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

Abstract

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 and cannot be correctly described by means of conventional DFT. The optimization of the range-separation parameter using the $\Delta$SCF 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.

arXiv commentslightly revised version

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Cited by in corpus (4)

• Density Functional Theory for Electronic Excited States
• TDDFT+$U$: Hubbard corrected approximate density-functional theory in the excited-state regime
• Quantum chemical study of the electronic properties of an Iridium-based photosensitizer bound to medium-sized silver clusters
• Site-selective and real-time observation of bimolecular electron transfer during photocatalytic water splitting