Charge Transfer Excitation Energies From Ground State Density Functional Theory Calculations

Abstract

Calculating charge transfer (CT) excitation energies with high accuracy and low computational cost is a challenging task. Kohn-Sham density functional theory (KS-DFT), due to its efficiency and accuracy, has achieved great success in describing ground state problems. To extend to excited state problems, our group recently demonstrated an approach with good numerical results to calculate low-lying and Rydberg excitation energies of an $N$-electron system from a ground state KS or generalized KS calculations of an $(N-1)$-electron system via its orbital energies. In present work, we explore further the same methodology to describe CT excitations. Numerical results from this work show that performance of conventional density functional approximations (DFAs) is not as good for CT excitations as for other excitations, due to the delocalization error. Applying localized orbital scaling correction (LOSC) to conventional DFAs, a recently developed method in our group to effectively reduce the delocalization error, can improve the results. Overall, the performance of this methodology is better than time dependant DFT (TDDFT) with conventional DFAs. In addition, it shows that results from LOSC-DFAs in this method reach similar accuracy to other methods, such as $Δ$SCF, $G_0W_0$ with Bethe-Salpeter equations, particle-particle random phase approximation, and even high-level wavefunction method like CC2. Our analysis show that the correct $1/R$ trend for CT excitation can be captured from LOSC-DFA calculations, stressing that the application of DFAs with minimal delocalization error is essential within this methodology. This work provides an efficient way to calculate CT excitation energies from ground state DFT.