Tuning Range-Separated Density Functional Theory for Photocatalytic Water Splitting Systems.

We discuss the system-specific optimization of long-range-separated density functional theory (DFT) for the prediction of electronic properties relevant for a photocatalytic cycle based on an Ir(III) photosensitizer (IrPS). Special attention is paid to the charge-transfer properties, which are of key importance for the photoexcitation dynamics but cannot be correctly described by means of conventional DFT. The optimization of the range-separation parameter using the ΔSCF method is discussed for IrPS including its derivatives and complexes with electron donors and acceptors used in photocatalytic hydrogen production. Particular attention is paid to the problems arising for a description of medium effects by means of a polarizable continuum model.