Communication: Becke’s virial exciton model gives accurate charge-transfer excitation energies

Abstract

First singlet (S 1 ) excitations are of primary importance in the photoluminescence spectra of organic chromophores. However, due to the multi-determinantal nature of the singlet excited states, standard Kohn-Sham density-functional theory (DFT) is not applicable. While linear-response time-dependent DFT is the method of choice for the computation of excitation energies, it fails severely for excitations with charge-transfer character. Becke’s recent virial exciton model [A. D. Becke, J. Chem. Phys. 148, 044112 (2018)] offers a promising solution to employ standard DFT for calculation of the S 1 excitation energy in molecular systems. Here, it is shown that the virial exciton model is free of charge-transfer error. It is equally reliable for S 1 excitations with significant charge-transfer character as for other classes of transitions.