Charge transfer excitations in TDDFT: A ghost-hunter index

This work presents a new index, M_AC , enabling the on-the-fly detection of ghost charge transfer (CT) states, a major problem in time-dependent density-functional theory calculations. This computationally inexpensive index, derived as a modification of the Mulliken estimation of transition energy for CT excitations, relies on two basic ingredients: an effective CT distance, computed using our density-based index (D_CT ), and an orbital weighted estimation of the Ionization Potential and Electron Affinity. Some model systems, representative of both intermolecular and intramolecular CT excitations, were chosen as test cases. The robustness of our approach was verified by analyzing the behavior of functionals belonging to different classes (GGA, global hybrids and range separated hybrids). The results obtained show that ghost states are correctly spotted, also in the delicate case of intramolecular excitations displaying substantial donor-bridge-acceptor delocalization, in a regime for which the standard Mulliken formulation attends its limits. © 2017 Wiley Periodicals, Inc.