Learning from the 4-(dimethylamino)benzonitrile twist: Two-parameter range-separated local hybrid functional with high accuracy for triplet and charge-transfer excitations.

Abstract

The recent ωLH22t range-separated local hybrid (RSLH) is shown to provide outstanding accuracy for the notorious benchmark problem of the two lowest excited-state potential energy curves for the amino group twist in 4-(dimethylamino)benzonitrile (DMABN). However, the design of ωLH22t as a general-purpose functional resulted in less convincing performance for triplet excitations, which is an important advantage of previous LHs. Furthermore, ωLH22t uses 8 empirical parameters to achieve broad accuracy. In this work, the RSLH ωLH23ct-sir is constructed with minimal empiricism by optimizing its local mixing function prefactor and range-separation parameter for only 8 excitation energies. ωLH23ct-sir maintains the excellent performance of ωLH22t for the DMABN twist and charge-transfer benchmarks but significantly improves the errors for triplet excitation energies (0.17 vs 0.24eV). Additional test calculations for the AE6BH6 thermochemistry test set and large dipole moment and static polarizability test sets confirm that the focus on excitation energies in the optimization of ωLH23ct-sir has not caused any dramatic errors for ground-state properties. Although ωLH23ct-sir cannot replace ωLH22t as a general-purpose functional, it is preferable for problems requiring a universally good description of localized and charge-transfer excitations of both singlet and triplet multiplicity. Current limitations on the application of ωLH23ct-sir and other RSLHs to the study of singlet-triplet gaps of emitters for thermally activated delayed fluorescence are discussed. This work also includes the first systematic analysis of the influence of the local mixing function prefactor and the range-separation parameter in an RSLH on different types of excitations.