Distinguishing between Charge-Transfer Mechanisms at Organic/Inorganic Interfaces Employing Hybrid Functionals

When modeling inorganic/organic interfaces with density functional theory (DFT), the outcome often depends on the chosen functional. Hybrid functionals, which employ a fraction of Hartree–Fock exchange α, tend to give better results than the more commonly applied semilocal functionals, because they remove or at least mitigate the unphysical electron self-interaction. However, the choice of α is not straightforward, as its effect on observables depends on the physical properties of the investigated system, such as the size of the molecule and the polarizability of the substrate. In this contribution, we demonstrate this impact exemplarily for tetrafluoro-1,4-benzoquinone on semiconducting (copper-I-oxide Cu2O) and metallic (Cu) substrates and explore how the simulated charge transfer depends on α. We determine the value α* that marks the transition point between spurious over-localization and over-delocalization of charges. This allows us to shed light on the interplay between the value of α* and the physi...