Single Excitation Energies Obtained from the Ensemble "HOMO-LUMO Gap": Exact Results and Approximations

J Phys Chem Lett. 2022 Mar 17;13(10):2452-2458. doi: 10.1021/acs.jpclett.2c00042. Epub 2022 Mar 10.

Abstract

In calculations based on density functional theory, the "HOMO-LUMO gap" (difference between the highest occupied and lowest unoccupied molecular orbital energies) is often used as a low-cost, ad hoc approximation for the lowest excitation energy. Here we show that a simple correction based on rigorous ensemble density functional theory makes the HOMO-LUMO gap exact in principle and significantly more accurate in practice. The introduced perturbative ensemble density functional theory approach predicts different and useful values for singlet-singlet and singlet-triplet excitations, using semilocal and hybrid approximations. Excitation energies are similar in quality to time-dependent density functional theory, especially at high fractions of exact exchange. The approach therefore offers an easy-to-implement and low-cost route to robust prediction of molecular excitation energies.