Theoretical Study of the Local and Charge-Transfer Excitations in Model Complexes of Pentacene‑C₆₀ Using Tuned Range-Separated Hybrid Functionals

The characteristics of the electronic excited states and the charge-transfer processes at organic–organic interfaces play an important role in organic electronic devices. However, charge-transfer excitations have proven challenging to describe with conventional density functional theory (DFT) methodologies due to the local nature of the exchange-correlation potentials often employed. Here, we examine the excited states of model pentacene-C₆₀ complexes using time-dependent DFT with, on one hand, one of the most popular standard hybrid functionals (B3LYP) and, on the other hand, several long-range corrected hybrid functionals for which we consider both default and nonempirically tuned range-separation parameters. The DFT results based on the tuned functionals are found to agree well with the available experimental data. The results also underline that the interface geometry of the complex has a strong effect on the energies and ordering of the singlet and triplet charge-transfer states