of the method for the Rydberg excited states of mono- to tetrafluorinatedmethanes, the valence and Rydberg excited states of benzene, and the Q, B, N, and L band positions offree-base porphin.
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